CN101633500A - Metal plating method for carbon nanotubes - Google Patents
Metal plating method for carbon nanotubes Download PDFInfo
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- CN101633500A CN101633500A CN200810021386A CN200810021386A CN101633500A CN 101633500 A CN101633500 A CN 101633500A CN 200810021386 A CN200810021386 A CN 200810021386A CN 200810021386 A CN200810021386 A CN 200810021386A CN 101633500 A CN101633500 A CN 101633500A
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- cnt
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- carbon nano
- metal plating
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Abstract
The invention discloses a metal plating method for carbon nanotubes. Mainly, the method adopts low-carbon-number alcohol solvents and surfactants having a functional group of thioalcohol or sulfonic acid and uses ultrasonic vibration to fully disperse the carbon nanotubes in electroless plating surface to completely coat a plating layer on the surfaces of the carbon nanotubes, thereby solving the problem of uneven plating layer distribution caused by the aggregation of carbon nanotubes in the prior art.
Description
[technical field]
System of the present invention is relevant with CNT (carbon nano-tube), especially means a kind of method of using the metal plating treatment agent to carry out metal plating in CNT (carbon nano-tube).
[background technology]
CNT (carbon nano-tube) (Carbon Nanotube; CNT) be Japanese NEC senior fellow Sumio Iijima (SumioIijima) professor when prepare C60 with arc discharge method 1991 Christian eras, the unexpected discovery during cluster of observing carbon with transmission electron microscope.According to different pattern of growth, the kenel of CNT (carbon nano-tube) generally is divided into the individual layer CNT (carbon nano-tube) that diameter is several nanometers, and diameter is the multi-layer nano carbon pipe of dozens of nanometer, and the two thickness of pipe is several nanometers only.According to the arrangement architecture difference of carbon atom in CNT (carbon nano-tube), can get the CNT (carbon nano-tube) of tool semi-conductor or conductor characteristics, it not only can be used at Field Emission Display for this, more can be applicable to aspects such as hydrogen storage material, biomedicine, transistor.In numerous technique of display, Field Emission Display (Field Emission Display; FED) being known as is the new technology of having an opportunity to replace LCD most.Similar traditional cathode tube (the Cathode-Ray Tube of the know-why of FED; CRT), therefore have less trigger voltage and higher current density; And emission principle is for utilizing the eletrode tip radius-of-curvature little, and electronics penetrates easily, and general electron beam gun also is to utilize this principle to get electronics; Therefore the principle of nano carbon pipe field-emission display is identical with electron beam gun, because CNT (carbon nano-tube) has less diameter, electronics is easier to be excited out, also so CNT (carbon nano-tube) (Carbon Nanotube; CNT) be a kind of material that has the good field emission characteristic in the equivalent material of present many emission.
For making its characteristic of CNT (carbon nano-tube) performance, in practical application, can utilize no electric metal method of coating to make the CNT (carbon nano-tube) surface plate a metal plating.And there is not the electric metal method of coating is form the metallic membrane method on the base material that does not have electroconductibility a kind of, general use be by be adhered in advance base material as catalyst rare metal (as: palladium) and activate relevant method, and do the pre-treatment that electroless plating is used.So far, the existing use a kind ofly makes Pd be adsorbed on method on the base material by handle the back the hydrochloric acid solution with SnCl2 by impregnated in the PdCl2 aqueous solution, or a kind ofly make Pd be supported on lip-deep method by the colloidal solution that contains Sn and Pd, but these methods have the problems such as treatment step of the required complexity of many use Sn.Therefore existing many at present methods that can form the silane coupling agent with functional group of misfit thing with these rare metals, as: Japan's special permission communique clear 59-52701 number, day disclosure special permission communique clear 60-181294 number, the content that day disclosure is speciallyyed permit clear 61-194183 number and Japan's special permission communique is disclosed for flat 3-44149 number, be and support use from the teeth outwards with precious metal (as: Pd) method as the catalyst of electroless plating, even the electroless plating method and the metal plating treatment agent thereof that can be applied to dusty material or specular material easily also arranged at present, disclose as Taiwan No. 438905 patents of bulletin.
But when utilizing aforementioned these no electric metal method of coating to make CNT (carbon nano-tube) plate metal plating, plate metal plating again after often CNT (carbon nano-tube) can't being uniformly dispersed individually, as Fig. 1 and shown in Figure 2, be exactly that CNT (carbon nano-tube) 10 is because of van der waals forces (van der Waals ' forces) and electrostatic force cause gathering to each other, so behind plated with nickel coating 20, the inabundant plated with nickel coating 20 in CNT (carbon nano-tube) 10 surfaces; So will be distributed to very even being not easy to CNT (carbon nano-tube) individually, so the technology of manufacturing of a lot of correlative study or practical application can be made in-and-out result, reproducibility is very unstable.
[summary of the invention]
Technical scheme to be solved by this invention provides the metal plating method that a kind of CNT (carbon nano-tube) is used the metal plating treatment agent, CNT (carbon nano-tube) is disperseed individually, and then make the abundant metal plating of body structure surface, improves CNT (carbon nano-tube) conduction transport property itself.
For addressing the above problem, the present invention can adopt following technical scheme: CNT (carbon nano-tube) is put into dispersion liquid and metal plating treatment agent in regular turn, or CNT (carbon nano-tube) put into the solution that metal plating treatment agent and dispersion liquid are arranged simultaneously, and utilize the ultrasound concussion to make the indivedual really dispersions of CNT (carbon nano-tube), carry out the CNT (carbon nano-tube) that electroless plating obtains this metal plating then, this dispersion liquid can be low carbon number alcohols solution.
Compared with prior art, the present invention has following beneficial effect: utilize the physics of CNT (carbon nano-tube) itself and unreactiveness good not can with the aitiogenic characteristic of other material, not only can make CNT (carbon nano-tube) when using the metal plating treatment agent at metal plating, what make can be uniformly dispersed, and can make the abundant metal plating of CNT (carbon nano-tube) body structure surface, solve coating problem pockety in the past, even use when Field Emission Display, can improve CNT (carbon nano-tube) originally under electric field action, have more very large field enhancement factor, make that electron beam is easier to be disengaged, and improve the magnitude of current density of emission.
The invention will be further described below in conjunction with graphic and embodiment.
[description of drawings]
To be known metal plating method be plated on synoptic diagram after the CNT (carbon nano-tube) with the nickel metal to Fig. 1;
Fig. 2 is the enlarged diagram after the nickel metal of Fig. 1 is plated on CNT (carbon nano-tube);
Fig. 3 is a schematic flow sheet of the present invention;
Fig. 4 is that the nickel metal of a preferred embodiment of the present invention is plated on the CNT (carbon nano-tube) synoptic diagram;
Fig. 5 is the enlarged diagram that the nickel metal of Fig. 4 is plated on CNT (carbon nano-tube).
[embodiment]
Please join Fig. 3 to shown in Figure 5, the metal plating method flow and the result of CNT (carbon nano-tube) of the present invention, wherein one embodiment of the present invention is to get the CNT (carbon nano-tube) 30 of suitable length earlier on utensil, CNT (carbon nano-tube) 30 is put into alcohol solution, take out after three seconds with the ultrasound concussion, ultrasound cleaned three seconds in the water, and the repeated washing step 3 is inferior.The composition of each the step chemical solution that is adopted in this embodiment and the operational condition of cooperation are as follows:
Operational condition:
(1) sodium hydroxide (NaOH), water (H
2O) with alcohols (C
nH
2n+1OH) mixing solutions (it is preferable to contain alcohol solution 5～30%), 80 ℃;
(2) sulfuric acid (H
2SO
4), water (H
2O) with alcohols (C
nH
2n+1OH) mixing solutions (it is preferable to contain alcohol solution 5～30%), room temperature;
(3) the palladium activated solution (contains Palladous chloride (PdCl
2), tin protochloride (SnCl
2), hydrochloric acid (HCl), water (H
2O) with alcohols (C
nH
2n+1OH) mixing solutions (it is preferable to contain alcohol solution 5～30%)), 30 ℃-45 ℃;
(4) single nickel salt (NiSO
4), trisodium phosphate (Na
4P
2O
7), sodium hypophosphite (NaH
2PO
2), the mixing solutions (it is preferable to contain alcohol solution 5%～30%) of water and alcohols, 50 ℃-60 ℃, pH10～11.
Step 1: the CNT (carbon nano-tube) that will clean is put into operational condition (one's) solution, carries out that ultrasound concussion continues after 10 seconds to soak and stir about after 3 minutes, the CNT (carbon nano-tube) water is cleaned and ultrasound concussion 5 seconds.
Step 2: then CNT (carbon nano-tube) is put into operational condition (twos') solution, carry out that ultrasound concussion continues after 10 seconds to soak and stir about after 1 minute, the CNT (carbon nano-tube) water is cleaned and ultrasound concussion 5 seconds.
Step 3: then CNT (carbon nano-tube) is put in regular turn operational condition (threes') solution, after carrying out ultrasound concussion respectively and continuing after 3 seconds to soak and stir approximate number minute, the CNT (carbon nano-tube) water cleaned and ultrasound concussion 5 seconds.
Step 4: the solution of at last CNT (carbon nano-tube) being put into operational condition (four), after carrying out ultrasound concussion and stirring a little simultaneously in 20 seconds, the CNT (carbon nano-tube) water is cleaned also ultrasound concussion 5 seconds, CNT (carbon nano-tube) is taken off oven dry promptly finish CNT (carbon nano-tube) 30 with nickel coating 40.
Above-mentioned by the solution of operational condition () to (four) and the use of metal plating treatment agent, and the metal plating method of utilization ultrasound concussion, not only can allow CNT (carbon nano-tube) 30 be uniformly dispersed, and make the abundant plated with nickel coating 40 of CNT (carbon nano-tube) 30 body structure surface tube walls, and then can improve CNT (carbon nano-tube) conduction transport property itself, solution causes coating problem pockety because of assembling between CNT (carbon nano-tube) in the past.
The metal plating method of the CNT (carbon nano-tube) of another embodiment of the present invention, the composition of each step and chemical solution and the operational condition that cooperates are as follows:
Operational condition:
(1) the palladium activated solution (contains Palladous chloride (PdCl
2), tin protochloride (SnCl
2), hydrochloric acid (HCl), water (H
2O) with alcohols (C
nH
2n+1OH) mixing solutions (containing alcohol solution 5%～30%)), 30 ℃-45 ℃ for best;
(2) single nickel salt (NiSO
4), trisodium phosphate (Na
4P
2O
7), sodium hypophosphite (NaH
2PO
2), the mixing solutions (containing alcohol solution 5%～30%) of water and alcohols for best, 50 ℃-60 ℃, pH10～11.
Step 1: CNT (carbon nano-tube) is cut into every section about 3～5mm, add an amount of nitric acid and vitriolic mixed solution (nitric acid: sulfuric acid=1: 3), with ultrasound concussion and be heated to 65 ℃～75 ℃ continue 90 minutes after, add the above water dilution of 4 times of amounts and filter again, with the CNT (carbon nano-tube) 30 collected again the water cleaning and filtering can obtain dispersive CNT (carbon nano-tube) 30 for several times.
Step 2: the CNT (carbon nano-tube) that will clean is put into operational condition (one's) solution in regular turn, carries out several minutes after-filtration of ultrasound concussion respectively, and water cleans CNT (carbon nano-tube) 30 several on the filter paper.
Step 3: the carbon pipe that will clean is put into operational condition (twos') solution, carries out 10 seconds after-filtration of ultrasound concussion, and water cleans the CNT (carbon nano-tube) back oven dry for several times on the filter paper, promptly finishes the CNT (carbon nano-tube) 30 with nickel coating 40.
The present invention not only can make CNT (carbon nano-tube) when using the metal plating treatment agent at metal plating, CNT (carbon nano-tube) can be uniformly dispersed, and can make the abundant coating of CNT (carbon nano-tube) body structure surface tube wall, solves coating problem of uneven distribution in the past.Certainly for the purpose of the present invention, the most important thing is various solution complexed metal coating treatment agents, and utilize the ultrasound concussion, impel CNT (carbon nano-tube) to disperse individually to use in each operational condition, in order to the enforcement of metal electroless plating method, and then obtain the CNT (carbon nano-tube) of this metal plating.The various solution that use in for example aforementioned each operational condition as alcohol solution, have the thiol-functional base interfacial agent, have sulfonic acid functional group's interfacial agent or have the thiol-functional base and the two interfacial agent that all has of sulfonic acid functional group (as: HS-(CH2) n-SO
3Na), this metal plating then is to carry out this electroless plating or use other metal plating treatment agent or the like with copper or nickel or gold, all belongs to scope of the present invention, does not repeat them here.
Claims (10)
1. the metal plating method of a CNT (carbon nano-tube), it comprises the following steps:
An amount of carbon nanotube is provided;
Aforementioned carbon nanotube is placed in dispersion liquid and the metal plating treatment agent, and utilizes the ultrasound concussion that carbon nanotube is uniformly dispersed individually;
Carry out electroless plating, obtain the carbon nanotube of this metal plating.
2. the metal plating method of CNT (carbon nano-tube) according to claim 1, wherein be to get carbon nanotube earlier to put into dispersion liquid, then together with carbon nanotube and dispersion liquid to shake in the ultrasound, after carbon nanotube being uniformly dispersed individually disperse, re-use the metal plating treatment agent and carry out electroless plating.
3. the metal plating method of CNT (carbon nano-tube) according to claim 1, it is characterized in that: earlier dispersion liquid is added the metal plating treatment agent, get the solution that an amount of CNT (carbon nano-tube) is put into metal plating treatment agent and dispersion liquid then, then utilizing the ultrasound concussion that CNT (carbon nano-tube) is uniformly dispersed individually again is scattered in the solution of metal plating treatment agent and dispersion liquid, carries out the CNT (carbon nano-tube) that electroless plating obtains this metal plating then.
4. as the metal plating method of CNT (carbon nano-tube) as described in the claim 1～3 any, it is characterized in that: dispersion liquid is an alcohol solution.
5. as the metal plating method of CNT (carbon nano-tube) as described in the claim 4, it is characterized in that: the molecular formula of dispersion liquid is C
nH
2n+1OH.
6. as the metal plating method of CNT (carbon nano-tube) as described in the claim 5, it is characterized in that: the n of molecular formula is less than 5.
7. as the metal plating method of CNT (carbon nano-tube) as described in the claim 1～3 any, it is characterized in that: the interfacial agent that has the thiol-functional base is a dispersion liquid.
8. as the metal plating method of CNT (carbon nano-tube) as described in the claim 1～3 any, it is characterized in that: the interfacial agent that has the sulfonic acid functional group is a dispersion liquid.
9. as the metal plating method of CNT (carbon nano-tube) as described in the claim 1～3 any, it is characterized in that: the interfacial agent that has thiol-functional base and sulfonic acid functional group is a dispersion liquid.
10. the metal plating method of using as CNT (carbon nano-tube) as described in the claim 9, it is characterized in that: sulfonic acid functional group's interfacial agent is HS-(CH2) n-SO
3Na.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810021386A CN101633500A (en) | 2008-07-21 | 2008-07-21 | Metal plating method for carbon nanotubes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810021386A CN101633500A (en) | 2008-07-21 | 2008-07-21 | Metal plating method for carbon nanotubes |
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|---|---|
| CN101633500A true CN101633500A (en) | 2010-01-27 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI547839B (en) * | 2014-04-23 | 2016-09-01 | 北京富納特創新科技有限公司 | Conductive mesh and touch panel using the same |
| US9570208B2 (en) | 2014-04-23 | 2017-02-14 | Beijing Funate Innovation Technology Co., Ltd. | Carbon nanotube composite wire |
| US9696335B2 (en) | 2014-04-23 | 2017-07-04 | Beijing Funate Innovation Technology Co., Ltd. | Hot wire anemometer having twisted carbon nanotube composite wire detecting element |
| US9702747B2 (en) | 2014-04-23 | 2017-07-11 | Beijing Funate Innovation Technology Co., Ltd. | Mass flowmeter having twisted carbon nanotube composite wire sensing elements |
| US9960141B2 (en) | 2014-04-23 | 2018-05-01 | Beijing Funate Innovation Technology Co., Ltd. | Binding wire and semiconductor package structure using the same |
| US10213857B2 (en) | 2014-04-23 | 2019-02-26 | Beijing Funate Innovation Technology Co., Ltd. | Wire cutting electrode and wire cutting device using the same |
| US10251219B2 (en) | 2014-04-23 | 2019-04-02 | Beijing Funate Innovation Technology Co., Ltd. | Defrosting glass, defrosting lamp and vehicle using the same |
-
2008
- 2008-07-21 CN CN200810021386A patent/CN101633500A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI547839B (en) * | 2014-04-23 | 2016-09-01 | 北京富納特創新科技有限公司 | Conductive mesh and touch panel using the same |
| US9570208B2 (en) | 2014-04-23 | 2017-02-14 | Beijing Funate Innovation Technology Co., Ltd. | Carbon nanotube composite wire |
| US9696335B2 (en) | 2014-04-23 | 2017-07-04 | Beijing Funate Innovation Technology Co., Ltd. | Hot wire anemometer having twisted carbon nanotube composite wire detecting element |
| US9702747B2 (en) | 2014-04-23 | 2017-07-11 | Beijing Funate Innovation Technology Co., Ltd. | Mass flowmeter having twisted carbon nanotube composite wire sensing elements |
| US9817435B2 (en) | 2014-04-23 | 2017-11-14 | Beijing Funate Innovation Technology Co., Ltd. | Conductive mesh and touch panel using the same |
| US9960141B2 (en) | 2014-04-23 | 2018-05-01 | Beijing Funate Innovation Technology Co., Ltd. | Binding wire and semiconductor package structure using the same |
| US10213857B2 (en) | 2014-04-23 | 2019-02-26 | Beijing Funate Innovation Technology Co., Ltd. | Wire cutting electrode and wire cutting device using the same |
| US10251219B2 (en) | 2014-04-23 | 2019-04-02 | Beijing Funate Innovation Technology Co., Ltd. | Defrosting glass, defrosting lamp and vehicle using the same |
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Open date: 20100127 |