CN110777331A - Preparation method of metal-coated carbon nano tube - Google Patents
Preparation method of metal-coated carbon nano tube Download PDFInfo
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- CN110777331A CN110777331A CN201911079240.4A CN201911079240A CN110777331A CN 110777331 A CN110777331 A CN 110777331A CN 201911079240 A CN201911079240 A CN 201911079240A CN 110777331 A CN110777331 A CN 110777331A
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- carbon nanotube
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
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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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
Abstract
A preparation method of a metal-coated carbon nanotube belongs to the technical field of nano materials. The preparation method of the metal-coated carbon nano tube comprises the following steps: s1, preparing the carbon nano tube into carbon nano tube paper with large aperture and large porosity; and S2, coating the metal simple substance on the carbon nanotube paper by adopting an evaporation process in an ultrahigh vacuum state or a cold sputtering process in a low vacuum state to obtain the metal-coated carbon nanotube paper with controllable ratio of nanoscale metal to carbon nanotubes and uniform composition. The invention improves the affinity of the carbon nano tube and the metal matrix, and is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to a technology in the field of nano materials, in particular to a preparation method of a metal-coated carbon nano tube.
Background
Carbon nanotubes have achieved a certain level of performance as reinforcing phases in composite materials such as Fe-based, Al-based, Cu-based, Mg-based, and Ni-based materials. However, due to strong van der waals force between the carbon nanotubes, the carbon nanotubes are very easy to agglomerate, and thus the carbon nanotubes are difficult to be uniformly dispersed in the composite material. As long as the carbon nanotubes are uniformly dispersed in the metal matrix and form effective interface bonding with the metal matrix by adopting a proper method, the carbon nanotubes can be used as a reinforcing phase to obviously improve the performance of the metal matrix composite.
Coating a metal coating on the surface of the carbon nanotube is an effective means for solving the above problems. For example, in the article "platinum deposition on carbon nanotubes" (for example, nobility, record, Mao Zong et al. science bulletin, 1999, 44(11): 1154-1157), "surface modification and nickel coating of carbon nanotubes" (for the easy army, Xiaohua, Jiangxing et al. Chinese non-ferrous metals bulletin, 2004, 14(3): 479-483), "research on coating carbon nanotubes with Ni-Co alloy" (Chenxiaohua, Yangyong, Zhang Gaoming et al. microfabrication technology, 1999, 2: 17-22), "chemical silver plating and SEM research on carbon nanotubes" (Chenxiaohua, Zhang Gao Ming, Li Mao et al. Hunan university of south university, 1999, 26(6): 14-18), etc., the acid treatment → activation of metals Sn and Pt and → sensitization chemical codeposition of carbon nanotubes are used, although different metal coatings are successfully coated on the surface of carbon nanotubes, but the used process is complicated, the price is high, and the toxic reagent is not environment-friendly, is not suitable for large-scale production and is difficult to industrialize when being commonly used; the article In situ chemical vapor deposition of metal on metal-grown carbon fibers and contamination of aluminum-matrix compounds recycled by coated fibers (Fumio Ogawa et al J Mater Sci, 2018, 53: 5036-5050) adopts an In situ chemical vapor deposition method to heat metal powder and iodine In a quartz tube to generate metal iodide vapor, and then annealing and depositing the metal iodide vapor to successfully deposit aluminum, nickel, silicon and titanium on the surface of VGCFs, however, the method is not only complicated In process, but also the equipment system is more complicated and expensive, and is not suitable for large-scale production.
The present invention has been made to solve the above-mentioned problems occurring in the prior art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of the metal-coated carbon nano tube, which improves the affinity of the carbon nano tube and a metal matrix and is suitable for large-scale industrial production.
The invention comprises the following steps:
s1, preparing the carbon nano tube into carbon nano tube paper with large aperture and large porosity;
s2, coating the carbon nanotube paper with a metal simple substance by adopting an evaporation process in an ultrahigh vacuum state or a cold sputtering process in a low vacuum state to obtain the metal-coated carbon nanotube paper with controllable ratio of nanoscale metal to carbon nanotubes and uniform composition.
In step S2, the evaporation process in the ultra-high vacuum state or the cold sputtering process in the low vacuum state is determined according to the melting point of the elemental metal to be coated.
Preferably, the thickness of the metal coating layer is 5-100 nm, and more preferably 20-50 nm.
Preferably, the carbon nanotube is at least one of a single-walled carbon nanotube and a multi-walled carbon nanotube, the diameter is 10-200 nm, and the length is 5-20 μm.
Preferably, the thickness of the carbon nanotube paper is 100-1000 μm, and more preferably 200-500 μm.
Preferably, the preparation method of the carbon nanotube paper comprises the following steps:
s11, mixing the carbon nano tube, the surfactant and the mixed solution of the deionized water and the alcohol, and uniformly stirring and dispersing to obtain carbon nano tube slurry;
s12, uniformly coating the carbon nanotube slurry prepared in the step S11 on the surface of the rough copper foil, and drying at 70-80 ℃;
and S13, tearing off the carbon nanotube film dried in the step S12 and rolling the carbon nanotube film into a carbon nanotube paper roll to obtain the carbon nanotube paper with large aperture and large porosity.
Preferably, the surfactant is a nonionic surfactant, and comprises at least one of PEG, PVP and PVA.
Preferably, the ratio of the deionized water to the alcohol is 1: 1-2.
Preferably, the metal-coated carbon nanotube paper can be used as a functional foil and also can be crushed to be used as functional powder; the pulverization method includes but is not limited to milling media type pulverization, ultramicro pulverization and air flow pulverization.
Technical effects
Compared with the prior art, the invention has the following technical effects:
1) the method is simple, efficient and environment-friendly, and can be used for producing the metal-coated carbon nanotube powder in a large scale to obtain the functional material with controllable M/C ratio and uniform composition of metal and carbon nanotubes in nano scale;
2) the nano metal layer uniformly coated on the surface of the carbon nano tube can effectively avoid the repulsion of metal crystal boundaries to the carbon nano tube, so that the carbon nano tube can easily enter metal when the metal-based composite material is prepared;
3) the method can greatly improve the affinity of the carbon nano tube and the metal matrix and can effectively solve the problem of uniform dispersion of the carbon nano tube in the metal matrix composite.
Drawings
FIG. 1 is an SEM photograph of a nano-silver coated carbon nanotube composite material prepared in example 1 of the present invention;
fig. 2 is an XRD spectrum of the nano-silver coated carbon nanotube composite material prepared in example 1 of the present invention.
Detailed Description
The invention is described in detail below with reference to the drawings and the detailed description.
Example 1
The embodiment relates to a preparation method of a metal-coated carbon nanotube, which comprises the following steps:
s1, preparing a powder by weight ratio of CNT: PEG: deionized water: uniformly mixing the raw materials with alcohol of 20:1:200:200, and stirring and dispersing to obtain carbon nanotube slurry; uniformly coating the obtained carbon nanotube slurry on the surface of a crude copper foil, drying at 70-80 ℃, tearing off a carbon nanotube film, and rolling into a carbon nanotube paper roll for later use;
s2, fixing the obtained carbon nano tube paper roll on a sample rack in a low-vacuum cold-state sputtering instrument, pre-installing 99.99% high-purity Ag targets in the sputtering instrument, rotating the sample rack at a constant speed of 1r/S, unreeling and winding at the same speed, sputtering with the power of 14W, and obtaining the carbon nano tube paper uniformly coated with nano silver after sputtering.
And (5) adding the carbon nano tube paper uniformly coated with the nano silver prepared in the step (S2) into a ball mill according to the ball-to-material ratio of 5:1 and the ratio of 3:4:3 of three zirconium balls, namely large, medium and small (20mm, 10mm and 5mm), performing low-energy ball milling, wherein the ball milling rotation speed is 200r/min, the ball milling time is 30min, and after the ball milling is finished, sieving through a 300-mesh sieve to collect materials, thus obtaining the nano silver coated carbon nano tube powder.
The prepared silver-coated carbon nanotube composite material was analyzed by a scanning electron microscope and an X-ray diffractometer, and the SEM image shown in fig. 1 and the XRD pattern shown in fig. 2 were obtained. It can be seen from fig. 1 that the nano silver is uniformly coated on the surface of the carbon nanotube. As can be seen from the XRD pattern of fig. 2, a diffraction peak of the carbon nanotube appears at 26.18 ° 2 Θ; characteristic diffraction peaks of silver appear at 38.12 degrees and 44.28 degrees of 2 theta, corresponding to diffraction surfaces (111) and (200), showing that the nano silver has a face-centered cubic structure, and the diffraction peaks are matched with an XRD standard card (JCPDS 04-0783) of Ag; no miscellaneous peak appears in the figure, which shows that the coated nano silver carbon nanotube composite material has higher purity. The grain size of the coated nano silver is calculated to be 20nm by DIFFAC.
Example 2
The embodiment relates to a preparation method of a metal-coated carbon nanotube, which comprises the following steps:
s1, preparing a powder by weight ratio of CNT: PVP: deionized water: uniformly mixing the raw materials with alcohol of 25:2:300:200, and stirring and dispersing to obtain carbon nanotube slurry; uniformly coating the obtained carbon nanotube slurry on the surface of a crude copper foil, drying at 70-80 ℃, tearing off a carbon nanotube film, and rolling into a carbon nanotube paper roll for later use;
s2, fixing the obtained carbon nanotube paper roll on a sample rack in a vacuum evaporation chamber, vacuumizing and simultaneously putting an aluminum ingot into a melting tank for melting, filtering molten aluminum and pumping into a crucible in the evaporation chamber, heating the crucible to evaporate metal aluminum at high temperature, unreeling and reeling the sample rack at a constant rate of 1r/S, and obtaining carbon nanotube paper uniformly coated with nano aluminum after evaporation.
For the carbon nanotube paper uniformly coated with nano aluminum prepared in the step S2, the ratio of the balls to the materials is 3: 1, adding three zirconium balls (20mm, 10mm and 5mm) of large, medium and small zirconium balls in a ratio of 3:4:3 into a ball mill, carrying out low-energy ball milling at a ball milling rotation speed of 200r/min for 50min, and sieving with a 300-mesh sieve after ball milling is finished to collect materials, thereby obtaining the nano-aluminum coated carbon nanotube powder.
It is to be emphasized that: the above embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiments according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (8)
1. A preparation method of a metal-coated carbon nanotube is characterized by comprising the following steps:
s1, preparing the carbon nano tube into carbon nano tube paper with large aperture and large porosity;
s2, coating the carbon nanotube paper with a metal simple substance by adopting an evaporation process in an ultrahigh vacuum state or a cold sputtering process in a low vacuum state to obtain the metal-coated carbon nanotube paper with controllable ratio of nanoscale metal to carbon nanotubes and uniform composition.
2. The method of claim 1, wherein in step S2, the evaporation under ultra-high vacuum or cold sputtering under low vacuum is selected according to the melting point of the metal to be coated.
3. The method of claim 1, wherein the thickness of the metal coated on the carbon nanotube paper is 5 to 100 nm.
4. The method of claim 1, wherein the carbon nanotubes are at least one of single-walled carbon nanotubes and multi-walled carbon nanotubes, and have a diameter of 10 to 200nm and a length of 5 to 20 μm.
5. The method of claim 3, wherein the carbon nanotube paper has a thickness of 100 to 1000 μm.
6. The method of claim 1, wherein the method of preparing the carbon nanotube paper comprises the steps of:
s11, mixing the carbon nano tube, the surfactant and the mixed solution of the deionized water and the alcohol, and uniformly stirring and dispersing to obtain carbon nano tube slurry;
s12, uniformly coating the carbon nanotube slurry prepared in the step S11 on the surface of the rough copper foil, and drying at 70-80 ℃;
and S13, tearing off the carbon nanotube film dried in the step S12 and rolling the carbon nanotube film into a carbon nanotube paper roll to obtain the carbon nanotube paper with large aperture and large porosity.
7. The method for preparing the metal-coated carbon nanotube according to claim 6, wherein the ratio of the deionized water to the alcohol is 1 to 2: 1.
8. the method of claim 1, wherein the metal-coated carbon nanotube paper is used as a functional foil or crushed as functional powder.
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| CN201911079240.4A CN110777331A (en) | 2019-11-07 | 2019-11-07 | Preparation method of metal-coated carbon nano tube |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113373341A (en) * | 2021-06-18 | 2021-09-10 | 苏州第一元素纳米技术有限公司 | Manufacturing process of carbon nano tube reinforced aluminum electric power fitting |
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Application publication date: 20200211 |