CN106270500B - A kind of carbon nano tube surface uniformly coats the method and device of metallic silver - Google Patents
A kind of carbon nano tube surface uniformly coats the method and device of metallic silver Download PDFInfo
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- CN106270500B CN106270500B CN201610868742.5A CN201610868742A CN106270500B CN 106270500 B CN106270500 B CN 106270500B CN 201610868742 A CN201610868742 A CN 201610868742A CN 106270500 B CN106270500 B CN 106270500B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1619—Apparatus for electroless plating
- C23C18/1632—Features specific for the apparatus, e.g. layout of cells and of its equipment, multiple cells
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- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1619—Apparatus for electroless plating
- C23C18/1628—Specific elements or parts of the apparatus
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
- C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
- C23C18/1886—Multistep pretreatment
- C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
Abstract
The present invention discloses the method and device that a kind of carbon nano tube surface uniformly coats metallic silver, first carry out carbon nanotube pretreatment, and prepare silver ammino solution and chemical plating solution, chemical plating is carried out using the device that the present invention uses, the device includes vacuum pump, receiving flask, quartz ampoule, ultrasonic atomizer, Microwave-assisted firing device, anti-microwave leakage device, carrier gas conveying device, two kinds of solution are subjected to ultrasonic atomizatio respectively, and two kinds of aerosols is made to contact with each other the raw reaction of hybrid concurrency, gained powder is washed repeatedly to neutrality, the carbon nanotube of coated with uniform metallic silver is obtained after drying；The present invention disperses carbon nanotube in spray droplet, improve carbon nanotube and silver-plated dispersibility, solution selfdecomposition phenomenon, the generation of bulky grain monomer silver and the generation of silver mirror reaction in conventional chemical electroplating method are avoided, prepared coating is uniform, and Argent grain size is in nanoscale；Integrated artistic is simple, and device is easy, and easy to operate, energy conservation and environmental protection can be realized volume production.
Description
Technical field
The invention discloses the method and devices that a kind of carbon nano tube surface uniformly coats metallic silver, belong to carbon nanotube
The silver-plated technical field of method.
Background technique
Carbon nanotube has caused people's extensive concern, carbon nanotube major diameter with higher since being found within 1991
It is fibrous material most thin at present, it has been showed than (diameter is within tens nanometers, and length is several microns and arrives several hundred microns)
Excellent mechanical property and unique electric property out.Carbon nanotube is coated with different substances, can be obtained another kind of
One-dimensional material, experiment show single 1.8 TPa of multilayer carbon nanotube young modulus average out to, show superpower mechanical property,
Bending strength reaches 14.2Gpa, shows superpower toughness, therefore carbon nanotube will have huge prospect in field of compound material.
In carbon nano tube surface plating metal, the further wetability and interface cohesion improved with matrix can be conducive to
The performances such as electric conductivity, corrosion stability, hardness, lubricity are improved, a kind of improved conductive material is can be used as, is also used as resistance to
Erosion, wear-resistant coating, thermal boundary and seal coating, microwave absorbing material etc..
Metallics is coated in carbon nanotube outer surface, will make to form continuous high-intensitive knot between carbon nanotube and Metal Substrate
It closes, overcomes carbon nanotube and the very poor disadvantage of metallic matrix associativity, this is to prepare superpower composite material not using carbon nanotube
The key link that can lack, because many metals can be transferred through chemical plating method and be deposited on nearly all substrate after treatment
On, therefore can use chemical plating method enveloped carbon nanometer tube, and so far, chemistry of the people to micron-sized particle or fiber
Plating has carried out more research, some technologies are mature, however, the chemical plating research for nano-scale particle but carries out
It obtains seldom, for carbon nanotube, surface curvature is big, and difficulties in dispersion, technical requirements are higher, the graphitization knot of height
Structure is difficult to obtain the preferable coating of continuity compactness, in the process of traditional chemical plating so that surface reaction activity is very low
In, carbon nanotube itself is difficult to evenly dispersed, and metal is also difficult uniformly to be plated on its surface, and anti-due to what is occurred in solution
There should be spatial non-uniformity, part metals particle is excessively grown up in the solution, cannot be according to the coating carbon nanotubes of anticipation.
It is following several from having known to document for the main solution of these problems: 1) that dispersion is added in chemical plating fluid
Agent can reduce relatively the generation of agglomeration traits in this way, but will affect the silver and the binding force of carbon nanotube of chemical plating.2)
The method combined using stirring and ultrasonic vibration, but be typically now that ultrasonic vibration device is placed in except container, concussion
Effect greatly weaken.3) solve to react too fast plating problem of non-uniform using the instillation speed for slowing down solution, but due to
In reaction solution, there are excessive concentration gradients, therefore instilling speed by control merely is to be difficult to solve problem above.
Summary of the invention
Of the existing technology in order to overcome the problems, such as, the purpose of the present invention is to provide a kind of carbon nano tube surfaces uniformly to wrap
The method of metallic silver is covered, specifically includes the following steps:
(1) pretreatment of carbon nanotube
The pretreatment that carbon nanotube is successively acidified, is sensitized and is activated, by pretreated carbon nanotube according to matter
It measures volume ratio 1:200g/mL to be added in dispersing agent, ultrasonic treatment obtains carbon nano tube suspension；
(2) preparation of silver ammino solution
Ammonium hydroxide to the suspension that mass fraction is 25% is added in the suspension that concentration is 15g/L-20g/L silver nitrate to clarify,
The NaOH solution for being again 5mol/L with concentration obtains main salt solution A after adjusting pH value to 10-11；
(3) preparation of chemical plating solution
By reducing agent and deionized water, 1:3-1:5 is mixed to get mixed solution B by volume, and the main salt of step (2) is molten
After the 3:1-5:1 mixing by volume of the carbon nano tube suspension of liquid A and step (1), ultrasonic vibration, which is uniformly mixed, obtains suspension
C；After the 3:1-5:1 mixing by volume of the carbon nano tube suspension of mixed solution B and step (1), shaken in ultrasonic instrument
It is uniformly mixed and obtains suspension D；
(4) chemical silvering of carbon nanotube
Choose main salt solution A and suspension D combination, mixed solution B and suspension C in combination, suspension C and suspension D group
It closes, one of these three combinations carry out subsequent chemistry plating reaction, and two kinds of solution in the combination of selection are carried out ultrasound respectively
Atomization, and two kinds of aerosols is made to contact with each other the raw reaction of hybrid concurrency, reaction process using microwave heating to 60-80 DEG C, gained
Powder washs repeatedly in deionized water to neutrality, obtains the carbon nanotube of coated with uniform metallic silver after dry.
Step (1) acidification is the ratio according to 1.5:100g/mL-3:100g/mL, and carbon nanotube is added in nitration mixture
Obtained mixture is again heated to 70 DEG C of reflux 3h, is then diluted and washed to neutrality with deionized water, the carbon nanometer that will be obtained
Pipe separation, the carbon nanotube after being acidified after dry, wherein nitration mixture is the concentrated sulfuric acid and mass fraction by mass fraction 98%
3:1 is mixed 65% concentrated nitric acid by volume.
Step (1) sensitization is the carbon nanotube after acidification to be added quick according to 1:100g/mL-2:100g/mL
Change after being ultrasonically treated in liquid, is diluted and washed to neutrality with deionized water, the carbon nanotube separation that will be obtained, 60 DEG C of dryings are for 24 hours
Carbon nanotube after being sensitized afterwards, wherein sensitizing solution by the deionized water of 100mL, mass fraction 37% concentrated hydrochloric acid 3.5mL,
1.9g SnCl2It is configured to.
Step (1) activation is that the carbon nanotube after sensitized treatment is added and lives according to 1:100g/mL-2:100g/mL
Change in liquid and be ultrasonically treated 30min-60min, diluted and washed to neutrality with deionized water, the carbon nanotube separation that will be obtained is done
Carbon nanotube after being activated after dry, wherein activating solution is by the deionized water of 100mL, the concentrated hydrochloric acid of mass fraction 37%
1.7mL、0.09g PdCl2It is configured to.
Dispersing agent described in step (1) is the mixture that dehydrated alcohol and water are mixed according to volume ratio 1:1.
Reducing agent described in step (3) be hydrazine hydrate, formaldehyde, D-glucose, sodium potassium tartrate tetrahydrate, hydrazine sulfate, ethylenediamine,
Glyoxal, sodium borohydride, aldolactol, triethanolamine, glycerine, tannic acid or Mitouer.
Step (4) described drying is dried for 24 hours at 50-60 DEG C.
Another object of the present invention is to provide the sides that the step (4) described carbon nano tube surface uniformly coats metallic silver
The device that device used in method, i.e. step (4) chemical plating is used, including vacuum pump 1, receiving flask 2, quartz ampoule 4, ultrasonic atomizatio
Device, Microwave-assisted firing device 7, anti-microwave leakage device 5, carrier gas conveying device 6, Microwave-assisted firing device 7 are wrapped in quartz ampoule 4
Outside, anti-microwave leakage device 5 is wrapped in 7 outside of Microwave-assisted firing device and 4 both ends of quartz ampoule, quartz ampoule 4 pass through anti-microwave
Leakage device 5, one end are connect with more than two ultrasonic atomizers and carrier gas conveying device 8 respectively, the other end and receiving flask 2
Connection, receiving flask 2 are also connect with vacuum pump 1, and the powder that completion is reacted in quartz ampoule 4 is extracted into receiving flask 2 by vacuum pump 1.
The carrier gas conveying device 6 is air blower, and anti-microwave leakage device 5 is metal-back, such as steel plate shell.
4 both ends of quartz ampoule are equipped with end cap 3, and end cap 3 is equipped with connecting hole or quartz ampoule 4 and is blocked by glass cement,
Connecting hole is left when closure, and the connection of two end devices is realized by connecting hole.
The purity of carbon nanotube of the present invention is 95-99.9%.
The present invention compared with prior art possessed by advantage and positive effect:
(1) experiment flow of the present invention is simple, and securely and reliably, equipment is simple, it is easy to accomplish serialization preparation.
(2) of the invention is that ultrasonic atomization technique can be such that the drop of reaction controls in 1-10 micron level, carbon nanometer
Pipe is sprayed with atomized drop, greatly improves the dispersibility of carbon nanotube.
(3) the method for the present invention has by the contact between drop, the raw reaction of hybrid concurrency, the volume and concentration of the drop of formation
Limit, thus can avoid the formation of incident solution selfdecomposition, silver mirror reaction and bulky grain silver simple substance in conventional chemical plating method
And so on.
(4) the opposite of two kinds of mist bodies is atomized and sprays into that speed is adjustable, and reaction process may be selected to apply microwave field in the present invention
To promote the progress of reaction, the regulation of electroless plating reaction speed, the grain size of easily controllable silver coating are realized.
Detailed description of the invention
Fig. 1 is the ullrasonic spraying chemical plating appts schematic diagram that the present invention uses；
Fig. 2 is schematic diagram at the ullrasonic spraying chemical plating appts quartz pipe end-cap of the invention used
Fig. 3 is the TEM figure of the carbon nanotube for the uniform cladding metallic silver that the embodiment of the present invention 1 obtains；
Fig. 4 is the XRD diagram of the carbon nanotube for the uniform cladding metallic silver that the embodiment of the present invention 1 obtains；
Fig. 5 is the TEM figure of the carbon nanotube for the uniform cladding metallic silver that the embodiment of the present invention 2 obtains；
Fig. 6 is the TEM figure of the carbon nanotube for the uniform cladding metallic silver that the embodiment of the present invention 3 obtains；
Fig. 7 is the TEM figure of the carbon nanotube for the uniform cladding metallic silver that the embodiment of the present invention 5 obtains；
In figure, 1- vacuum pump, 2- receiving flask, 3- end cap, 4- quartz ampoule, 5- microwave leakage prevention device, 6- carrier gas conveying dress
It sets, 7- Microwave-assisted firing device, 8- ultrasonic atomizer I, 9- ultrasonic atomizer II.
Specific embodiment
The present invention is described in further details with reference to the accompanying drawing, but protection scope of the present invention is not limited in
This.
Embodiment 1
The method that carbon nano tube surface of the present invention uniformly coats metallic silver, specifically includes the following steps:
The pretreatment of step 1) carbon nanotube
(1) acidification of carbon nanotube: by carbon nanotube be added nitration mixture in, nitration mixture by mass fraction 98% the concentrated sulfuric acid
Concentrated nitric acid 3:1 mixing by volume with mass fraction 65% is made into, and the additional amount of carbon nanotube is to add in the nitration mixture of every 100mL
Enter 1.5g carbon nanotube, 3h be then heated to reflux in 70 DEG C of water-bath, then diluted with deionized water and washs to neutrality,
The carbon nanotube separation that will be obtained, the carbon nanotube after being acidified after dry；
(2) ultrasound 30min in sensitizing solution sensitized treatment: is added according to 1:100g/mL in the carbon nanotube after acidification
It after processing, is diluted and is washed to neutrality with deionized water, the carbon nanotube separation that will be obtained, 60 DEG C of dryings are sensitized afterwards for 24 hours
Carbon nanotube afterwards, wherein sensitizing solution is concentrated hydrochloric acid 3.5mL, 1.9g SnCl of the deionized water of 100mL, mass fraction 37%2
It is mixed to get；
(3) it is activated: ultrasound 30min in activating solution is added according to 1:100g/mL in the carbon nanotube after sensitized treatment
After processing, is diluted and washed to neutrality with deionized water, the carbon nanotube separation that will be obtained, after the completion of obtaining pretreatment after dry
Carbon nanotube, wherein activating solution is concentrated hydrochloric acid 1.7mL, 0.09g PdCl of the deionization of 100mL, mass fraction 37%2Mixing
It obtains；
Carbon nanotube 1g after activation processing is added in the dispersing agent of 200mL, is ultrasonically treated 60min, obtains carbon nanometer
Pipe suspension, wherein dispersing agent is dehydrated alcohol and the mixture that deionized water is mixed according to volume ratio 1:1；
The preparation of step 2 silver ammino solution
Ammonium hydroxide to the silver nitrate that mass fraction is 25% is added in the silver nitrate suspension that 100mL concentration is 15g/L to suspend
Liquid clarification, then the NaOH solution for being 5mol/L with concentration adjust pH value to obtaining main salt solution A after 10；
The preparation of step 3) chemical plating solution
By reducing agent formaldehyde and deionized water, 1:3 is mixed to get mixed solution B by volume, by mixed solution B and step
(1) it after the 4:1 mixing by volume of carbon nano tube suspension, is shaken in ultrasonic instrument and is uniformly mixed acquisition suspension D；
The chemical plating of step 4) carbon nanotube
The device that chemical plating adopted in this step is used, as shown in Figure 1, 2, including vacuum pump 1, receiving flask 2, end cap 3,
Quartz ampoule 4, microwave leakage prevention device 5, carrier gas conveying device 6, Microwave-assisted firing device 7, ultrasonic atomizer I 8, ultrasonic atomizer
II 9, Microwave-assisted firing device 7 is wrapped in outside quartz ampoule 4, and anti-microwave leakage device 5 is wrapped in outside Microwave-assisted firing device 7
And 4 both ends of quartz ampoule, 4 both ends of quartz ampoule pass through anti-microwave leakage device 5,4 both ends of quartz ampoule are equipped with end cap 3, and end cap 3 is equipped with
Connecting hole, the end cap 3 of 4 one end of quartz ampoule are connect with ultrasonic atomizer I 8, ultrasonic atomizer II 9 and carrier gas conveying device 6 respectively,
The end cap 3 of the other end is connect with receiving flask 2, and receiving flask 2 is also connect with vacuum pump 1, and vacuum pump 1 will react in quartz ampoule 4 to be completed
Powder be extracted into receiving flask 2, anti-microwave leakage device 7 be metal foil shell；
Main salt solution A and suspension D are added in ultrasonic atomizer I 8 and ultrasonic atomizer II 9 respectively, energization is surpassed
Atomized drop is sent into quartz ampoule 4 using carrier gas conveying device air blower 6 using air as carrier gas, is sprayed into maximum by sound atomization
Condensation rate is greater than 3 ml/mins, uses Microwave-assisted firing device 7 to control the temperature in quartz ampoule 4 as 60 DEG C, passes through vacuum pump 1
Powder extraction after reaction is collected into receiving flask 2, the powder of collection is washed with deionized water to after neutrality repeatedly, in temperature
Degree for 24 hours, obtains the carbon nanotube of coated with uniform metallic silver for drying in 60 DEG C of baking ovens.
Fig. 3 is the TEM figure of the carbon nanotube for the coated with uniform metallic silver that the present embodiment obtains, and as seen from the figure, carbon is received
The silver coating of mitron is mainly the surface that carbon nanotube is wrapped in silver-colored cluster and graininess, and the silver reunited occur in few places
Grain；Fig. 4 is the XRD diffracting spectrum of the carbon nanotube of the obtained coated with uniform metallic silver of the present embodiment, it is seen that carbon nanometer
The strong peak of master of XRD diffracting spectrum after pipe chemical silvering is corresponding with the base peak map of silver of FCC, illustrates carbon nanotube
Learn the silver-colored crystal that silver-plated silver coating is FCC.
Embodiment 2
The method that carbon nano tube surface of the present invention uniformly coats metallic silver, specifically includes the following steps:
The pretreatment of step 1) carbon nanotube
(1) acidification of carbon nanotube: by carbon nanotube be added nitration mixture in, nitration mixture by mass fraction 98% the concentrated sulfuric acid
Concentrated nitric acid 3:1 mixing by volume with mass fraction 65% is made into, and the additional amount of carbon nanotube is to add in the nitration mixture of every 100mL
Enter 2g carbon nanotube, 3h is then heated to reflux in 70 DEG C of water-bath, then diluted with deionized water and washs to neutrality, it will
Obtained carbon nanotube separation, the carbon nanotube after being acidified after dry；
(2) ultrasound 30min in sensitizing solution sensitized treatment: is added according to 2:100g/mL in the carbon nanotube after acidification
It after processing, is diluted and is washed to neutrality with deionized water, the carbon nanotube separation that will be obtained, 60 DEG C of dryings are sensitized afterwards for 24 hours
Carbon nanotube afterwards, wherein sensitizing solution is concentrated hydrochloric acid 3.5mL, 1.9g SnCl of the deionized water of 100mL, mass fraction 37%2
It is mixed to get；
(3) it is activated: ultrasound 30min in activating solution is added according to 2:100g/mL in the carbon nanotube after sensitized treatment
After processing, is diluted and washed to neutrality with deionized water, the carbon nanotube separation that will be obtained, after the completion of obtaining pretreatment after dry
Carbon nanotube, wherein activating solution is concentrated hydrochloric acid 1.7mL, 0.09g PdCl of the deionization of 100mL, mass fraction 37%2Mixing
It obtains；
Carbon nanotube 1g after activation processing is added in the dispersing agent of 200mL, is ultrasonically treated 60min, obtains carbon nanometer
Pipe suspension, wherein dispersing agent is dehydrated alcohol and the mixture that deionized water is mixed according to volume ratio 1:1；
The preparation of step 2 silver ammino solution
Ammonium hydroxide to the silver nitrate that mass fraction is 25% is added in the silver nitrate suspension that 100mL concentration is 20g/L to suspend
Liquid clarification, then the NaOH solution for being 5mol/L with concentration adjust pH value to obtaining main salt solution A after 11；
The preparation of step 3) chemical plating solution
By reducing agent hydrazine hydrate and deionized water, 1:4 is mixed to get mixed solution B by volume, by the main salt of step (2)
After the 3:1 mixing by volume of the carbon nano tube suspension of solution A and step (1), ultrasonic vibration, which is uniformly mixed, obtains suspension C；
The chemical plating of step 4) carbon nanotube
The device that chemical plating adopted in this step is used is same as Example 1, and only quartz ampoule 4 is ground, both ends
It is blocked using glass cement, there are connecting holes on glass cement, and mixed solution B and suspension C are added to I 8 He of ultrasonic atomizer respectively
It in ultrasonic atomizer II 9, is powered and carries out ultrasonic atomizatio, will be atomized using carrier gas conveying device air blower 6 using air as carrier gas
Drop is sent into quartz ampoule 4, is sprayed into maximum condensation rate and is greater than 3 ml/mins, controls quartz ampoule 4 using Microwave-assisted firing device 7
Interior temperature is 70 DEG C, and the powder extraction after reaction is collected into receiving flask 2 by vacuum pump 1, the powder of collection is spent
Ionized water is washed repeatedly to after neutrality, is that for 24 hours, the carbon for obtaining coated with uniform metallic silver is received for drying in 60 DEG C of baking ovens in temperature
Mitron.
Fig. 5 is the carbon nanotube TEM figure that the embodiment of the present invention 2 obtains coated with uniform metallic silver, and as seen from the figure, carbon is received
The silver coating of mitron is mainly the surface that carbon nanotube is wrapped in the silver-colored shape of particle；Carbon nanotube chemical plating known to XRD analysis
The strong peak of master of XRD diffracting spectrum after silver is corresponding with the base peak map of silver of FCC, illustrates that carbon nanotube chemical is silver-plated
Silver coating is the silver-colored crystal of FCC.
Embodiment 3
The method that carbon nano tube surface of the present invention uniformly coats metallic silver, specifically includes the following steps:
The pretreatment of step 1) carbon nanotube
(1) acidification of carbon nanotube: by carbon nanotube be added nitration mixture in, nitration mixture by mass fraction 98% the concentrated sulfuric acid
Concentrated nitric acid 3:1 mixing by volume with mass fraction 65% is made into, and the additional amount of carbon nanotube is to add in the nitration mixture of every 100mL
Enter 3g carbon nanotube, 3h is then heated to reflux in 70 DEG C of water-bath, then diluted with deionized water and washs to neutrality, it will
Obtained carbon nanotube separation, the carbon nanotube after being acidified after dry；
(2) ultrasound in sensitizing solution sensitized treatment: is added according to 1.5:100g/mL in the carbon nanotube after acidification
After 30min processing, is diluted and washed to neutrality with deionized water, the carbon nanotube separation that will be obtained, 60 DEG C of dryings obtain afterwards for 24 hours
Carbon nanotube after sensitization, wherein sensitizing solution is concentrated hydrochloric acid 3.5mL, 1.9g of the deionized water of 100mL, mass fraction 37%
SnCl2It is mixed to get；
(3) it is activated: ultrasound 60min in activating solution is added according to 2:100g/mL in the carbon nanotube after sensitized treatment
After processing, is diluted and washed to neutrality with deionized water, the carbon nanotube separation that will be obtained, after the completion of obtaining pretreatment after dry
Carbon nanotube, wherein activating solution is concentrated hydrochloric acid 1.7mL, 0.09g PdCl of the deionization of 100mL, mass fraction 37%2Mixing
It obtains；
Carbon nanotube 1g after activation processing is added in the dispersing agent of 200mL, is ultrasonically treated 60min, obtains carbon nanometer
Pipe suspension, wherein dispersing agent is dehydrated alcohol and the mixture that deionized water is mixed according to volume ratio 1:1；
The preparation of step 2 silver ammino solution
Ammonium hydroxide to the silver nitrate that mass fraction is 25% is added in the silver nitrate suspension that 100mL concentration is 18g/L to suspend
Liquid clarification, then the NaOH solution for being 5mol/L with concentration adjust pH value to obtaining main salt solution A after 10；
The preparation of step 3) chemical plating solution
By reducing agent sodium borohydride and deionized water, 1:5 is mixed to get mixed solution B by volume, by the master of step (2)
After the 4:1 mixing by volume of the carbon nano tube suspension of salting liquid A and step (1), ultrasonic vibration, which is uniformly mixed, obtains suspension
C；After the 5:1 mixing by volume of the carbon nano tube suspension of mixed solution B and step (1), mixing is shaken in ultrasonic instrument
Uniformly obtain suspension D；
The chemical plating of step 4) carbon nanotube
The device that chemical plating adopted in this step is used is same as Example 1, respectively adds suspension C and suspension D
Into ultrasonic atomizer I 8 and ultrasonic atomizer II 9, it is powered and carries out ultrasonic atomizatio, it will be empty using carrier gas conveying device air blower 6
Atomized drop is sent into quartz ampoule 4 by gas as carrier gas, is sprayed into maximum condensation rate and is greater than 3 ml/mins, is added using microwave-assisted
It is 80 DEG C that hot device 7, which controls the temperature in quartz ampoule 4, and the powder extraction after reaction is collected into receiving flask 2 by vacuum pump 1,
The powder of collection is washed with deionized water to after neutrality repeatedly, is that drying for 24 hours, it is uniform to obtain surface in 55 DEG C of baking ovens in temperature
Coat the carbon nanotube of metallic silver.
Fig. 6 is the carbon nanotube TEM figure for the coated with uniform metallic silver that the embodiment of the present invention 3 obtains, as seen from the figure, carbon
The silver coating of nanotube is mainly the surface that granular silver is wrapped in carbon nanotube, and the silver of macro aggregate occur in some places
Grain.XRD analysis result is identical with embodiment 1.
Embodiment 4
The method that carbon nano tube surface of the present invention uniformly coats metallic silver, specifically includes the following steps:
The pretreatment of step 1) carbon nanotube
(1) acidification of carbon nanotube: by carbon nanotube be added nitration mixture in, nitration mixture by mass fraction 98% the concentrated sulfuric acid
Concentrated nitric acid 3:1 mixing by volume with mass fraction 65% is made into, and the additional amount of carbon nanotube is to add in the nitration mixture of every 100mL
Enter 3g carbon nanotube, 3h is then heated to reflux in 70 DEG C of water-bath, then diluted with deionized water and washs to neutrality, it will
Obtained carbon nanotube separation, the carbon nanotube after being acidified after dry；
(2) ultrasound in sensitizing solution sensitized treatment: is added according to 1.5:100g/mL in the carbon nanotube after acidification
After 30min processing, is diluted and washed to neutrality with deionized water, the carbon nanotube separation that will be obtained, 60 DEG C of dryings obtain afterwards for 24 hours
Carbon nanotube after sensitization, wherein sensitizing solution is concentrated hydrochloric acid 3.5mL, 1.9g of the deionized water of 100mL, mass fraction 37%
SnCl2It is mixed to get；
(3) it is activated: ultrasound 50min in activating solution is added according to 2:100g/mL in the carbon nanotube after sensitized treatment
After processing, is diluted and washed to neutrality with deionized water, the carbon nanotube separation that will be obtained, after the completion of obtaining pretreatment after dry
Carbon nanotube, wherein activating solution is concentrated hydrochloric acid 1.7mL, 0.09g PdCl of the deionization of 100mL, mass fraction 37%2Mixing
It obtains；
Carbon nanotube 1g after activation processing is added in the dispersing agent of 200mL, is ultrasonically treated 60min, obtains carbon nanometer
Pipe suspension, wherein dispersing agent is dehydrated alcohol and the mixture that deionized water is mixed according to volume ratio 1:1；
The preparation of step 2 silver ammino solution
Ammonium hydroxide to the silver nitrate that mass fraction is 25% is added in the silver nitrate suspension that 100mL concentration is 20g/L to suspend
Liquid clarification, then the NaOH solution for being 5mol/L with concentration adjust pH value to obtaining main salt solution A after 10；
The preparation of step 3) chemical plating solution
By reducing agent tannic acid and deionized water, 1:4 is mixed to get mixed solution B by volume, and the main salt of step (2) is molten
After the 5:1 mixing by volume of the carbon nano tube suspension of liquid A and step (1), ultrasonic vibration, which is uniformly mixed, obtains suspension C；
The chemical plating of step 4) carbon nanotube
The device that chemical plating adopted in this step is used is same as Example 1, respectively by mixed solution B and suspension C
It is added in ultrasonic atomizer I 8 and ultrasonic atomizer II 9, is powered and carries out ultrasonic atomizatio, it will using carrier gas conveying device air blower 6
Atomized drop is sent into quartz ampoule 4 by air as carrier gas, is sprayed into maximum condensation rate and is greater than 3 ml/mins, use is microwave-assisted
It is 70 DEG C that heater 7, which controls the temperature in quartz ampoule 4, and the powder extraction after reaction is collected into receiving flask 2 by vacuum pump 1
In, the powder of collection is washed with deionized water to after neutrality repeatedly, is that drying for 24 hours, obtains surface in 50 DEG C of baking ovens in temperature
The uniformly carbon nanotube of cladding metallic silver.
Fig. 7 is the TEM figure of the carbon nanotube for the coated with uniform metallic silver that the embodiment of the present invention 4 obtains, as seen from the figure,
The silver coating of carbon nanotube is mainly the surface that granular silver is wrapped in carbon nanotube, a small number of Argent grains reunited occurs；XRD
It is identical with embodiment 1 to analyze result.
Embodiment 5
The method that carbon nano tube surface of the present invention uniformly coats metallic silver, specifically includes the following steps:
The pretreatment of step 1) carbon nanotube
(1) acidification of carbon nanotube: by carbon nanotube be added nitration mixture in, nitration mixture by mass fraction 98% the concentrated sulfuric acid
Concentrated nitric acid 3:1 mixing by volume with mass fraction 65% is made into, and the additional amount of carbon nanotube is to add in the nitration mixture of every 100mL
Enter 2.5g carbon nanotube, 3h be then heated to reflux in 70 DEG C of water-bath, then diluted with deionized water and washs to neutrality,
The carbon nanotube separation that will be obtained, the carbon nanotube after being acidified after dry；
(2) ultrasound 30min in sensitizing solution sensitized treatment: is added according to 2:100g/mL in the carbon nanotube after acidification
It after processing, is diluted and is washed to neutrality with deionized water, the carbon nanotube separation that will be obtained, 60 DEG C of dryings are sensitized afterwards for 24 hours
Carbon nanotube afterwards, wherein sensitizing solution is concentrated hydrochloric acid 3.5mL, 1.9g SnCl of the deionized water of 100mL, mass fraction 37%2
It is mixed to get；
(3) it is activated: ultrasound in activating solution is added according to 1.5:100g/mL in the carbon nanotube after sensitized treatment
It after 30min processing, is diluted and is washed to neutrality with deionized water, the carbon nanotube separation that will be obtained is pre-processed after dry
Carbon nanotube after the completion, wherein activating solution is concentrated hydrochloric acid 1.7mL, 0.09g of the deionization of 100mL, mass fraction 37%
PdCl2It is mixed to get；
Carbon nanotube 1g after activation processing is added in the dispersing agent of 200mL, is ultrasonically treated 60min, obtains carbon nanometer
Pipe suspension, wherein dispersing agent is dehydrated alcohol and the mixture that deionized water is mixed according to volume ratio 1:1；
The preparation of step 2 silver ammino solution
Ammonium hydroxide to the silver nitrate that mass fraction is 25% is added in the silver nitrate suspension that 100mL concentration is 20g/L to suspend
Liquid clarification, then the NaOH solution for being 5mol/L with concentration adjust pH value to obtaining main salt solution A after 10；
The preparation of step 3) chemical plating solution
By reducing agent sodium potassium tartrate tetrahydrate and deionized water, 1:5 is mixed to get mixed solution B by volume, by step (2)
After the 3:1 mixing by volume of the carbon nano tube suspension of main salt solution A and step (1), ultrasonic vibration is uniformly mixed and is suspended
Liquid C；After the 3:1 mixing by volume of the carbon nano tube suspension of mixed solution B and step (1), shaken in ultrasonic instrument mixed
It closes and uniformly obtains suspension D；
The chemical plating of step 4) carbon nanotube
The device that chemical plating adopted in this step is used is same as Example 2, respectively adds suspension C and suspension D
Into ultrasonic atomizer I 8 and ultrasonic atomizer II 9, it is powered and carries out ultrasonic atomizatio, it will be empty using carrier gas conveying device air blower 6
Atomized drop is sent into quartz ampoule 4 by gas as carrier gas, is sprayed into maximum condensation rate and is greater than 3 ml/mins, is added using microwave-assisted
It is 60 DEG C that hot device 7, which controls the temperature in quartz ampoule 4, and the powder extraction after reaction is collected into receiving flask 2 by vacuum pump 1,
The powder of collection is washed with deionized water to after neutrality repeatedly, is that drying for 24 hours, it is uniform to obtain surface in 60 DEG C of baking ovens in temperature
Coat the carbon nanotube of metallic silver.
The TEM of the carbon nanotube for the coated with uniform metallic silver that the present embodiment 5 obtains schemes, as seen from the figure, carbon nanotube
Silver coating be mainly that the surface of carbon nanotube is wrapped in silver-colored cluster and granular silver, there is the silver reunited in few places
Grain；XRD analysis result is identical with embodiment 1.
Embodiment described above is only several embodiments of the invention, and the description thereof is more specific and detailed, but can not
Therefore limitations on the scope of the patent of the present invention are interpreted as, it is noted that for those of ordinary skill in the art,
Without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection model of the invention
It encloses.
Claims (9)
1. a kind of method that carbon nano tube surface uniformly coats metallic silver, which is characterized in that specifically includes the following steps:
(1) pretreatment of carbon nanotube
The pretreatment that carbon nanotube is successively acidified, is sensitized and is activated, by pretreated carbon nanotube according to mass body
Product is added in dispersing agent than 1:200g/mL, and ultrasonic treatment obtains carbon nano tube suspension；The acidification is according to 1.5:100g/
Carbon nanotube is added mixture obtained in nitration mixture, is again heated to 70 DEG C of reflux 3h, then uses by the ratio of mL-3:100g/mL
Deionized water is diluted and is washed to neutrality, the carbon nanotube separation that will be obtained, the carbon nanotube after being acidified after dry, wherein
Nitration mixture is by the concentrated nitric acid 3:1 mixing by volume of the concentrated sulfuric acid and mass fraction 65% of mass fraction 98%；
(2) preparation of silver ammino solution
The ammonium hydroxide that mass fraction is 25% is added in the suspension that concentration is 15g/L-20g/L silver nitrate extremely to clarify, then is with concentration
The NaOH solution of 5mol/L obtains main salt solution A after adjusting pH value to 10-11；
(3) preparation of chemical plating solution
By reducing agent and deionized water, 1:3-1:5 is mixed to get mixed solution B by volume, by the main salt solution A of step (2) and
After the 3:1-5:1 mixing by volume of the carbon nano tube suspension of step (1), ultrasonic vibration, which is uniformly mixed, obtains suspension C；It will mix
After the carbon nano tube suspension 3:1-5:1 mixing by volume for closing solution B and step (1), concussion mixing is equal in ultrasonic instrument
Even acquisition suspension D；
(4) chemical plating of carbon nanotube
Main salt solution A and suspension D combination, mixed solution B and suspension C in combination, suspension C and suspension D combination are chosen, this
One of three kinds of combinations carry out subsequent chemistry plating reaction, and two kinds of solution in the combination of selection are carried out ultrasonic atomizatio respectively,
And two kinds of aerosols is made to contact with each other the raw reaction of hybrid concurrency, using microwave heating to 60-80 DEG C, gained powder exists reaction process
It is washed repeatedly in deionized water to neutrality, obtains the carbon nanotube of coated with uniform metallic silver after dry.
2. the method that carbon nano tube surface uniformly coats metallic silver according to claim 1, which is characterized in that step (1) institute
Stating sensitization is the ratio according to 1:100g/mL-2:100g/mL, and ultrasound in sensitizing solution is added in the carbon nanotube after acidification
It after processing, is diluted and is washed to neutrality with deionized water, the carbon nanotube separation that will be obtained, 60 DEG C of dryings are sensitized afterwards for 24 hours
Carbon nanotube afterwards, wherein sensitizing solution is by the deionized water of 100mL, concentrated hydrochloric acid 3.5mL, 1.9g SnCl of mass fraction 37%2
It is configured to.
3. the method that carbon nano tube surface uniformly coats metallic silver according to claim 1, which is characterized in that step (1) institute
Stating activation is the ratio according to 1:100g/mL-2:100g/mL, and ultrasound in activating solution is added in the carbon nanotube after sensitized treatment
30min-60min is handled, is diluted and is washed to neutrality with deionized water, the carbon nanotube separation that will be obtained is lived after dry
Carbon nanotube after change, wherein activating solution is by the deionized water of 100mL, concentrated hydrochloric acid 1.7mL, 0.09g of mass fraction 37%
PdCl2It is configured to.
4. the method that carbon nano tube surface uniformly coats metallic silver according to claim 1, which is characterized in that the dispersion
Agent is the mixture that dehydrated alcohol and water are mixed according to volume ratio 1:1.
5. the method that carbon nano tube surface uniformly coats metallic silver according to claim 1, which is characterized in that step (3) institute
The reducing agent stated be hydrazine hydrate, formaldehyde, D-glucose, sodium potassium tartrate tetrahydrate, hydrazine sulfate, ethylenediamine, glyoxal, sodium borohydride,
Aldolactol, triethanolamine, glycerine, tannic acid or Mitouer.
6. the method that carbon nano tube surface uniformly coats metallic silver according to claim 1, which is characterized in that step (4) institute
Stating drying is dried for 24 hours at 50-60 DEG C.
7. the method that carbon nano tube surface uniformly coats metallic silver according to claim 1, which is characterized in that step (4) institute
State the device that chemical plating is used, including vacuum pump, receiving flask, quartz ampoule, ultrasonic atomizer, Microwave-assisted firing device, anti-microwave
Leakage device, carrier gas conveying device, Microwave-assisted firing device are wrapped in outside quartz ampoule, and anti-microwave leakage device is wrapped in microwave
Outside auxiliary heater and quartz ampoule both ends, quartz ampoule both ends pass through anti-microwave leakage device, one end respectively with two or more
Ultrasonic atomizer connected with carrier gas conveying device, the other end is connect with receiving flask, and receiving flask is also controlled to a vacuum pump.
8. the method that carbon nano tube surface uniformly coats metallic silver according to claim 7, which is characterized in that the carrier gas is defeated
Sending device is air blower, and anti-microwave leakage device is metal shell.
9. the method that carbon nano tube surface uniformly coats metallic silver according to claim 7, which is characterized in that the quartz ampoule
Both ends are equipped with end cap, and end cap is equipped with connecting hole or quartz ampoule by glass cement closure, and when closure leaves connecting hole.
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| CN112888287A (en) * | 2021-01-12 | 2021-06-01 | 无锡东恒新能源科技有限公司 | Preparation method of electromagnetic shielding material |
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