CN104962841B - The interface and preparation method of a kind of carbon nanotube metal based composite materials - Google Patents
The interface and preparation method of a kind of carbon nanotube metal based composite materials Download PDFInfo
- Publication number
- CN104962841B CN104962841B CN201510275357.5A CN201510275357A CN104962841B CN 104962841 B CN104962841 B CN 104962841B CN 201510275357 A CN201510275357 A CN 201510275357A CN 104962841 B CN104962841 B CN 104962841B
- Authority
- CN
- China
- Prior art keywords
- cnt
- nano
- particle
- preparation
- carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides the interface and preparation method of a kind of carbon nano-tube reinforced metal-matrix composite material, described interface carries out local modification using nano-particle to carbon nano tube surface fault location, hinder fault location that interfacial reaction occurs, the interfacial reaction of appropriateness obtains good interface cohesion and metallic matrix between by carbon nano tube surface structural integrity.Methods described：It is prepared by the treatment of carbon nano tube surface local activation and dispersion liquid；Carbon nano tube dispersion liquid is mixed with Nano sol, is stirred, ultrasonically treated, filtration drying obtains the CNT that nano-particle is locally modified；The CNT of modification is evenly spread among metallic matrix, then densified acquisition composite.The present invention forms discontinuous, partial modification thing film in carbon nano tube surface, introduced nano-modified particle volume content is low, do not reunite, the densification of composite, but energy Effective Regulation interfacial reaction are not interfered with, CNT is given full play to enhancing potentiality.
Description
Technical field
The present invention relates to metal-base composites technical field, in particular it relates to a kind of carbon nano-tube reinforced metal-matrix is multiple
The interface and preparation method of condensation material.
Background technology
Composite is one of effective way that metal material realizes high performance and functionalization.CNT (CNT) conduct
One-dimensional tubular nanometer material, it is lightweight, it is preferable metal-base composites with extremely excellent mechanics and thermal conductivity
High-strength light performance enhancement body.Therefore, the metals such as CNT and aluminium, copper, magnesium, titanium and alloy are combined, are expected to obtain a new generation light
Matter is high-strength and has the metal-base composites of functional characteristic concurrently, has wide application in space flight, traffic, electronics and military field
Prospect.
But so far, enhancing effect of the CNT embodied in metal-base composites is still poor with theory expectation
Away from larger, most important of which is that between CNT and metallic matrix and there is interfacial reaction regulation and control problem, difficult
To give full play to the invigoration effect of CNT.On the one hand, do not occur completely between the metal such as CNT and copper, magnesium chemical anti-
Should, interface compatibility is poor, and interface bond strength is low；On the other hand, it is prone to chemistry between the metal such as CNT and aluminium, titanium
Reaction, many times even by the depleted all generation Al of CNT4C3, the carbide such as TiC.Both the above situation, i.e., it is complete
The full interfacial reaction that interfacial reaction or many degree do not occur, will all damage the enhancing benefit of CNT：Weak interface combination cannot have
Effect transmission load, and excessively interfacial reaction causes that CNT damages aggravation, it is easy to fracture failure.Therefore, how few consumption/
On the premise of damaging CNT, regulation and control interfacial reaction obtains preferable interface bond strength, multiple as carbon nano tube metal base
The key issue that condensation material further develops.
Research shows that existing compound preparation process inevitably introduces a large amount of on the surface of CNT and end
Defect, and fault location is CNT/preferential place for occurring of metal interface reaction.Therefore, to the defect of carbon nano tube surface
Modify is to improve the maximally efficient approach of interface cohesion, regulation and control interfacial reaction.Existing literature search is found, carbon is received
It is the technical way for reaching above target that mitron carries out surface coated treatment." the Aluminum matrix of document 1
Composites reinforced by molybdenum-coatedcarbon nanotubes " (plating molybdenum CNT enhancings
Aluminum matrix composite) (International Journal of Minerals, Metallurgy, and Materials,
2011,18(6):One layer of continuous thickness uniformly 695-702.) is coated in carbon nano tube surface using metal organic chemical vapor deposition
It is the metal molybdenum of 20-30nm, and is prepared for plating molybdenum CNT aluminum matrix composite using discharge plasma sintering.Due to excess
The introducing of coating, causing the consistency of composite reduces, and final relative density only has 95%.Additionally, the technique is used
Metallorganic is extremely toxic substance, easily causes environmental pollution." the Coating of carbon nanotubes with of document 2
Tungsten by physicalvapor deposition " (physical vapour deposition (PVD) plates tungsten in carbon nano tube surface) (Solid
state communications,2000,115(1):51-55.) one is deposited using physical vapour deposition (PVD) in carbon nano tube surface
The continuous thickness of layer is the tungsten of 10-20nm.Physical vapor deposition device that the technique is used is complicated, and continuous film draws
Enter to cause CNT to be unable to directly contact with metallic matrix, be unfavorable for that CNT strengthens the performance of benefit.Document 3
" Coating carbon nanotubes with iron oxide using methanol-thermal reaction " (alcohol
Hot method plates iron oxide in carbon nano tube surface) (Materials Letters, 2007,61 (3):697-700.) use the hot method of alcohol
The iron oxide of needle-like is introduced in carbon nano tube surface, CNT is wrapped up, but locally there is substantial amounts of reunion in it, is unfavorable for causing
The performance of densification and reinforcement benefit.
It can be seen that, the above method tends to for face coat to regulate and control into continuous film distribution, without to carbon nano tube surface
The form and content of coating are regulated and controled, and thus lack Fine design and Effective Regulation to interfacial structure, bring following deficiency
Part：
(1) because the specific surface area of CNT is big, when continuous film is formed, the volume content of introduced modifier is much
More than CNT itself, the composition of composite system is changed；
(2) modifier can completely intercept the directly contact of CNT and metallic matrix in continuous film distribution, when serious also
Modifier can be produced to reunite, the combination of influence CNT and metallic matrix, causing the consistency of composite reduces, carbon nanometer
The enhancing benefit of pipe cannot be played effectively；
(3) above method is unfriendly to environment, while complex process, it is difficult to control.
The content of the invention
For defect of the prior art, the invention provides a kind of interface of carbon nanotube metal based composite materials
And preparation method, only introduce a small amount of nano-particle carries out local modification to carbon nano tube surface defect, does not interfere with composite
Densification, but can Effective Regulation interfacial reaction, enable CNT give full play to its enhancing potentiality.
To achieve the above object, the present invention uses following technical scheme：
A kind of Interface Design of carbon nanotube metal based composite materials, the method is abandoned existing to carbon nano tube surface
Face coat is regulated and controled into the thinking of continuous film distribution when defect is modified, but dexterously using nano-particle to carbon nanometer
Pipe surface fault location carries out local modification, hinders fault location that interfacial reaction occurs, and passes through at carbon nano tube surface structural integrity
The interfacial reaction of appropriateness obtains good interface cohesion between metallic matrix.
The present invention forms discontinuous, partial modification thing film in carbon nano tube surface fault location, hinders boundary at this
Face is reacted, and is made at the structural integrity of carbon nano tube surface and metallic matrix directly contact, and generation at this is made by process control
The interfacial reaction of appropriateness obtains good interface cohesion.
The nanoparticle content that interface of the present invention is introduced is very low, as shown in table 1, with general continuous membrane modifying
Compare, the nanoparticle content that interface of the invention is introduced is low more than 10 times.Therefore, carbon nano tube metal base is not interfered with
The interface cohesion of composite and densification；The surface defect of Nanoparticle Modified CNT, can effectively prevent CNT
Interfacial reaction and metallic matrix between, the carbon nanotube metal based composite materials excellent performance for obtaining.
Preferably, described nano-particle is metal oxide or metal complex or silica, such as do not received with carbon
Mitron reacts and the metal oxide small with the diffusion coefficient of CNT.Selection metal oxide or complex compound are (through height
Metal oxide can be also changed into after temperature treatment) on the one hand because ensure that its compatibility with matrix, still further aspect
Due to diffusion coefficient very little of the CNT in metal oxide, and reaction is typically not susceptible to, therefore, it is possible to effectively obstruction
The generation of interfacial reaction.
Preferably, the particle diameter of described nano-particle is 1-50nm, and preferably, the particle diameter of described nano-particle is 1-
10nm.The particle diameter of nano-particle is smaller to be more readily adsorbed in carbon nano tube surface fault location, while the content for introducing is also lower, grain
Footpath is excessive to be easily caused nano-particle itself reunion generation sedimentation, does not have modification.
Preferably, the carbon nanotube diameter is 5-100nm, preferably, a diameter of 10- of described CNT
50nm.The diameter of CNT is excessive to be unfavorable for that it disperses, and the too small surface activation process of diameter can be caused to its structure and performance
Very big damage, therefore select the CNT of diameter 10-50nm.
According to a second aspect of the present invention, there is provided a kind of preparation method of carbon nanotube metal based composite materials, the method exists
On the basis of above-mentioned interface, comprise the following steps：
Step one, the treatment of carbon nano tube surface local activation, prepares carbon nano tube dispersion liquid or use is prepared in advance
Carbon nano tube dispersion liquid；
Step 2, prepares modifier Nano sol or using the modifier Nano sol for preparing in advance, and carbon is received
Mitron dispersion liquid mixes with Nano sol, stirs, then carries out ultrasonically treated, filtration drying, obtains nano-particle and locally repaiies
The CNT of decorations；
Step 3, the CNT of the local modification of nano-particle is evenly spread among metallic matrix, then densified
Obtain carbon nanotube metal based composite materials.
Preferably, described metallic matrix is aluminium and its alloy.
Preferably, the mass fraction of the CNT in the composite is 0.5~10%, preferably, described carbon
The mass fraction of nanotube is 1~5%.
Preferably, described preparation method carries out activation process by acid solution to carbon nano tube surface so that CNT
Surface defect turns into active site.
Preferably, it is described to stir, mechanical agitation can be used.
Preferably, the modifier Nano sol, modifier is metal oxide or metal complex or silica.
Preferably, in the step 2, after CNT is mixed with Nano sol, anion surfactant is added
(SDS, SDBS etc.), suppresses CNT reunion each other so that activity of the nano-particle uniform adsorption in CNT
Point on.
Principle of the invention：Described interface is the angle from regulation and control interfacial reaction and improvement interface cohesion,
Although the introducing of continuous film can suppress interfacial reaction, because the specific surface area of CNT is big, volume high is inevitably resulted in
The introducing of content continuous film and additional interfaces, making the densification of composite reduces, and hinders the knot of CNT and metallic matrix
Close；The nanoparticle content that Nanoparticle Modified is introduced is very low, does not interfere with the densification of composite.Meanwhile, nano-particle
Modification energy Effective Regulation interfacial reaction.
Because carbon nano tube surface and end are inevitably present defect, described preparation method is received by acid solution to carbon
Nanotube surface carries out activation process so that carbon nano tube surface defect turns into active site.Because fault location has surface energy high,
As the preferential attachment point of nano-particle.After CNT is mixed with Nano sol, it is aided with mechanical agitation and ultrasound, Nano sol
Metastable state destroyed, the anion surfactant (SDS, SDBS etc.) of addition can suppress CNT each other
Reunite so that nano-particle uniform adsorption is on the active site of CNT.Nano-particle is preferential in carbon nano tube surface defect
Place's attachment, obtains the CNT of Nanoparticle Modified.The CNT of Nanoparticle Modified is distributed in metallic matrix again,
Obtain the carbon nanotube metal based composite materials of Nanoparticle Modified.
Continuous film modified for existing, the introduction volume of modifier can be by formula relative to the volume fraction of CNT
(1) calculate：
Wherein, r is CNT radius, and L is length of carbon nanotube, and Δ r is the thickness of continuous film, and α is that continuous film is relative
In the volume fraction of CNT.
For Nanoparticle Modified, the introduction volume of modifier can be by formula relative to the volume fraction of CNT
(2) calculate：
Wherein, r is CNT radius, and L is length of carbon nanotube, and Δ r is the radius of nano-particle, and c% is carbon nanometer
Pipe surface defect density, β is volume fraction of the nano-particle relative to CNT.
With a diameter of 30nm, as a example by surface defect concentration is 5% CNT, i.e. r=15nm, c%=5%.According to
Formula (1) (2) is it can be calculated that for the continuous film and nano-particle of different-thickness, the introduction volume of modifier is received relative to carbon
The volume fraction of mitron is as shown in table 1.
The modifier introduction volume of table 1 and modifier scaling relation
| Δr/nm | 2 | 5 | 10 | 15 | 20 |
| α | 27% | 67% | 133% | 200% | 267% |
| β | 2% | 5% | 9% | 14% | 18% |
As it can be seen from table 1 for continuous film, because nano-particle is only repaiied to carbon nano tube surface fault location
Decorations, the introduction volume of nano-particle seldom, does not interfere with the densification process of composite.Nano-particle can with CNT it
Between form good combination, while from the nano-particle good with metallic matrix wetability, CNT can be improved with gold
Belong to the interface cohesion of matrix.On the other hand, modification of the nano-particle for carbon nano tube surface defect so that nano-particle
Interfacial reaction can be slowed down, it is ensured that the integrality of CNT as elements diffusion and the barrier layer of interfacial reaction.Therefore, with
The carbon nanotube metal based composite materials for not carrying out nano-particle point modification are compared, and interface can be slowed down using Nanoparticle Modified
Reaction, improves interface cohesion, improves the combination property of carbon nanotube metal based composite materials.
Compared with prior art, the present invention has following beneficial effect：
(1) interface cohesion and the densification of carbon nanotube metal based composite materials can be improved；
(2) surface defect of CNT can be modified, improves the enhancing benefit of CNT；
(3) interfacial reaction of energy Effective Regulation CNT and metallic matrix；
(4) process is simple, it is environment-friendly, be conducive to further genralrlization.
Brief description of the drawings
The detailed description made to non-limiting example with reference to the following drawings by reading, further feature of the invention,
Objects and advantages will become more apparent upon：
Fig. 1 is interface schematic diagram of the present invention；
Fig. 2 is the carbon nano-tube modified transmission electron microscope micrograph of the aluminum oxide prepared in the embodiment of the present invention 1.
Fig. 3 is the transmission electron microscope micrograph of the Wolfram oxide modified CNT of preparation in the embodiment of the present invention 2.
Specific embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
As shown in figure 1, the invention provides the interface and preparation method of a kind of carbon nanotube metal based composite materials,
The method carries out surface to CNT and is modified using Nano sol, and the CNT of Nanoparticle Modified is distributed into Metal Substrate
Among body, the carbon nanotube metal based composite materials of Nanoparticle Modified are obtained.
In example 1 below -5 and comparing embodiment 1-3：
A diameter of 30-50nm of CNT, length is 10-20 μm, and matrix is that the pure aluminium powder of purity 99.9% or 5083 are closed
Bronze, the mass fraction of CNT is 1.0%.In other embodiments can also be using other diameters and length, quality point
Several CNTs.
In order to verify the relation between modifier introduction volume and carbon nano tube surface defect, using nitric acid and sulfuric acid (volume
Than 3：1) surface acidification has been carried out to CNT, by control acidificatoin time regulated and controled carbon nano tube surface defect it is dense
Degree.Carbon nano tube surface carboxyl-content is determined by X-ray photoelectron spectroscopic analysis instrument dense to characterize carbon nano tube surface defect
Degree.Activation process can also be carried out to carbon nano tube surface using other acid solutions in other embodiments, as long as can realize logical
Overactivation treatment so that carbon nano tube surface defect turns into active site.
Additionally, determining the modifier content of carbon nano tube surface introducing using weight-loss method, test result shows modifier
The content of introducing increases with the increase of carbon nano tube surface defect content.Finally, using powder metallurgical technique, through overmulling
Powder, pressed compact, sintering are prepared for CNT aluminum matrix composite.And by electrochemical reaction and each embodiment of gas Chromatographic Determination
The interfacial reaction degree of middle sample, as a result as shown in table 2.What table 3 was given is the lastness of the sample of the preparation in each embodiment
Energy.
The interfacial reaction degree of material in each embodiment of table 2
Material final performance in each embodiment of table 3
The present invention is elaborated by following examples：
Embodiment 1
Using nitric acid and sulfuric acid (volume ratio 3：1) surface acidification 5h is carried out to CNT, and prepares CNT
Dispersion liquid, the concentration of the dispersion liquid is 0.5~4g/200mL；Certainly can also be in other embodiments other concentration ranges；
Preparation of nano alumina sol (mol ratio Al：H2O=1:100, control to be modified by regulating and controlling to add the amount of colloidal sol
The introduction volume of thing), carbon nano tube dispersion liquid is added dropwise in nano alumina sol, and magnetic agitation 30min, it is laggard
The ultrasonically treated 2h of row, filtration drying obtains the carbon nanotube powder of nano aluminium oxide modification.
Then it is that 99.9% pure aluminium powder mixes with purity, pressed compact, 570 DEG C sinter 2 hours, the nano aluminium oxide of preparation
The CNT aluminum matrix composite consistency of modification is 99.3%, and yield strength is 298MPa, and tensile strength is 415MPa, is prolonged
It is 9.9% to stretch rate.It is 8.0% by electrochemical reaction and its interfacial reaction degree of gas Chromatographic Determination.
As shown in Fig. 2 being the carbon nano-tube modified transmission electron microscope micrograph of the aluminum oxide prepared in embodiment 1, aluminum oxide
Nano particle is uniformly discretely attached to carbon nano tube surface, and local modification is carried out to CNT.
Embodiment 2
Using nitric acid and sulfuric acid (volume ratio 3：1) surface acidification 8h is carried out to CNT, and prepares CNT
Dispersion liquid.
Preparation of nano alumina sol, carbon nano tube dispersion liquid is added dropwise in nano alumina sol, and magnetic force
Stirring 30min, carries out ultrasonically treated 2h afterwards, and filtration drying obtains the carbon nanotube powder of nano aluminium oxide modification.
Then it is that 99.9% pure aluminium powder mixes with purity, pressed compact, 570 DEG C sinter 2 hours, the nano aluminium oxide of preparation
The CNT aluminum matrix composite consistency of modification is 99.1%, and yield strength is 320MPa, and tensile strength is 440MPa, is prolonged
It is 7.0% to stretch rate.It is 9.0% by electrochemical reaction and its interfacial reaction degree of gas Chromatographic Determination.
As shown in figure 3, being the transmission electron microscope micrograph of the Wolfram oxide modified CNT of preparation in embodiment 2, tungsten oxide
Nano particle is uniformly discretely attached to carbon nano tube surface, and local modification is carried out to CNT.
Embodiment 3
Using nitric acid and sulfuric acid (volume ratio 3：1) surface acidification 5h is carried out to CNT, and prepares CNT
Dispersion liquid.
Preparation of nano tungsten oxide colloidal sol, carbon nano tube dispersion liquid is added dropwise in nanometer tungsten oxide colloidal sol, and magnetic force
Stirring 30min, carries out ultrasonically treated 2h afterwards, and filtration drying obtains the carbon nanotube powder of nanometer tungsten oxide modification.
Then it is that 99.9% pure aluminium powder mixes with purity, pressed compact, 570 DEG C sinter 2 hours, the nanometer tungsten oxide of preparation
The consistency of the CNT aluminum matrix composite of modification is 99.1%, and yield strength is 295MPa, and tensile strength is 408MPa,
Elongation percentage is 8.5%.It is 7.5% by electrochemical reaction and its interfacial reaction degree of gas Chromatographic Determination.
Embodiment 4
Using nitric acid and sulfuric acid (volume ratio 3：1) surface acidification 8h is carried out to CNT, and prepares CNT
Dispersion liquid.Preparation of nano tungsten oxide colloidal sol, carbon nano tube dispersion liquid is added dropwise in nanometer tungsten oxide colloidal sol, and magnetic force is stirred
30min is mixed, ultrasonically treated 2h is carried out afterwards, filtration drying obtains the carbon nanotube powder of nanometer tungsten oxide modification.Then with it is pure
The pure aluminium powder spent for 99.9% mixes, pressed compact, the CNT aluminium of the nanometer tungsten oxide modification of 570 DEG C of sintering preparation in 2 hours
The consistency of based composites is 98.5%, and yield strength is 310MPa, and tensile strength is 430MPa, and elongation percentage is 6.0%.It is logical
It is 8.0% to cross electrochemical reaction and its interfacial reaction degree of gas Chromatographic Determination.
Embodiment 5
Using nitric acid and sulfuric acid (volume ratio 3：1) surface acidification 5h is carried out to CNT, and prepares CNT
Dispersion liquid.Preparation of nano alumina sol, carbon nano tube dispersion liquid is added dropwise in nano alumina sol, and magnetic force is stirred
30min is mixed, ultrasonically treated 2h is carried out afterwards, filtration drying obtains the carbon nanotube powder of nano aluminium oxide modification.Then with it is pure
5083 alloy powders spent for 99.9% mix, pressed compact, the carbon nanometer of the nano aluminium oxide modification of 570 DEG C of sintering preparation in 2 hours
Pipe aluminum matrix composite consistency is 99.1%, and yield strength is 345MPa, and tensile strength is 455MPa, and elongation percentage is 8.0%.
It is 6.0% by electrochemical reaction and its interfacial reaction degree of gas Chromatographic Determination.
Comparing embodiment 1
Surface activation process is carried out to CNT using strong acid, carbon nanotube powder is obtained after filtering, drying.Then with
Purity is 99.9% pure aluminium powder mixing, pressed compact, the densification of the CNT aluminium composite material of preparation in 2 hours of 570 DEG C of sintering
It is 99.5% to spend, and yield strength is 247MPa, and tensile strength is 358MPa, and elongation percentage is 12.1%.By electrochemical reaction and
Its interfacial reaction degree of gas Chromatographic Determination is 25.0%.
Comparing embodiment 2
Surface activation process is carried out to CNT using strong acid, carbon nanotube powder is obtained after filtering, drying, then use
Physical vapour deposition (PVD) is the pellumina of 10-20nm in carbon nano tube surface deposit thickness.Then be with purity 99.9% it is pure
Aluminium powder mixes, pressed compact, the cause of the CNT aluminum matrix composite of the continuous aluminium oxide modification of 570 DEG C of sintering preparation in 2 hours
Density is 95.2%, and yield strength is 274MPa, and tensile strength is 382MPa, and elongation percentage is 3.5%.By electrochemical reaction and
Its interfacial reaction degree of gas Chromatographic Determination is 5.8%.
Comparing embodiment 3
Surface activation process is carried out to CNT using strong acid, carbon nanotube powder is obtained after filtering, drying, then use
Physical vapour deposition (PVD) is the oxidation tungsten film of 10-20nm in carbon nano tube surface deposit thickness.Then be with purity 99.9% it is pure
Aluminium powder mixes, pressed compact, the cause of the CNT aluminum matrix composite of the continuous oxidation tungsten modification of 570 DEG C of sintering preparation in 2 hours
Density is 94.7%, and yield strength is 270MPa, and tensile strength is 381MPa, and elongation percentage is 3.1%.By electrochemical reaction and
Its interfacial reaction degree of gas Chromatographic Determination is 6.2%.
Embodiment 6
From a diameter of 10-20nm, length is 5-10 μm of CNT, and matrix is 2024 aluminium alloys of 99.9% purity
Powder, uses the inventive method to prepare the CNT aluminum matrix composite that mass fraction is for 2.0%, and concrete technology is as follows：
Acidification is carried out to carbon nano tube surface using liquor potassic permanganate, carbon nano tube dispersion liquid is prepared, oxygen is prepared
Change tin oxide sol, carbon nano tube dispersion liquid is added dropwise in nano oxidized tin oxide sol, and magnetic agitation 30min, carry out afterwards
Ultrasonically treated 2h, filtration drying obtains the carbon nanotube powder of nano tin dioxide modification.Then it is the 2024 of 99.9% with purity
Al alloy powder mixes, pressed compact, the CNT aluminum matrix composite of the nano tin dioxide modification of 570 DEG C of sintering preparation in 2 hours
Consistency is 97.5%, and yield strength is 410MPa, and tensile strength is 590MPa, and elongation percentage is 5.5%.By electrochemical reaction
Its interfacial reaction degree is 6.7% with gas Chromatographic Determination.
Embodiment 7
From a diameter of 100-150nm, length is 10-20 μm of CNT, and matrix is 6061 aluminium of 99.9% purity
Alloyed powder, uses the inventive method to prepare the CNT aluminum matrix composite that mass fraction is for 3.0%, and concrete technology is as follows：
Carrying out surface to CNT using concentrated nitric acid carries out acidification, prepares carbon nano tube dispersion liquid, prepares dioxy
Change titanium colloidal sol, carbon nano tube dispersion liquid is added dropwise in nano-oxide colloidal sol, and magnetic agitation 30min, carry out afterwards
Ultrasonically treated 2h, filtration drying obtains the carbon nanotube powder of nano titanium oxide modification.Then it is 99.9% with purity
6061 Al alloy powders mix, pressed compact, the CNT aluminum-base composite of the nano titanium oxide modification of 570 DEG C of sintering preparation in 2 hours
The consistency of material is 98.1%, and yield strength is 350MPa, and tensile strength is 460MPa, and elongation percentage is 5.1%.By electrification
It is 7.2% to learn reaction and its interfacial reaction degree of gas Chromatographic Determination.
Comparing embodiment compared with the present invention, due to modifying carbon nano tube surface or using continuous film modified,
Under identical material component and preparation process condition, the consistency and mechanical property of material in comparing embodiment, typically than this hair
The low intensity 15-20% of the CNT aluminum matrix composite of bright preparation.Wherein, the carbon nano-tube modified aluminum-base composite material of continuous film
Material densification is difficult, and elongation percentage is greatly reduced；And Nanoparticle Modified CNT aluminum matrix composite, in elongation percentage reduction very
In the case of small, intensity is greatly improved.By determining its interfacial reaction degree it can be found that not carrying out what surface was modified
CNT/Al interfacial reactions degree is 25.0%, is obtained very well using Nanoparticle Modified and continuous film modified CNT/Al interfacial reactions
Control, the extent of reaction be 6~8%.In sum, interface of the present invention and preparation method can improve interface knot
Close, regulate and control interfacial reaction degree, and consistency and combination are unaffected so that the power of carbon nanotube metal based composite materials
Performance is learned to be largely increased.
Specific embodiment of the invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can within the scope of the claims make various deformations or amendments, this not shadow
Sound substance of the invention.
Claims (13)
1. a kind of preparation method of the carbon nanotube metal based composite materials based on Interface Design, it is characterised in that：It is described
Interface Design refers to that local modification is carried out to carbon nano tube surface fault location using nano-particle, hinders fault location that circle occurs
Face is reacted, and the interfacial reaction for passing through the appropriateness and metallic matrix between at carbon nano tube surface structural integrity obtains good interface
With reference to；
The preparation method includes：
Step one, carbon nano tube surface local activation treatment prepares carbon nano tube dispersion liquid or using the carbon for preparing in advance
Nanotube dispersion liquid；
Step 2, prepares modifier Nano sol or using the modifier Nano sol for preparing in advance, and by CNT
Dispersion liquid mixes with Nano sol, stirs, then carries out ultrasonically treated, filtration drying, obtains what nano-particle was locally modified
CNT；
Step 3, the CNT of the local modification of nano-particle is evenly spread among metallic matrix, then densified acquisition
Carbon nanotube metal based composite materials.
2. the preparation method of carbon nanotube metal based composite materials according to claim 1, it is characterised in that：Described gold
Category matrix is aluminium and its alloy.
3. the preparation method of carbon nanotube metal based composite materials according to claim 1, it is characterised in that：It is described compound
The mass fraction of CNT is 0.5~10% in material.
4. the preparation method of carbon nanotube metal based composite materials according to claim 3, it is characterised in that：Described carbon
The mass fraction of nanotube is 1~5%.
5. the preparation method of the carbon nanotube metal based composite materials according to claim any one of 1-4, it is characterised in that：
Described preparation method carries out activation process by acid solution to carbon nano tube surface so that carbon nano tube surface defect turns into activity
Point, fault location has surface energy high, as the preferential attachment point of nano-particle.
6. the preparation method of the carbon nanotube metal based composite materials according to claim any one of 1-4, it is characterised in that：
In the step 2, after CNT is mixed with Nano sol, anion surfactant is added, suppress CNT mutual
Between reunion so that nano-particle uniform adsorption is on the active site of CNT.
7. the preparation method of the carbon nanotube metal based composite materials according to claim any one of 1-4, it is characterised in that：
The modifier Nano sol, the wherein introduction volume of modifier relative to CNT volume fraction by based on below equation
Calculate：
Wherein, r is CNT radius, and L is length of carbon nanotube, and Δ r is the radius of nano-particle, and c% is CNT table
Planar defect concentration, β is volume fraction of the nano-particle relative to CNT.
8. the preparation method of the carbon nanotube metal based composite materials according to claim any one of 1-4, it is characterised in that：
The carbon nanotube diameter is 5-100nm.
9. the preparation method of carbon nanotube metal based composite materials according to claim 8, it is characterised in that：Described carbon
A diameter of 10-50nm of nanotube.
10. the preparation method of the carbon nanotube metal based composite materials according to claim any one of 1-4, its feature exists
In：Described nano-particle is metal oxide or metal complex or silica.
The preparation method of 11. carbon nanotube metal based composite materials according to claim 10, it is characterised in that：Described
The particle diameter of nano-particle is 1-50nm.
The preparation method of 12. carbon nanotube metal based composite materials according to claim 11, it is characterised in that：Described
The particle diameter of nano-particle is 1-10nm.
The preparation method of 13. carbon nanotube metal based composite materials according to claim any one of 1-4, its feature exists
In：Good combination is formed between the nano-particle energy and CNT, while from good with metallic matrix wetability
Nano-particle, can improve the interface cohesion of CNT and metallic matrix；Nano-particle is repaiied for carbon nano tube surface defect
Decorations are acted on so that nano-particle slows down interfacial reaction, it is ensured that CNT as elements diffusion and the barrier layer of interfacial reaction
Integrality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510275357.5A CN104962841B (en) | 2015-05-26 | 2015-05-26 | The interface and preparation method of a kind of carbon nanotube metal based composite materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510275357.5A CN104962841B (en) | 2015-05-26 | 2015-05-26 | The interface and preparation method of a kind of carbon nanotube metal based composite materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104962841A CN104962841A (en) | 2015-10-07 |
| CN104962841B true CN104962841B (en) | 2017-06-09 |
Family
ID=54216924
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510275357.5A Active CN104962841B (en) | 2015-05-26 | 2015-05-26 | The interface and preparation method of a kind of carbon nanotube metal based composite materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104962841B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105385871B (en) * | 2015-10-22 | 2018-01-19 | 上海交通大学 | A kind of preparation method of polynary nanometer complex intensifying heat resisting aluminium base composite material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101372330B (en) * | 2008-10-08 | 2011-03-23 | 长沙理工大学 | Method for coating carbon nano-tube with metal doped zinc oxide nano-particle |
| CN103789564B (en) * | 2014-01-23 | 2015-10-14 | 上海交通大学 | A kind of method for preparing powder metallurgy of carbon nano tube reinforced aluminum alloy composite material |
-
2015
- 2015-05-26 CN CN201510275357.5A patent/CN104962841B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104962841A (en) | 2015-10-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tajzad et al. | Production methods of CNT-reinforced Al matrix composites: a review | |
| Liu et al. | Well-dispersion of CNTs and enhanced mechanical properties in CNTs/Cu-Ti composites fabricated by Molecular Level Mixing | |
| CN106399766B (en) | A kind of carbon nanotube and graphene collaboration reinforced aluminum matrix composites and preparation method | |
| US11639542B2 (en) | Multi-scale and multi-phase dispersion strengthened iron-based alloy, and preparation and characterization methods thereof | |
| Guo et al. | Comprehensive performance regulation of Cu matrix composites with graphene nanoplatelets in situ encapsulated Al2O3 nanoparticles as reinforcement | |
| CN106312057A (en) | Powder metallurgy preparation method for nano-particle reinforced ultra-fine grain metal-matrix composite | |
| Chen et al. | Synthesis and magnetic characterization of Co-NiO-Ni core-shell nanotube arrays | |
| Hao et al. | Effect of mechanical alloying time and rotation speed on evolution of CNTs/Al-2024 composite powders | |
| Oliver et al. | Spark plasma sintering of aluminium composites—a review | |
| Zuo et al. | Simultaneous improvement of electrical conductivity and mechanical property of Cr doped Cu/CNTs composites | |
| Lal et al. | An alternative improved method for the homogeneous dispersion of CNTs in Cu matrix for the fabrication of Cu/CNTs composites | |
| Hu et al. | Secondary phases strengthening-toughening effects in the Mo–TiC–La2O3 alloys | |
| CN106191494B (en) | Carbon nanotube enhances the metallurgical preparation method of titanium matrix composite | |
| CN105838913A (en) | Graphene/nickel composite material and preparation method thereof | |
| Zhang et al. | Influence of acid-treated time of carbon nanotubes on mechanical property in carbon nanotubes reinforced copper matrix composites | |
| Yu et al. | Effect of interfacial reaction on Young's modulus in CNT/Al nanocomposite: A quantitative analysis | |
| Zhang et al. | Microstructure and properties of Al 2 O 3 dispersion-strengthened copper fabricated by reactive synthesis process | |
| Shu et al. | Microstructure and mechanical properties of nano-carbon reinforced Mo–Cu–Zr composites | |
| Liu et al. | Effect of graphene addition on properties of Cu-based composites for electrical contacts | |
| Dong et al. | Fabrication and reduction process of dispersive Er2O3 doped Mo super-fine powders comparing with La2O3 doped Mo powders | |
| Xu et al. | Properties and microstructure of oxide dispersion strengthened tungsten alloy prepared by liquid-phase method: a review | |
| CN102814503B (en) | Method for preparing dispersion strengthening ferritic alloy steel powder of nanometer yttrium oxide particles | |
| CN104962841B (en) | The interface and preparation method of a kind of carbon nanotube metal based composite materials | |
| Xiong et al. | Research on the performance of rGO-CNTs synergistically enhanced copper matrix composites | |
| Li et al. | Inhibiting GNPs breakage during ball milling for a balanced strength-ductility match in GNPs/Al composites |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |