CN109957674A - Based on the method that orientation cracking CNTs prepares CNTs-GR/Cu based composites under particle protective effect - Google Patents
Based on the method that orientation cracking CNTs prepares CNTs-GR/Cu based composites under particle protective effect Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
- C22C2026/002—Carbon nanotubes
Abstract
The present invention relates to a kind of methods that orientation cracking CNTs prepares CNTs-GR/Cu based composites under protective effect based on particle, belong to nanocomposite technical field.The method of the invention is mainly based upon under the protective effect of the solid particle of the surface CNTs nesting; the CNTs for keeping both ends exposed in special lysate is cracked; and both ends crack the GR to be formed and intermediate uncracked CNTs and are connected with each other by C-C key; realize effective combination of CNTs and GR; and utilize the unique two-dimensional drape surface GR; increase the contact area of itself and copper-based matrix; improve interface bond strength; transmitting load effect is effectively played, makes CNTs-GR/Cu based composites that superior performance be presented.
Description
Technical field
The present invention relates to one kind to prepare CNTs-GR/Cu based composites based on orientation cracking CNTs under particle protective effect
Method, belong to nanocomposite technical field.
Background technique
Effect of the discontinuous phase reinforced metal based composites (DRMMCs) in single reinforcement (ceramic particle, staple fiber)
Under, substrate performance is improved.In recent years, being adjusted to the microstructure of DRMMCs and then optimize its comprehensive performance becomes
Research focus, wherein it is to break through one of the approach of the problem that the collaboration of multi-element mixed reinforcement, which plays invigoration effect,.Existing research report
Mechanics and electricity of the mixing reinforcement of road, carbon nanotube (CNTs) and graphene (GR) composition to epoxy resin composite material
Performance is significantly increased.However, metal-base composites is since the wetability between reinforcement and matrix is poor, and simple solution is mixed
Conjunction method can not achieve the combination of GR and CNTs, therefore can not obtain significant synergistic effect, and GR-CNTs is caused to mix reinforcement
It is bad to the reinforcing effect of metallic matrix.Therefore, reasonable spatial design realizes that being effectively combined between two kinds of reinforcements is hair
Wave the key of synergistic effect.
Kosynkin study group reports CNTs can be certainly export-oriented along CNTs axial vector direction under the action of lysate
Interior layer-by-layer cracking can make CNTs that different degrees of cracking occur, obtain two by the concentration and reaction time that control lysate
The GR+CNTs or be all cracked into GR that member mixes.If the GR+CNTs that this cracking mode obtains is distributed to metallic matrix
In, it perhaps can play the role of strengthening matrix.But the property intrinsic due to CNTs, multi wall structure is between layers
It is only combined by lesser Van der Waals force, the anti-shearing sliding between each layer is weaker, can equally make when load further increases outer
The CNTs of GR and internal layer that layer is formed are detached from, and therefore, the binary hybrid buildup body that this cracking mode obtains still lacks
Effective combination between GR and CNTs.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of based on orientation cracking CNTs under particle protective effect
Determining for CNTs is realized in the method for preparing CNTs-GR/Cu based composites, the protective effect that this method is mainly based upon solid particle
It obtains mixing continuous reinforcement by the GR-CNTs that C-C is keyed to cracking, and utilizes the unique two-dimensional drape surface GR, increase
The contact area of big itself and copper-based matrix, improves interface bond strength, effectively plays transmitting load effect, makes CNTs-GR/Cu base
Superior performance is presented in composite material.
The purpose of the present invention is what is be achieved through the following technical solutions.
A method of CNTs-GR/Cu based composites are prepared based on orientation cracking CNTs under particle protective effect, it is described
Method and step is as follows:
(1) acidification of CNTs
Dose volume is than the concentrated nitric acid (mass fraction 65%~68%) and the concentrated sulfuric acid (mass fraction 95% for 1:3~1:5
~98%) mix acid liquor I；CNTs is added in mix acid liquor I, and stands 2h~12h under the conditions of 60 DEG C~80 DEG C, is washed
It washs, dry, the CNTs being acidified；
(2) solid particle nesting CNTs
Prepare respectively the CNTs aqueous solution of acidification, concentration that mass fraction is 0.01%~0.1% be 0.01 mol/L~
The metal salt solution and concentration of 1mol/L is the solution M of 0.5mol/L~3mol/L, and by three kinds of solution according to VCNTs:
VMetal salt solution: VSolution M=(0.1~0.5): 1:(1~3) volume ratio carry out mixing and metal salt solution react with solution M generate sink
It forms sediment；
The precipitating that a) if reaction generates is identical as solid particle, solids is directly collected, it is multiple to obtain CNTs/ solid particle
Close object；
If what b) reaction generated is precipitated as hydroxide and solid particle when being oxide, solids is first collected, is reheated
It decomposes and generates corresponding oxide, obtain CNTs/ solid particle compound；
If what c) reaction generated is precipitated as hydroxide and solid particle when being protoxide, after the completion of precipitation reaction, first
Glucose solution reduction is added and generates corresponding protoxide, regathers solids, obtains CNTs/ solid particle compound；
(3) orientation cracking CNTs
First by CNTs/ solid particle compound be added volume ratio be 1:5~1:10 concentrated phosphoric acid (mass fraction 83%~
98%) and in the mix acid liquor II of the concentrated sulfuric acid (mass fraction 95%~98%), KMnO then is added under condition of ice bath4Powder
End is again heated to 60 DEG C~80 DEG C and keeps the temperature 1h~3h, is cooled to room temperature, and excessive hydrogen peroxide is added and removes KMnO4Also originate in
Object MnO2, filter, washed with the dilute hydrochloric acid solution that mass fraction is not more than 5%, is dry, it is compound to obtain GR-CNTs/ solid particle
Object；
Wherein, KMnO4In the dense H of unit volume2SO4Middle mass fraction is 0.5%~7%, CNTs and KMnO4Quality
Than for 1:5~1:10；
(4) removal of solid particle
No less than 5min is added in hydrofluoric acid in GR-CNTs/ solid particle compound, removes the uncracked surface CNTs
Remaining solid particle is filtered, washed, is freeze-dried, and obtains GR-CNTs and mixes continuous reinforcement；
(5) PM technique prepares GR-CNTs/Cu based composites
GR-CNTs mix continuous reinforcement and copper-based powder ball milling mixing it is uniform after, then be placed in 500 DEG C~900 DEG C and
Heat-insulation pressure keeping 0.5h~1h under the conditions of 30MPa~300MPa obtains GR-CNTs/Cu based composites.
In step (1), the CNTs is double-walled CNTs or/and multi wall CNTs.
In step (2), it can be BaCl that the metal salt solution, which is the water-soluble salt solution of Ba, Ag, Al or Cu,2、Ba
(NO3)2、AgNO3、AlCl3、Al(NO3)3、Al2(SO4)3、CuCl2、Cu(NO3)3Or CuSO4, solution M is to contain Cl-, SO4 2Or
The water-soluble salt solution or NH of OH-3·H2Solid particle in O, CNTs/ solid particle compound can for AgCl,
BaSO4、Al2O3, CuO or Cu2O。
In step (3), CNTs/ solid particle compound adds KMnO after stirring 0.5h~1h in mix acid liquor II again4Powder
End.
In step (5), the partial size of copper-based powder is 100 mesh~500 mesh, copper-based powder be fine copper powder, copper powder and other
The mixed powder or copper alloy powder of metal powder；GR-CNTs, which mixes continuous reinforcement and accounts for the mass fraction of copper-based powder, is
0.1wt%~2wt%；During ball milling mixing, ratio of grinding media to material is 5:1~20:1, and rotational speed of ball-mill is 100r/min~250r/min,
Ball-milling Time 0.5h~12h.
The utility model has the advantages that
The method of the invention is mainly based upon under the protective effect of the solid particle of the surface CNTs nesting, in special cracking
The CNTs for making both ends exposed in liquid is cracked, and both ends crack the GR to be formed and intermediate uncracked CNTs passes through C-C key
It is connected with each other, realizes effective combination of CNTs and GR, and utilize the unique two-dimensional drape surface GR, increase itself and copper-based matrix
Contact area, improves interface bond strength, effectively plays transmitting load effect, CNTs-GR/Cu based composites is presented more excellent
Different performance.
Detailed description of the invention
Fig. 1 is HRTEM (high-resolution transmission electron microscope) figure that CNTs is acidified in embodiment 1.
Fig. 2 is CNTs-GR/Al in embodiment 12O3SEM (scanning electron microscope) figure of compound.
Fig. 3 is the HRTEM figure that CNTs-GR mixes continuous reinforcement in embodiment 1.
Fig. 4 is CNTs-GR/Cu in embodiment 22The SEM of O compound schemes.
Fig. 5 is the TEM figure that CNTs-GR mixes continuous reinforcement in embodiment 2.
Specific embodiment
The present invention is further elaborated with reference to the accompanying drawings and detailed description, wherein the method is as without especially
Explanation is conventional method, and the raw material can be gotten from open business unless otherwise instructed.
In following embodiment:
Concentrated nitric acid: 65wt%；
The concentrated sulfuric acid: 98wt%；
Concentrated phosphoric acid: 98wt%；
Multi-walled carbon nanotube: purity 99.9%, O.D. × L:(20nm ± 5nm) × (2 μm ± 0.5 μm), Chinese Academy of Sciences Chengdu
Organic chemistry research institute；
Scanning electron microscope: Nova Nano-450, U.S. FEI；
Transmission electron microscope: Tecnai G2-TF30, U.S. FEI；
The performance characterization of the CNTs-GR/Cu based composites prepared in embodiment: scientific & technical corporation is ground using Shang Hairun
MC010 type hardness tester meter carries out vickers hardness test, wherein loaded load 9.8N, load time 15s；Use Xiamen electricity section
The Sigma-2008 conductivity meter of company carries out conductivity test, wherein test sample is the cylindrical body of Φ 4mm × 2mm；Using
Universal testing machine (AUTO-STC8800) carries out stretching experiment at room temperature, wherein strain rate is 2.0 × 10-3s-1。
Embodiment 1
Based on Al2O3Orientation cracking CNTs prepares the specific steps of CNTs-GR/Cu composite material such as under particle protective effect
Under:
(1) acidification of CNTs
Mix acid liquor I of the dose volume than concentrated nitric acid and the concentrated sulfuric acid for 1:3；1g multi wall CNTs is added to 240mL to mix
It closes in acid solution I, and stands 12h at 60 DEG C, washing, dry, the CNTs being acidified, as shown in Figure 1；
(2)Al2O3Particle nesting CNTs
The 0.01g CNTs being acidified is evenly spread in 50mL deionized water, is then 0.01mol/L with 500mL concentration
Al (NO3)3The NaOH solution hybrid reaction that solution and 500mL concentration are 0.5mol/L, collects solids after reacting 30min,
And solids is placed at 250 DEG C and calcines 1h, obtain CNTs/ Al2O3Compound；
(3) orientation cracking CNTs
First by 3g CNTs/Al2O3Compound is added in the mix acid liquor II of the concentrated phosphoric acid that volume ratio is 1:5 and the concentrated sulfuric acid,
It is stirred after 40min and 3g KMnO is added under condition of ice bath again4Powder is then heated to 60 DEG C and keeps the temperature 3h, is cooled to
Above-mentioned reaction solution is poured into the hydrogen peroxide that 500mL mass fraction is 30% and stirs 0.5h by room temperature, is filtered and with 5wt%'s
Dilute hydrochloric acid solution washing, drying, obtain GR-CNTs/ Al2O3Compound, as shown in Figure 2；
(4)Al2O3The removal of particle
By GR-CNTs/Al2O3Compound is added in the HF that mass fraction is 3% and etches 30min, removes uncracked CNTs
Al remained on surface2O3Particle is filtered, washed, is freeze-dried, and obtains GR-CNTs and mixes continuous reinforcement, as shown in Figure 3；
(5) PM technique prepares GR-CNTs/Cu composite material
GR-CNTs is mixed into continuous reinforcement and partial size is quality of 300 mesh~500 mesh pure copper powder according to 0.4:100
Ball milling pearl is added than being mixed, and according to the ratio of grinding media to material of 10:1, then the ball milling 0.5h at 250r/min；It again will be after ball milling
Mixed powder be placed in graphite jig, and the hot pressed sintering 1h under 700 DEG C and 50MPa obtains GR-CNTs/Cu composite wood
Material.
As shown in Figure 1, the acidification of CNTs can remove raw material CNTs non-pure material and its outer wall it is amorphous
Carbon-coating, and high energy active site is formed under the oxidation of strong acid, thus the nesting for subsequent solid particle on the surface CNTs
Forming core site is provided.Fig. 2 shows under the action of special lysate, is exposed to the CNTs at solid particle both ends due to shortage
The protection of grain, and the axial ecto-entad along tube wall successively cracks, such as arrow indicating positions in figure.At the quarter of 3% HF solution
Under erosion effect, solid particle is completely removed, and is formed the GR that multilayer has obvious fold after the cracking of the both ends CNTs, is effectively increased
The contact area of CNTs and pure copper powder matrix, and in solid particle protection zone range, CNTs is not cracked, keeps its script
One-dimensional tubular structure (as shown by the arrows in Figure 3) so that both ends crack the GR to be formed and intermediate uncracked CNTs is logical
Cross the interconnection of C-C key.
Embodiment 2
Based on Cu2Orientation cracking CNTs prepares the specific steps of CNTs-GR/Cu-Ti composite material under O particle protective effect
It is as follows:
(1) acidification of CNTs
Mix acid liquor I of the dose volume than concentrated nitric acid and the concentrated sulfuric acid for 1:5；1g multi wall CNTs is added to 200mL to mix
It closes in acid solution I, and stands 2h at 80 DEG C, washing, dry, the CNTs being acidified；
(2)Cu2O particle nesting CNTs
The 0.05g CNTs being acidified is evenly spread in 50mL deionized water, is then 0.5mol/L's with 100mL concentration
Cu(NO3)2Solution and 300mL concentration are the NaOH solution hybrid reaction of 3mol/L, react and add 10mL concentration after 5min and be
The glucose solution of 0.45mol/L is further continued for reaction 45min, collects solids, obtain CNTs/Cu2O composite granule；
(3) orientation cracking CNTs
First by 4g CNTs/Cu2O compound is added in the mix acid liquor II of the concentrated phosphoric acid that volume ratio is 1:10 and the concentrated sulfuric acid,
Then 5g KMnO is added under condition of ice bath4Powder is again heated to 80 DEG C and keeps the temperature 1h, is cooled to room temperature, and above-mentioned reaction is molten
Liquid, which pours into the hydrogen peroxide that 1000mL mass fraction is 30%, stirs 0.5 h, filter and washed with the dilute hydrochloric acid solution of 5wt%,
It is dry, obtain GR-CNTs/Cu2O compound, as shown in Figure 4；
(4)Cu2The removal of O particle
By GR-CNTs/Cu2O compound, which is added in the hydrofluoric acid that mass fraction is 3%, etches 30min, removes uncracked
CNTs Cu remained on surface2O particle is filtered, washed, is freeze-dried, and obtains GR-CNTs and mixes continuous reinforcement, such as Fig. 5 institute
Show；
(5) PM technique prepares GR-CNTs/Cu-Ti composite material
By GR-CNTs mix continuous reinforcement and partial size be 100 mesh~300 mesh Cu-1.0wt%Ti alloy powder according to
The mass ratio of 0.3:100 is mixed, and ball milling pearl is added according to the ratio of grinding media to material of 20:1, then the ball milling at 100r/min
12h；The mixed powder after ball milling is placed in graphite jig again, and the hot pressed sintering 0.5h under 700 DEG C and 50MPa, is obtained
GR-CNTs/Cu-Ti composite material.
Fig. 4 shows to be exposed to Cu2Protection of the CNTs at O particle both ends due to lacking solid particle, and along the axial direction of tube wall
Ecto-entad successively cracks, and fully opens, such as arrow indicating positions in figure.Under the corrasion of HF, Cu2O particle is complete
Full removal forms the GR that multilayer has obvious fold after the cracking of the both ends CNTs, effectively increase CNTs and Cu-1.0wt%Ti and close
The contact area of bronze body, and in solid particle protection zone range, CNTs is not cracked, keeps the one-dimensional tubulose of its script
Structure (as shown by the arrows in Figure 5), so that both ends crack the GR to be formed and the uncracked CNTs in centre is mutual by C-C key
Connection.
Comparative example 1
0.05g GR, 0.05g CNTs and 25g partial size are mixed for 300 mesh~500 mesh pure copper powder, and according to 10:1's
Ball milling pearl is added in ratio of grinding media to material, then the ball milling 0.5h at 250r/min；The mixed powder after ball milling is placed in graphite jig again,
And the hot pressed sintering 1h under 700 DEG C and 50MPa, obtain discontinuous hybrid buildup GR-CNTs/Cu composite material.
Comparative example 2
It is that 100 mesh~300 mesh Cu-1.0wt%Ti alloy powder mixes by 0.04g GR, 0.04g CNTs and 24g partial size
It closes, and ball milling pearl is added according to the ratio of grinding media to material of 20:1, then the ball milling 12h at 100r/min；Again by the mixed powder after ball milling
It is placed in graphite jig, and 0.5 h of hot pressed sintering under 700 DEG C and 50MPa, obtains discontinuous hybrid buildup GR-CNTs/
Cu-Ti composite material.
The composite material prepared in embodiment 1, embodiment 2, comparative example 1 and comparative example 2 is tested for the property respectively,
The results are shown in Table 1.According to the test result of table 1 it is found that GR-CNTs prepared by the present invention mix continuous reinforcement compared to
Discontinuous hybrid buildup body more can effectively enhance the intensity and hardness of copper-based matrix.It can be seen that CNTs two from TEM testing result
The GR that end check solution is formed effectively is combined with intermediate uncracked CNTs by C-C key, and utilizes the unique two-dimensional surface of GR, is increased
The contact area of big itself and copper-based matrix, improves interface bond strength, makes to mix continuous CNTs-GR/Cu based composites presentation
Superior performance.And it is due to cracking end shape that slight decrease, which occurs, in the conductivity for mixing continuous CNTs-GR/Cu based composites
At GR will increase the interfacial contact area with matrix, thus electronics is caused in the transition process of displacement scatter and hinder
Hinder.
Table 1
In conclusion the above is merely preferred embodiments of the present invention, being not intended to limit the scope of the present invention.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (9)
1. a kind of method that orientation cracking CNTs prepares CNTs-GR/Cu based composites under protective effect based on particle, feature
Be: steps are as follows for the method,
(1) CNTs is added to mixed by concentrated nitric acid and the concentrated sulfuric acid according to the volume ratio progress mixed preparing mix acid liquor I of 1:3~1:5
It closes in acid solution I, and stands 2h~12h under the conditions of 60 DEG C~80 DEG C, washing, dry, the CNTs being acidified；
(2) prepare respectively the CNTs aqueous solution of acidification, concentration that mass fraction is 0.01%~0.1% be 0.01mol/L~
The metal salt solution and concentration of 1mol/L be 0.5mol/L~3mol/L solution M, and by three kinds of solution according to (0.1~
0.5) volume ratio: 1:(1~3) carries out mixing and metal salt solution reacts generation precipitating with solution M；
The precipitating that a) if reaction generates is identical as solid particle, solids is directly collected, it is compound to obtain CNTs/ solid particle
Object；
If what b) reaction generated is precipitated as hydroxide and solid particle when being oxide, solids is first collected, reheats and decomposes
Corresponding oxide is generated, CNTs/ solid particle compound is obtained；
If what c) reaction generated is precipitated as hydroxide and solid particle when being protoxide, after the completion of precipitation reaction, first it is added
Glucose solution reduction generates corresponding protoxide, regathers solids, obtains CNTs/ solid particle compound；
(3) concentrated phosphoric acid and the concentrated sulfuric acid first consolidate CNTs/ according to the volume ratio progress mixed preparing mix acid liquor II of 1:5~1:10
Body particle composites are added in mix acid liquor II, and KMnO then is added under condition of ice bath4Powder is again heated to 60 DEG C~80 DEG C
And 1h~3h is kept the temperature, excessive hydrogen peroxide is first added after being cooled to room temperature, then successively filter, is dilute no more than 5% with mass fraction
Hydrochloric acid solution washing, drying, obtain GR-CNTs/ solid particle compound；Wherein, KMnO4In the dense H of unit volume2SO4Middle matter
Amount score is 0.5%~7%, CNTs and KMnO4Mass ratio be 1:5~1:10；
(4) no less than 5min is added in hydrofluoric acid in GR-CNTs/ solid particle compound, is filtered, washed, is freeze-dried, obtains
GR-CNTs mixes continuous reinforcement；
(5) GR-CNTs is first mixed into continuous reinforcement and copper-based powder ball milling mixing is uniform, then be placed in 500 DEG C~900 DEG C and
Heat-insulation pressure keeping 0.5h~1h under the conditions of 30MPa~300MPa obtains GR-CNTs/Cu based composites.
2. according to claim 1 prepare CNTs-GR/Cu base composite wood based on orientation cracking CNTs under particle protective effect
The method of material, it is characterised in that: in step (1), the CNTs is double-walled CNTs or/and multi wall CNTs.
3. according to claim 1 prepare CNTs-GR/Cu base composite wood based on orientation cracking CNTs under particle protective effect
The method of material, it is characterised in that: in step (2), the metal salt solution is the water-soluble salt solution of Ba, Ag, Al or Cu, solution
M is to contain Cl-、SO4 2-Or OH-Water-soluble salt solution or NH3·H2O。
4. according to claim 1 prepare CNTs-GR/Cu base composite wood based on orientation cracking CNTs under particle protective effect
The method of material, it is characterised in that: the solid particle in CNTs/ solid particle compound is AgCl, BaSO4、Al2O3, CuO or
Cu2O。
5. according to claim 1 prepare CNTs-GR/Cu base composite wood based on orientation cracking CNTs under particle protective effect
The method of material, it is characterised in that: in step (3), after CNTs/ solid particle compound stirs 0.5h~1h in mix acid liquor II
Again plus KMnO4Powder.
6. according to claim 1 prepare CNTs-GR/Cu base composite wood based on orientation cracking CNTs under particle protective effect
The method of material, it is characterised in that: in step (5), copper-based powder be fine copper powder, copper powder and other metal powders mixed powder or
Copper alloy powder.
7. according to claim 1 prepare CNTs-GR/Cu base composite wood based on orientation cracking CNTs under particle protective effect
The method of material, it is characterised in that: in step (5), the partial size of copper-based powder is 100 mesh~500 mesh.
8. according to claim 1 prepare CNTs-GR/Cu base composite wood based on orientation cracking CNTs under particle protective effect
The method of material, it is characterised in that: in step (5), GR-CNTs, which mixes continuous reinforcement and accounts for the mass fraction of copper-based powder, is
0.1wt%~2wt%.
9. according to claim 1 prepare CNTs-GR/Cu base composite wood based on orientation cracking CNTs under particle protective effect
The method of material, it is characterised in that: in step (5), during GR-CNTs mixes continuous reinforcement and copper-based powder ball milling mixing,
Ratio of grinding media to material is 5:1~20:1, and rotational speed of ball-mill is 100r/min~250r/min, Ball-milling Time 0.5h~12h.
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