CN108746653A - A kind of method that solution combustion method prepares CNT-Cu composite granules - Google Patents
A kind of method that solution combustion method prepares CNT-Cu composite granules Download PDFInfo
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- CN108746653A CN108746653A CN201810541795.5A CN201810541795A CN108746653A CN 108746653 A CN108746653 A CN 108746653A CN 201810541795 A CN201810541795 A CN 201810541795A CN 108746653 A CN108746653 A CN 108746653A
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- 239000002131 composite material Substances 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 83
- 239000008187 granular material Substances 0.000 title claims abstract description 58
- 238000009841 combustion method Methods 0.000 title claims abstract description 43
- 239000010949 copper Substances 0.000 claims abstract description 83
- 239000000243 solution Substances 0.000 claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 70
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 69
- 239000000843 powder Substances 0.000 claims abstract description 45
- 238000002485 combustion reaction Methods 0.000 claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000008569 process Effects 0.000 claims abstract description 19
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 18
- 229930006000 Sucrose Natural products 0.000 claims abstract description 18
- 239000005720 sucrose Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 16
- 239000010431 corundum Substances 0.000 claims abstract description 16
- 238000001704 evaporation Methods 0.000 claims abstract description 16
- 230000008020 evaporation Effects 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000013019 agitation Methods 0.000 claims abstract description 8
- 238000009835 boiling Methods 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 230000009467 reduction Effects 0.000 claims description 18
- 229910002651 NO3 Inorganic materials 0.000 claims description 13
- 239000000126 substance Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 6
- LKDRXBCSQODPBY-VRPWFDPXSA-N D-fructopyranose Chemical compound OCC1(O)OC[C@@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-VRPWFDPXSA-N 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 238000006073 displacement reaction Methods 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- 239000000463 material Substances 0.000 abstract description 12
- 230000008859 change Effects 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 11
- 239000005416 organic matter Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 239000002671 adjuvant Substances 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000000693 micelle Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- -1 nitrate anion Ion Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 230000001902 propagating effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- 230000002269 spontaneous effect Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
This application provides a kind of methods that solution combustion method prepares CNT-Cu composite granules, are related to field of composite material preparation.Include the following steps：(1) copper nitrate, the carbon nanotube of functionalization, sucrose and deionized water are mixed into ultrasonic agitation 30min, so that each component is uniformly mixed, obtains mixed solution；(2) mixed solution in step (1) is poured into corundum crucible to heat, solution obtains presoma composite powder through moisture evaporation, boiling, bubble after-combustion；(3) precursor powder for using the reducing process in aqueous solution powder mixing method to obtain solution combustion in step (2) is restored to obtain carbon nanotube copper composite powder.The method that the application solution combustion method prepares CNT-Cu composite granules, it is simple for process, rapid reaction, it is efficient, at low cost, product purity is high, and each component can reach the uniform mixing on molecular level, and material undergoes larger temperature change in a short time in combustion process may generate metastable phase, to improve alternate bond strength.
Description
Technical field
This application involves the preparation methods of composite material more particularly to a kind of solution combustion method to prepare CNT-Cu composite granules
Method.
Background technology
The excellent conduction of carbon nanotube, heat conduction and high specific strength, low-density and low thermal coefficient of expansion so that it not only exists
As the reinforcement of high molecular material, and all shows huge application as metal-base composites reinforcement aspect and dive
Power.However, comparing polymer, carbon nanotube and metal wetability are poor, almost inconsistent, and there are carbon nanotube hardly possiblies for composite material
With evenly dispersed, interface cohesion is poor etc., therefore how problems take effective preparation method and process means to realize carbon nanotube
It evenly dispersed in Copper substrate and improve its interface bond strength and becomes the research of carbon nanotube reinforced copper-base composite material
Direction.
In order to prepare high performance carbon nanotube reinforced copper-base composite material, researchers have done a large amount of work.Mesh
The preceding method for preparing carbon nanotube reinforced copper-base composite material mainly have powder metallurgic method, molecular level be legal, metal injection at
Type method etc..Mechanical ball mill is main blending processes of powders in powder metallurgy process, is rotation or vibration using ball-milling medium, to original
Material carries out strong shock, grinding and stirring, to make each component be uniformly mixed.Research find material tensile strength and
Vickers hardness is greatly improved, but it is only the 75% of fine copper that the conductivity of material, which declines larger, and in this high energy
Under mechanical force long duration of action, the structure of carbon nanotube is often destroyed.Using the method for chemical nickel plating to carbon nanotube
It has carried out surface to be modified to reduce its apparent activation energy, has improved its compatibility with metal.Although this method can change well
The boundary moisture of kind carbon nanotube and Copper substrate, but plating nickel preprocessing technology is complicated, nickel plating technology parameter is unstable, it is difficult to
Nano level one-dimensional carbon pipe surface obtains the coating with certain thickness stable and uniform, it is difficult to industrialization.Molecular level mixes
The carbon nanotube of functionalization is mixed with mantoquita, makes copper absorption to the official of carbon nano tube surface by method in the solution
Oxide that is upper and being converted into copper in situ under the action of reducing agent can be rolled into a ball to restore again to obtain composite powder, but this clock method
It is more complicated, and it is larger that caustic soda sodium hydroxide environmental pollution is added in preparation process, it is also difficult to it completely removes, it is difficult to scale
Metaplasia is produced.
The deficiency cumbersome, with high costs for CNTs/Cu composite preparation process, Wang Cirong use powder smelting
Gold injection molding method prepares composite material and is explored to preparation process.But this method is in the mistake of sintering degreasing
Carbon nanotube is easy to reunite again in journey, and agglomerated material is difficult to densification.These difficulties greatly restrict carbon nanotube enhancing
The research and development of metal-base composites.Therefore new complex technique route is researched and developed just to be of great significance.
Invention content
(1) technical problems to be solved
The technical problem to be solved by the present invention is to be difficult to the compound problem of scale for existing carbon nanotube and metal, carry
Go out a kind of method that CNT-Cu composite granules are prepared by solution combustion method, porous flake prepared by solution combustion method aoxidizes sub-
Copper is mixed to prepare composite powder with carbon nanotube, and the evenly dispersed of carbon nanotube is realized under the booster action of electrostatic,
Preparation process is greatlied simplify, prepare with scale is suitble to.
(2) technical solution
This application provides a kind of methods that solution combustion method prepares CNT-Cu composite granules, which is characterized in that including with
Lower step：
(1) copper nitrate, the carbon nanotube of functionalization, sucrose and deionized water are mixed into ultrasonic agitation 25-35min, made
Each component is uniformly mixed, and obtains mixed solution；
(2) mixed solution in step (1) is poured into corundum crucible to heat, solution is through moisture evaporation, boiling, bubble
After-combustion obtains presoma composite powder；
(3) use the precursor powder that the reducing process in aqueous solution powder mixing method obtains solution combustion in step (2) into
Row reduction obtains carbon nanotube copper composite powder.
In some embodiments of the present application, the carbon nanotube of copper nitrate, functionalization in the step (1), sucrose
Component ratio is 33.20-33.88：0-0.2：8；Surplus is deionized water.
In some embodiments of the present application, the heating temperature of corundum crucible is 1350-1800 DEG C in the step (2).
In some embodiments of the present application, the heating time of corundum crucible is 30-65min in the step (2).
In some embodiments of the present application, the reduction chemical formula in the step (3) is Cu (NO3) 23H2O+ (5
Ψ/12) C6H12O6+2.5 (Ψ -1) O2=CuO+ (5 Ψ/2) CO2+ (Ψ/2 3+5) H2O+N2.
In some embodiments of the present application, the copper nitrate occurs displacement with silver nitrate solution by copper and reacts obtained,
Chemical formula is：Cu+2AgNO3=2Ag+Cu (NO3) 2.
In some embodiments of the present application, time of the solution through moisture evaporation is 15-35min in the step (2).
In some embodiments of the present application, environment temperature of the solution through moisture evaporation is 20-35 in the step (2)
℃。
In some embodiments of the present application, carbon nanotube copper composite powder is in porous laminated structure in the step (3).
In some embodiments of the present application, copper nitrate in the step (1), the carbon nanotube of functionalization, sucrose and
Deionized water mixing ultrasonic agitation 30min.
(3) advantageous effect
It can be seen from the above technical proposal that the application at least has the advantages that one of them：
(1) method that solution combustion method provided by the present application prepares CNT-Cu composite granules, method and process is simple, and reaction is fast
Speed, efficient, at low cost, product purity is high, and each component can reach the uniform mixing on molecular level, and material in combustion process
Material undergoes larger temperature change in a short time may generate metastable phase, to improve alternate bond strength.
(2) method that solution combustion method provided by the present application prepares CNT-Cu composite granules, combustion process generate a large amount of gas
Body, when effusion, necessarily leave a large amount of stomata, and product mostly porous structure in the form of sheets has higher specific surface, activity
Also higher.
(3) method that solution combustion method provided by the present application prepares CNT-Cu composite granules, is prepared using solution combustion method
Copper oxide powder be in porous laminated structure, this unique structure maintains the seperated high specific surface area of nanometer, at the same
Higher accessible area is showed in plane.
(4) method that solution combustion method provided by the present application prepares CNT-Cu composite granules, copper oxide powder is water-soluble
Positively charged micelle can be formed in liquid, encounter electronegative carbon nanotube and will produce electrostatic and attract each other, formed and be evenly distributed
Composite granule, carbon nanotube and network-like state, at low cost, product purity is high.
Description of the drawings
Fig. 1 is the flow diagram for the method that the application solution combustion method prepares CNT-Cu composite granules.
Fig. 2 be the application solution combustion method prepare in the methods of CNT-Cu composite granules carbon nanotube in specific embodiment 1/
Technique effect figure after copper composite powder burning.
Fig. 3 is that the application solution combustion method prepares carbon nano tube/copper in the method specific embodiments 1 of CNT-Cu composite granules
Technique effect figure after composite powder reduction.
Specific implementation mode
This application provides a kind of methods that solution combustion method prepares CNT-Cu composite granules, and method and process is simple, reaction
Quickly, efficient, at low cost, product purity is high, and each component can reach the uniform mixing on molecular level.
To make the purpose, technical scheme and advantage of the application be more clearly understood, below in conjunction with specific embodiment, and reference
The application is further described in attached drawing.
In an exemplary embodiment of the disclosure, provides a kind of solution combustion method and prepare CNT-Cu composite granules
Method is individually below described in detail each component part of the present embodiment：
Specific embodiment 1：
As shown in Figure 1, this application provides a kind of method that solution combustion method prepares CNT-Cu composite granules, a kind of solution
The method that combustion method prepares CNT-Cu composite granules, which is characterized in that include the following steps：
(1) copper nitrate, the carbon nanotube of functionalization, sucrose and deionized water are mixed into ultrasonic agitation 25min, makes each group
Divide and be uniformly mixed, obtains mixed solution；
(2) mixed solution in step (1) is poured into corundum crucible to heat, solution is through moisture evaporation, boiling, bubble
After-combustion obtains presoma composite powder；
(3) use the precursor powder that the reducing process in aqueous solution powder mixing method obtains solution combustion in step (2) into
Row reduction obtains carbon nanotube copper composite powder.Present invention process principle is to utilize nitrate (oxidant) and organic matter (reducing agent)
The exothermic characteristic that mixture has, the spontaneous generation redox reaction of energy under certain external temperature induced conditions, finally
Obtain required product.Simple for process, rapid reaction is efficient, at low cost, and product purity is high, and each component can reach molecular level
On uniform mixing, and material undergoes larger temperature change and may generate metastable phase in a short time in combustion process, from
And improve alternate bond strength.In addition, combustion process generates bulk gas, a large amount of stomata is necessarily left when escaping,
Product mostly porous structure in the form of sheets has higher specific surface, activity also higher.
Fig. 2 is the SEM shapes that the application solution combustion method prepares composite granule after burning in the methods of CNT-Cu composite granules
Looks.As shown in Fig. 2, the presence of carbon nanotube can be observed in the powder after burning using this method, illustrate that it is fired in high temperature
It is not burned off during burning.It oxygen that the bulk gas for being primarily due to generate in combustion process has completely cut off in air and takes away
A large amount of heat makes the product after burning cool down rapidly.Further looking at Fig. 2 can find, carbon nano tube surface has been adsorbed largely
Particle is not kept completely separate both after reduction.
Fig. 3 is the SEM that the application solution combustion method prepares the composite granule after reduction in the methods of CNT-Cu composite granules
Pattern.As shown in figure 3, the functional group of carbon nano tube surface produces chemical reaction with copper ion during combustion reaction,
Substantially increase its bond strength.But due to the unique one-dimensional nano structure of carbon nanotube and larger draw ratio, hold very much
Easily it is intertwined, it is difficult to single to scatter, Fig. 2 also demonstrates that this point, carbon nanotube are mutually wound three-dimensional network,
Grain is inlayed wherein and is combined together with carbon nanotube.
Further, the copper nitrate in the step (1), the carbon nanotube of functionalization, the component ratio of sucrose are 33.20：
0：8；Surplus is deionized water.
Further, the heating temperature of corundum crucible is 1350 DEG C in the step (2).
Further, the heating time of corundum crucible is 30min in the step (2).
Further, for the step (3) during solution combustion, organic matter sucrose is as reduction combustion adjuvant, nitrate anion
Ion carries out the redox exothermic reaction of self- propagating as oxidant, and reaction is carried out by following chemical equation：Cu
(NO3) 23H2O+ (5 Ψ/12) C6H12O6+2.5 (Ψ -1) O2=CuO+ (5 Ψ/2) CO2+ (Ψ/2 3+5) H2O+N2；
In above-mentioned reaction equation, as Ψ=2, it may appear that fuel-rich situation, when fuel-rich, a large amount of heat is released in reaction
Amount, reaction process is acutely rapid, and ignition temperature can be relatively higher；This experiment is used as reduction combustion adjuvant using organic matter sucrose,
It can be reacted completely, and reaction process is fast, and impurity is few, and purity is high.
Further, the copper nitrate is occurred to replace to react and is made by copper with silver nitrate solution, and chemical formula is：Cu+
2AgNO3=2Ag+Cu (NO3) 2.
Further, time of the solution through moisture evaporation is 15min in the step (2).
Further, environment temperature of the solution through moisture evaporation is 20 DEG C in the step (2).
Further, carbon nanotube copper composite powder is in porous laminated structure in the step (3), and this unique structure is protected
The seperated high specific surface area of nanometer has been held, while having showed higher accessible area in the plane.And this Cu oxide
Powder can form positively charged micelle in aqueous solution, encounter electronegative carbon nanotube and will produce electrostatic and attract each other, and be formed
The composite granule being evenly distributed, carbon nanotube and network-like state.The composite granule can be used as powder raw material to prepare high-performance
Cu-base composites and face coat.
CNT-Cu composite granules made from the method for CNT-Cu composite granules are prepared by a kind of solution combustion method of the application
Test performance contrast table be shown in Table 1.
Specific embodiment 2：
As shown in Figure 1, this application provides a kind of method that solution combustion method prepares CNT-Cu composite granules, a kind of solution
The method that combustion method prepares CNT-Cu composite granules, which is characterized in that include the following steps：
(1) copper nitrate, the carbon nanotube of functionalization, sucrose and deionized water are mixed into ultrasonic agitation 30min, makes each group
Divide and be uniformly mixed, obtains mixed solution；
(2) mixed solution in step (1) is poured into corundum crucible to heat, solution is through moisture evaporation, boiling, bubble
After-combustion obtains presoma composite powder；
(3) use the precursor powder that the reducing process in aqueous solution powder mixing method obtains solution combustion in step (2) into
Row reduction obtains carbon nanotube copper composite powder.Present invention process principle is to utilize nitrate (oxidant) and organic matter (reducing agent)
The exothermic characteristic that mixture has, the spontaneous generation redox reaction of energy under certain external temperature induced conditions, finally
Obtain required product.Simple for process, rapid reaction is efficient, at low cost, and product purity is high, and each component can reach molecular level
On uniform mixing, and material undergoes larger temperature change and may generate metastable phase in a short time in combustion process, from
And improve alternate bond strength.In addition, combustion process generates bulk gas, a large amount of stomata is necessarily left when escaping,
Product mostly porous structure in the form of sheets has higher specific surface, activity also higher.
Fig. 2 is the SEM shapes that the application solution combustion method prepares composite granule after burning in the methods of CNT-Cu composite granules
Looks.As shown in Fig. 2, the presence of carbon nanotube can be observed in the powder after burning using this method, illustrate that it is fired in high temperature
It is not burned off during burning.It oxygen that the bulk gas for being primarily due to generate in combustion process has completely cut off in air and takes away
A large amount of heat makes the product after burning cool down rapidly.Further looking at Fig. 2 can find, carbon nano tube surface has been adsorbed largely
Particle is not kept completely separate both after reduction.
Fig. 3 is the SEM that the application solution combustion method prepares the composite granule after reduction in the methods of CNT-Cu composite granules
Pattern.As shown in figure 3, the functional group of carbon nano tube surface produces chemical reaction with copper ion during combustion reaction,
Substantially increase its bond strength.But due to the unique one-dimensional nano structure of carbon nanotube and larger draw ratio, hold very much
Easily it is intertwined, it is difficult to single to scatter, Fig. 2 also demonstrates that this point, carbon nanotube are mutually wound three-dimensional network,
Grain is inlayed wherein and is combined together with carbon nanotube.
Further, the copper nitrate in the step (1), the carbon nanotube of functionalization, the component ratio of sucrose are 33.88：
0.2：8；Surplus is deionized water.
Further, the heating temperature of corundum crucible is 1800 DEG C in the step (2).
Further, the heating time of corundum crucible is 65min in the step (2).
Further, for the step (3) during solution combustion, organic matter sucrose is as reduction combustion adjuvant, nitrate anion
Ion carries out the redox exothermic reaction of self- propagating as oxidant, and reaction is carried out by following chemical equation：Cu
(NO3) 23H2O+ (5 Ψ/12) C6H12O6+2.5 (Ψ -1) O2=CuO+ (5 Ψ/2) CO2+ (Ψ/2 3+5) H2O+N2；
In above-mentioned reaction equation, the amount of Ψ=0.5, lean combustion, organic matter is too low, and reaction is released total heat and subtracted relatively
Few, reaction process is slow, and reaction temperature is relatively low, and impurity cannot volatilize effusion completely, product purity decline.When organic matter contains
When measuring too low, combustion reaction can be caused to be difficult into enforcement the failure of an experiment.
Further, the copper nitrate is occurred to replace to react and is made by copper with silver nitrate solution, and chemical formula is：Cu+
2AgNO3=2Ag+Cu (NO3) 2.
Further, time of the solution through moisture evaporation is 35min in the step (2).
Further, environment temperature of the solution through moisture evaporation is 35 DEG C in the step (2).
Further, carbon nanotube copper composite powder is in porous laminated structure in the step (3), and this unique structure is protected
The seperated high specific surface area of nanometer has been held, while having showed higher accessible area in the plane.And this Cu oxide
Powder can form positively charged micelle in aqueous solution, encounter electronegative carbon nanotube and will produce electrostatic and attract each other, and be formed
The composite granule being evenly distributed, carbon nanotube and network-like state.The composite granule can be used as powder raw material to prepare high-performance
Cu-base composites and face coat.
CNT-Cu composite granules made from the method for CNT-Cu composite granules are prepared by a kind of solution combustion method of the application
Test performance contrast table be shown in Table 1.
Specific embodiment 3：
As shown in Figure 1, this application provides a kind of method that solution combustion method prepares CNT-Cu composite granules, a kind of solution
The method that combustion method prepares CNT-Cu composite granules, which is characterized in that include the following steps：
(1) copper nitrate, the carbon nanotube of functionalization, sucrose and deionized water are mixed into ultrasonic agitation 35min, makes each group
Divide and be uniformly mixed, obtains mixed solution；
(2) mixed solution in step (1) is poured into corundum crucible to heat, solution is through moisture evaporation, boiling, bubble
After-combustion obtains presoma composite powder；
(3) use the precursor powder that the reducing process in aqueous solution powder mixing method obtains solution combustion in step (2) into
Row reduction obtains carbon nanotube copper composite powder.Present invention process principle is to utilize nitrate (oxidant) and organic matter (reducing agent)
The exothermic characteristic that mixture has, the spontaneous generation redox reaction of energy under certain external temperature induced conditions, finally
Obtain required product.Simple for process, rapid reaction is efficient, at low cost, and product purity is high, and each component can reach molecular level
On uniform mixing, and material undergoes larger temperature change and may generate metastable phase in a short time in combustion process, from
And improve alternate bond strength.In addition, combustion process generates bulk gas, a large amount of stomata is necessarily left when escaping,
Product mostly porous structure in the form of sheets has higher specific surface, activity also higher.
Fig. 2 is the SEM shapes that the application solution combustion method prepares composite granule after burning in the methods of CNT-Cu composite granules
Looks.As shown in Fig. 2, the presence of carbon nanotube can be observed in the powder after burning using this method, illustrate that it is fired in high temperature
It is not burned off during burning.It oxygen that the bulk gas for being primarily due to generate in combustion process has completely cut off in air and takes away
A large amount of heat makes the product after burning cool down rapidly.Further looking at Fig. 2 can find, carbon nano tube surface has been adsorbed largely
Particle is not kept completely separate both after reduction.
Fig. 3 is the SEM that the application solution combustion method prepares the composite granule after reduction in the methods of CNT-Cu composite granules
Pattern.As shown in figure 3, the functional group of carbon nano tube surface produces chemical reaction with copper ion during combustion reaction,
Substantially increase its bond strength.But due to the unique one-dimensional nano structure of carbon nanotube and larger draw ratio, hold very much
Easily it is intertwined, it is difficult to single to scatter, Fig. 2 also demonstrates that this point, carbon nanotube are mutually wound three-dimensional network,
Grain is inlayed wherein and is combined together with carbon nanotube.
Further, the copper nitrate in the step (1), the carbon nanotube of functionalization, the component ratio of sucrose are 33.20-
33.88：0-0.2：8；Surplus is deionized water.
Further, the heating temperature of corundum crucible is 1600 DEG C in the step (2).
Further, the heating time of corundum crucible is 52min in the step (2).
Further, for the step (3) during solution combustion, organic matter sucrose is as reduction combustion adjuvant, nitrate anion
Ion carries out the redox exothermic reaction of self- propagating as oxidant, and reaction is carried out by following chemical equation：Cu
(NO3) 23H2O+ (5 Ψ/12) C6H12O6+2.5 (Ψ -1) O2=CuO+ (5 Ψ/2) CO2+ (Ψ/2 3+5) H2O+N2；
In above-mentioned reaction equation, Ψ=5, in above-mentioned reaction equation, when fuel-rich, a large amount of heat is released in reaction,
Reaction process is acutely rapid, and ignition temperature can be relatively higher；This experiment is used as reduction combustion adjuvant using organic matter sucrose, can
Reaction completely, reaction process is fast, and impurity is few, and purity is high.Further, the copper nitrate is replaced by copper and silver nitrate solution
Reaction is made, and chemical formula is：Cu+2AgNO3=2Ag+Cu (NO3) 2.
Further, time of the solution through moisture evaporation is 23min in the step (2).
Further, environment temperature of the solution through moisture evaporation is 25 DEG C in the step (2).
Further, carbon nanotube copper composite powder is in porous laminated structure in the step (3), and this unique structure is protected
The seperated high specific surface area of nanometer has been held, while having showed higher accessible area in the plane.And this Cu oxide
Powder can form positively charged micelle in aqueous solution, encounter electronegative carbon nanotube and will produce electrostatic and attract each other, and be formed
The composite granule being evenly distributed, carbon nanotube and network-like state.The composite granule can be used as powder raw material to prepare high-performance
Cu-base composites and face coat.
CNT-Cu composite granules made from the method for CNT-Cu composite granules are prepared by a kind of solution combustion method of the application
Test performance contrast table be shown in Table 1.
Table 1
| Test performance | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Conductivity IACS% | 91 | 93.5 | 92 |
| Vickers hardness (HV) | 51 | 58 | 53 |
Table 1 as it can be seen that using CNT-Cu composite granules made of the application, indices conform to current standards and want
It asks, simple for process, rapid reaction is efficient, at low cost, and product purity is high, and each component can reach uniform mixed on molecular level
It closes, and material undergoes larger temperature change and may generate metastable phase in a short time in combustion process, alternate combination is strong
Degree effectively improves.
So far, attached drawing is had been combined the present embodiment is described in detail.According to above description, those skilled in the art
There should be clear understanding to the application.
It should be noted that in attached drawing or specification text, the realization method for not being painted or describing is affiliated technology
Form known to a person of ordinary skill in the art, is not described in detail in field.In addition, the above-mentioned definition to each element and method is simultaneously
It is not limited only to various concrete structures, shape or the mode mentioned in embodiment.
It should also be noted that, the demonstration of the parameter comprising particular value can be provided herein, but these parameters are without definite etc.
In corresponding value, but analog value can be similar in acceptable error margin or design constraint.The side mentioned in embodiment
Only it is the direction of refer to the attached drawing to term, such as "upper", "lower", "front", "rear", "left", "right" etc., is not used for limiting this
The protection domain of application.In addition, unless specifically described or the step of must sequentially occur, the sequences of above-mentioned steps there is no restriction in
It is listed above, and can change or rearrange according to required design.And above-described embodiment can be based on design and reliability
Consider, the collocation that is mixed with each other is used using or with other embodiment mix and match, i.e., the technical characteristic in different embodiments can be with
Freely form more embodiments.
Particular embodiments described above has carried out further in detail the purpose, technical solution and advantageous effect of the application
It describes in detail bright, it should be understood that the foregoing is merely the specific embodiment of the application, is not intended to limit this application, it is all
Within spirit herein and principle, any modification, equivalent substitution, improvement and etc. done should be included in the guarantor of the application
Within the scope of shield.
Claims (10)
1. a kind of method that solution combustion method prepares CNT-Cu composite granules, which is characterized in that include the following steps：
(1) copper nitrate, the carbon nanotube of functionalization, sucrose and deionized water are mixed into ultrasonic agitation 25-35min, makes each group
Divide and be uniformly mixed, obtains mixed solution；
(2) mixed solution in step (1) is poured into corundum crucible to heat, solution is through moisture evaporation, boiling, bubble after-burning
Burning obtains presoma composite powder；
(3) precursor powder for using the reducing process in aqueous solution powder mixing method to obtain solution combustion in step (2) is gone back
Original obtains carbon nanotube copper composite powder.
2. the method that solution combustion method according to claim 1 prepares CNT-Cu composite granules, which is characterized in that the step
Suddenly the copper nitrate in (1), the carbon nanotube of functionalization, the component ratio of sucrose are 33.20-33.88：0-0.2：8；Surplus be go from
Sub- water.
3. the method that solution combustion method according to claim 1 prepares CNT-Cu composite granules, which is characterized in that the step
Suddenly the heating temperature of corundum crucible is 1350-1800 DEG C in (2).
4. the method that solution combustion method according to claim 1 prepares CNT-Cu composite granules, which is characterized in that the step
Suddenly the heating time of corundum crucible is 30-65min in (2).
5. the method that solution combustion method according to claim 1 prepares CNT-Cu composite granules, which is characterized in that the step
Suddenly the reduction chemical formula in (3) is Cu (NO3) 23H2O+ (5 Ψ/12) C6H12O6+2.5 (Ψ -1) O2=CuO+ (5 Ψ/2)
CO2+(3+5Ψ/2)H2O+N2。
6. the method that solution combustion method according to claim 1 prepares CNT-Cu composite granules, which is characterized in that the nitre
Sour copper occurs displacement with silver nitrate solution by copper and reacts obtained, and chemical formula is：Cu+2AgNO3=2Ag+Cu (NO3) 2.
7. the method that solution combustion method according to claim 1 prepares CNT-Cu composite granules, which is characterized in that the step
Suddenly time of the solution through moisture evaporation is 15-35min in (2).
8. the method that solution combustion method according to claim 1 prepares CNT-Cu composite granules, which is characterized in that the step
Suddenly environment temperature of the solution through moisture evaporation is 20-35 DEG C in (2).
9. the method that solution combustion method according to claim 1 prepares CNT-Cu composite granules, which is characterized in that the step
Suddenly carbon nanotube copper composite powder is in porous laminated structure in (3).
10. the method that solution combustion method according to claim 1 prepares CNT-Cu composite granules, which is characterized in that described
Copper nitrate, the carbon nanotube of functionalization, sucrose and deionized water mixing ultrasonic agitation 30min in step (1).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110306167A (en) * | 2019-06-06 | 2019-10-08 | 沈阳航空航天大学 | A method for in-situ growth of CNT layer to enhance the strength of light alloy bonding interface |
| CN113426995A (en) * | 2021-06-07 | 2021-09-24 | 西湖大学 | Combustible 3D direct writing ink and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056321A (en) * | 2005-08-25 | 2007-03-08 | Tokai Rubber Ind Ltd | Copper ultrafine particle production method and conductive paste |
| CN101029147A (en) * | 2007-03-05 | 2007-09-05 | 四川大学 | Metal compound/carbon nano-composite material and its production |
| CN101757927A (en) * | 2010-01-07 | 2010-06-30 | 深圳大学 | Carbon film-coated Cu-Bi/CNT composite powder and preparation method thereof |
| CN103506119A (en) * | 2013-09-26 | 2014-01-15 | 太原理工大学 | Method for rapidly preparing carbon nanotube-loaded cuprous oxide photocatalyst |
| CN105645375A (en) * | 2015-12-17 | 2016-06-08 | 天津工业大学 | Method for direct growth of porous carbon nanotubes on nano-porous copper |
| CN107454815A (en) * | 2017-06-09 | 2017-12-08 | 安徽理工大学 | Cu2O/MWCNTs composites, preparation method and electro-magnetic wave absorption application |
-
2018
- 2018-05-30 CN CN201810541795.5A patent/CN108746653A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007056321A (en) * | 2005-08-25 | 2007-03-08 | Tokai Rubber Ind Ltd | Copper ultrafine particle production method and conductive paste |
| CN101029147A (en) * | 2007-03-05 | 2007-09-05 | 四川大学 | Metal compound/carbon nano-composite material and its production |
| CN101757927A (en) * | 2010-01-07 | 2010-06-30 | 深圳大学 | Carbon film-coated Cu-Bi/CNT composite powder and preparation method thereof |
| CN103506119A (en) * | 2013-09-26 | 2014-01-15 | 太原理工大学 | Method for rapidly preparing carbon nanotube-loaded cuprous oxide photocatalyst |
| CN105645375A (en) * | 2015-12-17 | 2016-06-08 | 天津工业大学 | Method for direct growth of porous carbon nanotubes on nano-porous copper |
| CN107454815A (en) * | 2017-06-09 | 2017-12-08 | 安徽理工大学 | Cu2O/MWCNTs composites, preparation method and electro-magnetic wave absorption application |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110306167A (en) * | 2019-06-06 | 2019-10-08 | 沈阳航空航天大学 | A method for in-situ growth of CNT layer to enhance the strength of light alloy bonding interface |
| CN110306167B (en) * | 2019-06-06 | 2021-06-04 | 沈阳航空航天大学 | A method for in-situ growth of CNT layer to enhance the strength of light alloy bonding interface |
| CN113426995A (en) * | 2021-06-07 | 2021-09-24 | 西湖大学 | Combustible 3D direct writing ink and preparation method and application thereof |
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