CN102320591A - Method for directly growing mesh carbon nanotubes on copper substrate - Google Patents
Method for directly growing mesh carbon nanotubes on copper substrate Download PDFInfo
- Publication number
- CN102320591A CN102320591A CN201110168334A CN201110168334A CN102320591A CN 102320591 A CN102320591 A CN 102320591A CN 201110168334 A CN201110168334 A CN 201110168334A CN 201110168334 A CN201110168334 A CN 201110168334A CN 102320591 A CN102320591 A CN 102320591A
- Authority
- CN
- China
- Prior art keywords
- temperature
- copper substrate
- copper matrix
- mesh carbon
- copper
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for directly growing mesh carbon nanotubes on a copper substrate, which belongs to a preparation method for carbon nano materials. The method comprises the following steps of: carrying out argon plasma preprocessing on the copper substrate to prepare a Co catalyst solution, impregnating the copper substrate in the Co catalyst solution, vacuum drying, then putting the copper substrate in a reaction furnace, filling mixed gas of ethyne, argon and hydrogen for carrying out catalytic pyrolysis reaction, and obtaining one layer of mesh carbon nano tubes on the surface of the copper substrate. The invention has the advantages that the prepared mesh carbon nanotubes directly grow on a copper plate, no blocking layer needs to be added, the generated carbon nanotubes have high purity, and the preparation technology is simple.
Description
Technical field
The present invention relates to the method for direct growth mesh carbon nanotube on a kind of copper matrix, belong to the technology of preparing of carbon nanomaterial.
Background technology
(carbon nanotubes's carbon nanotube CNTs) since 1991 come to light, has got most of the attention with its unique and potential structural performance, electrology characteristic and mechanical characteristics.The intensity of carbon nanotube is higher more than 100 times than steel approximately, and proportion has only 1/6 of steel; Simultaneously carbon nanotube also has high toughness, and is very soft, so it is considered to following " super fiber ", is reinforcement material fabulous in the matrix material.
At present, the method for preparing carbon nanotube mainly contains: arc discharge method (arc discharge), laser evaporation method (laser ablation) and chemical Vapor deposition process (chemical vapor deposition, CVD) etc.Compare preceding two kinds of methods, chemical Vapor deposition process is owing to have advantages such as cost is low, technology simple controllable, and being considered to has one of method of prospects for commercial application most, also is simultaneously the first-selected technology of growth specific arrangement CNTs.Adopt CVD method growth CNTs normally at first insulation or semiconductor substrate (like aluminum oxide, Si, SiO
2Deng) go up deposition layer of metal catalyst particle, decompose carbon source for growth CNTs then under certain condition, perhaps adopt metal as matrix, between conducting base and catalyzer, add Al
2O
3Etc. the diffusion of thin intermediate blocking-up catalyzer and the metallic matrix CNFs that grows.Yet, for many application,, require material to have very high conduction and heat conductivility like indicating meter, battery electrode, chip interconnect and Electronic Packaging etc., this just needs CNTs to be connected with conducting base (metal etc.).And, reduce contact resistance between metallic matrix and the CNTs and also be one of main challenge that the nano electron device design faces.
Be to connect CNTs and metallic matrix, reduce contact resistance, obvious and effective method is exactly direct growth CNTs on metallic matrix.Direct growth CNTs on metallic matrix; Because metallic matrix is different from non-conductive matrixes such as pottery, most of metal active higher at high temperature reacts with catalyzer easily; Thereby influence its activity; The growth of restriction CNTs, so the reaction of control catalyst and matrix, keeping catalyst activity is the key of preparation CNTs on metallic matrix.Though direct growth on multiple metals such as Ag, W, Cu and alloy substrates such as Parthangal has gone out CNTs, must contain a certain amount of Al in the composite catalyst that is adopted
2O
3, Al
2O
3Blocking effect to Fe and matrix is the prerequisite of growth CNTs.How to control the reaction of metal base and catalyzer, controllable growth goes out CNTs and remains the main challenge that faces at present on the high-conductive metal matrix.
Summary of the invention
The object of the invention is to provide the method for direct growth mesh carbon nanotube on a kind of copper matrix, and it is simple that this method has process, and the carbon nanotube of preparation has the good and purity advantages of higher of quality.
The present invention realizes that through following technical scheme the method for direct growth mesh carbon nanotube on a kind of copper matrix is characterized in that comprising following process:
1) the copper matrix is polished after, use deionized water, acetone and ethanol ultrasonic cleaning respectively, then temperature 25-30 ℃ down dry, and carry out argon plasma and handle 0.5-10min;
2) Xiao Suangu is added in the deionized water preparation 0.005-0.05mol/L cobalt nitrate aqueous solution;
3) the copper matrix of step 1) being handled is inserted step 2) solution in; Flood 20-40 second, in vacuum drying oven, descended dry 1-4 hour, put it in the quartz boat at 80-100 ℃; Flat-temperature zone at crystal reaction tube; Under argon shield, rise to temperature 200-400 ℃, calcining at constant temperature 1-4 hour, obtained the copper matrix that load has catalyzer with 10 ℃/min of temperature rise rate;
4) there is the copper matrix of catalyzer to spread in the quartz boat the prepared load of step 3); Quartz boat is placed the crystal reaction tube flat-temperature zone; Under argon shield, rise to 700 ℃-850 ℃ of temperature with 10 ℃/min of temperature rise rate crystal reaction tube after, be that 250-300mL/min carries out catalytic cracking reaction 0.2h-1h to the gas mixture that crystal reaction tube feeds argon gas, hydrogen and acetylene gas with the flow velocity; Wherein, The volume ratio of argon gas, hydrogen and acetylene gas is (150-300): (10-100): (10-100), under argon atmosphere, furnace temperature is reduced to room temperature then, obtain the mesh carbon nanotube of growing on the copper matrix.
The present invention has the following advantages: adopting Cu material commonly used in the electronic industry is matrix; The doping of pretreatment mode, catalyzer through the control matrix and growth technique etc.; Directly on the copper matrix, growing the mesh carbon nanotube that quality is good and purity is high under the situation of not adding any diffusion barrier tomography; And preparation process and equipment are simple, are easy to realize and promote.
Description of drawings
Fig. 1 is the SEM photo of the mesh carbon nanotube that adopts the inventive method embodiment one and make as catalyzer with Co
Embodiment
Embodiment one
With the diameter 12mm of polishing, the ultrasonic cleaning 20 minutes in zero(ppm) water, acetone and absolute ethyl alcohol respectively of thickness 3mm copper sheet is carried out two minutes argon plasma with the copper sheet of cleaning-drying then and is handled; Take by weighing the 0.192g cobalt nitrate hexahydrate; Dissolve in the 100mL deionized water, be mixed with the solution of 0.005mol/L, again copper sheet was flooded 20 seconds in this solution; Place 100 ℃ of following vacuum-dryings of vacuum drying oven one hour then, on copper sheet, obtained the presoma of catalyzer; There is the copper sheet of catalyst precursor to place the constant temperature zone, middle part of diameter 60mm silica tube Reaktionsofen load; Feed argon shield, raise the temperature to 300 ℃, under this temperature, kept two hours with 10 ℃/min; Make the nitrate salt calcining on copper sheet surface complete; Again temperature is elevated to 800 ℃ with 10 ℃/min, feeds the mixed gas of acetylene, argon gas and hydrogen then, the flow of three kinds of gases is asked 40mL/min, 150mL/min, 60mL/min respectively; At 800 ℃ of 30min that grow down, growth obtains mesh carbon nanotube on copper sheet.
Embodiment two
With the diameter 12mm of polishing, the ultrasonic cleaning 20 minutes in zero(ppm) water, acetone and absolute ethyl alcohol respectively of thickness 3mm copper sheet is carried out one minute argon plasma with the copper sheet of cleaning-drying then and is handled; Take by weighing the 0.192g cobalt nitrate hexahydrate; Dissolve in the 50mL deionized water, be mixed with the solution of 0.01mol/L, again copper sheet was flooded 20 seconds in this solution; Place 100 ℃ of following vacuum-dryings of vacuum drying oven one hour then, on copper sheet, obtained the presoma of catalyzer; There is the copper sheet of catalyst precursor to place the constant temperature zone, middle part of diameter 60mm silica tube Reaktionsofen load; Feed argon shield, raise the temperature to 400 ℃, under this temperature, kept one hour with 10 ℃/min; Make the nitrate salt calcining on copper sheet surface complete; Again temperature is elevated to 750 ℃ with 10 ℃/min, feeds the mixed gas of acetylene, argon gas and hydrogen then, the flow of three kinds of gases is asked 20mL/min, 150mL/min, 80mL/min respectively; At 750 ℃ of 40min that grow down, growth obtains mesh carbon nanotube on copper sheet.
Embodiment three
With the diameter 12mm of polishing, the ultrasonic cleaning 20 minutes in zero(ppm) water, acetone and absolute ethyl alcohol respectively of thickness 3mm copper sheet is carried out two minutes argon plasma with the copper sheet of cleaning-drying then and is handled; Take by weighing the 0.383g cobalt nitrate hexahydrate; Dissolve in the 50mL deionized water, be mixed with the solution of 0.02mol/L, again copper sheet was flooded 20 seconds in this solution; Place 80 ℃ of following vacuum-dryings of vacuum drying oven one hour then, on copper sheet, obtained the presoma of catalyzer; There is the copper sheet of catalyst precursor to place the constant temperature zone, middle part of diameter 60mm silica tube Reaktionsofen load; Feed argon shield, raise the temperature to 350 ℃, under this temperature, kept two hours with 10 ℃/min; Make the nitrate salt calcining on copper sheet surface complete; Again temperature is elevated to 850 ℃ with 10 ℃/min, feeds the mixed gas of acetylene, argon gas and hydrogen then, the flow of three kinds of gases is asked 30mL/min, 200mL/min, 50mL/min respectively; At 850 ℃ of 30min that grow down, growth obtains mesh carbon nanotube on copper sheet.
Embodiment four
With the diameter 12mm of polishing, the ultrasonic cleaning 20 minutes in zero(ppm) water, acetone and absolute ethyl alcohol respectively of thickness 3mm copper sheet is carried out one minute argon plasma with the copper sheet of cleaning-drying then and is handled; Take by weighing the 0.96g cobalt nitrate hexahydrate; Dissolve in the 50mL deionized water, be mixed with the solution of 0.05mol/L, again copper sheet was flooded 20 seconds in this solution; Place 100 ℃ of following vacuum-dryings of vacuum drying oven one hour then, on copper sheet, obtained the presoma of catalyzer; There is the copper sheet of catalyst precursor to place the constant temperature zone, middle part of diameter 60mm silica tube Reaktionsofen load; Feed argon shield, raise the temperature to 250 ℃, under this temperature, kept three hours with 10 ℃/min; Make the nitrate salt calcining on copper sheet surface complete; Again temperature is elevated to 800 ℃ with 10 ℃/min, feeds the mixed gas of acetylene, argon gas and hydrogen then, the flow of three kinds of gases is asked 50mL/min, 150mL/min, 50mL/min respectively; At 800 ℃ of 20min that grow down, growth obtains mesh carbon nanotube on copper sheet.
Embodiment five
With the diameter 12mm of polishing, the ultrasonic cleaning 20 minutes in zero(ppm) water, acetone and absolute ethyl alcohol respectively of thickness 3mm copper sheet is carried out one minute argon plasma with the copper sheet of cleaning-drying then and is handled; Take by weighing the 0.192g cobalt nitrate hexahydrate; Dissolve in the 50mL deionized water, be mixed with the solution of 0.01mol/L, again copper sheet was flooded 20 seconds in this solution; Place 80 ℃ of following vacuum-dryings of vacuum drying oven two hours then, on copper sheet, obtained the presoma of catalyzer; There is the copper sheet of catalyst precursor to place the constant temperature zone, middle part of diameter 60mm silica tube Reaktionsofen load; Feed argon shield, raise the temperature to 300 ℃, under this temperature, kept two hours with 10 ℃/min; Make the nitrate salt calcining on copper sheet surface complete; Again temperature is elevated to 700 ℃ with 10 ℃/min, feeds the mixed gas of acetylene, argon gas and hydrogen then, the flow of three kinds of gases is asked 30mL/min, 160mL/min, 80mL/min respectively; At 700 ℃ of 40min that grow down, growth obtains mesh carbon nanotube on copper sheet.
Claims (1)
1. the method for direct growth mesh carbon nanotube on the copper matrix is characterized in that comprising following process:
1) the copper matrix is polished after, use deionized water, acetone and ethanol ultrasonic cleaning respectively, then temperature 25-30 ℃ down dry, and carry out argon plasma and handle 0.5-10min;
2) Xiao Suangu is added in the deionized water preparation 0.005-0.05mol/L cobalt nitrate aqueous solution;
3) the copper matrix of step 1) being handled is inserted step 2) solution in; Flood 20-40 second, in vacuum drying oven, descended dry 1-4 hour, put it in the quartz boat at 80-100 ℃; Flat-temperature zone at crystal reaction tube; Under argon shield, rise to temperature 200-400 ℃, calcining at constant temperature 1-4 hour, obtained the copper matrix that load has catalyzer with 10 ℃/min of temperature rise rate;
4) there is the copper matrix of catalyzer to spread in the quartz boat the prepared load of step 3); Quartz boat is placed the crystal reaction tube flat-temperature zone; Under argon shield, rise to 700 ℃-850 ℃ of temperature with 10 ℃/min of temperature rise rate crystal reaction tube after, be that 250-300mL/min carries out catalytic cracking reaction 0.2h-1h to the gas mixture that crystal reaction tube feeds argon gas, hydrogen and acetylene gas with the flow velocity; Wherein, The volume ratio of argon gas, hydrogen and acetylene gas is (150-300): (10-100): (10-100), under argon atmosphere, furnace temperature is reduced to room temperature then, obtain the mesh carbon nanotube of growing on the copper matrix.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110168334 CN102320591B (en) | 2011-06-22 | 2011-06-22 | Method for directly growing mesh carbon nanotubes on copper substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201110168334 CN102320591B (en) | 2011-06-22 | 2011-06-22 | Method for directly growing mesh carbon nanotubes on copper substrate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102320591A true CN102320591A (en) | 2012-01-18 |
| CN102320591B CN102320591B (en) | 2013-01-23 |
Family
ID=45448471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201110168334 Expired - Fee Related CN102320591B (en) | 2011-06-22 | 2011-06-22 | Method for directly growing mesh carbon nanotubes on copper substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102320591B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658153A (en) * | 2012-04-20 | 2012-09-12 | 天津工业大学 | Preparation method of copper substrate surface growth fullerene doped porous carbon nanofibers |
| CN103831549A (en) * | 2014-03-19 | 2014-06-04 | 哈尔滨工业大学 | Method for preparing carbon nano tube reinforced copper-based composite brazing filler metal based on in-situ reaction |
| CN104058382A (en) * | 2013-03-19 | 2014-09-24 | 海洋王照明科技股份有限公司 | Preparation method for carbon nanotube |
| CN104058390A (en) * | 2013-03-19 | 2014-09-24 | 海洋王照明科技股份有限公司 | Preparation method for graphene |
| CN104058383A (en) * | 2013-03-19 | 2014-09-24 | 海洋王照明科技股份有限公司 | Preparation method for carbon nanotube |
| CN108666046A (en) * | 2017-03-31 | 2018-10-16 | 上海新昇半导体科技有限公司 | A kind of composite carbon nanometer tube superconducting core wire rod structure and preparation method thereof |
| CN109734075A (en) * | 2019-03-25 | 2019-05-10 | 杭州英希捷科技有限责任公司 | A method of carbon nano pipe array is prepared using solution catalyst |
| CN110576187A (en) * | 2019-09-19 | 2019-12-17 | 天津大学 | preparation method for in-situ synthesis of three-dimensional graphene/one-dimensional carbon nanotube loaded copper nanoparticle material |
| CN114160764A (en) * | 2021-11-22 | 2022-03-11 | 昆明理工大学 | Method for producing composite material by adopting continuous casting |
| CN115963151A (en) * | 2022-10-25 | 2023-04-14 | 绍兴市特种设备检测院 | Hydrogen sensor and intelligent monitoring system |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1888103A (en) * | 2006-07-17 | 2007-01-03 | 天津大学 | Vapor depositing in-situ reaction process for preparing carbon nanotube reinforced copper-base composite material |
| CN1903711A (en) * | 2006-07-17 | 2007-01-31 | 天津大学 | Method of preparing carbon nano tube by Ni/RE/Cu catalyst chemical gaseous phase sedimentation |
-
2011
- 2011-06-22 CN CN 201110168334 patent/CN102320591B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1888103A (en) * | 2006-07-17 | 2007-01-03 | 天津大学 | Vapor depositing in-situ reaction process for preparing carbon nanotube reinforced copper-base composite material |
| CN1903711A (en) * | 2006-07-17 | 2007-01-31 | 天津大学 | Method of preparing carbon nano tube by Ni/RE/Cu catalyst chemical gaseous phase sedimentation |
Non-Patent Citations (1)
| Title |
|---|
| 康建立 等: "碳纳米管增强铜基复合材料的制备", 《第九次全国热处理大会论文集》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102658153A (en) * | 2012-04-20 | 2012-09-12 | 天津工业大学 | Preparation method of copper substrate surface growth fullerene doped porous carbon nanofibers |
| CN102658153B (en) * | 2012-04-20 | 2014-04-02 | 天津工业大学 | Preparation method of copper substrate surface growth fullerene doped porous carbon nanofibers |
| CN104058382A (en) * | 2013-03-19 | 2014-09-24 | 海洋王照明科技股份有限公司 | Preparation method for carbon nanotube |
| CN104058390A (en) * | 2013-03-19 | 2014-09-24 | 海洋王照明科技股份有限公司 | Preparation method for graphene |
| CN104058383A (en) * | 2013-03-19 | 2014-09-24 | 海洋王照明科技股份有限公司 | Preparation method for carbon nanotube |
| CN103831549A (en) * | 2014-03-19 | 2014-06-04 | 哈尔滨工业大学 | Method for preparing carbon nano tube reinforced copper-based composite brazing filler metal based on in-situ reaction |
| CN108666046A (en) * | 2017-03-31 | 2018-10-16 | 上海新昇半导体科技有限公司 | A kind of composite carbon nanometer tube superconducting core wire rod structure and preparation method thereof |
| CN109734075A (en) * | 2019-03-25 | 2019-05-10 | 杭州英希捷科技有限责任公司 | A method of carbon nano pipe array is prepared using solution catalyst |
| CN110576187A (en) * | 2019-09-19 | 2019-12-17 | 天津大学 | preparation method for in-situ synthesis of three-dimensional graphene/one-dimensional carbon nanotube loaded copper nanoparticle material |
| CN114160764A (en) * | 2021-11-22 | 2022-03-11 | 昆明理工大学 | Method for producing composite material by adopting continuous casting |
| CN115963151A (en) * | 2022-10-25 | 2023-04-14 | 绍兴市特种设备检测院 | Hydrogen sensor and intelligent monitoring system |
| CN115963151B (en) * | 2022-10-25 | 2024-01-19 | 绍兴市特种设备检测院 | Hydrogen sensor and intelligent monitoring system |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102320591B (en) | 2013-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102320591B (en) | Method for directly growing mesh carbon nanotubes on copper substrate | |
| CN103773985B (en) | A kind of efficient original position prepares the method that Graphene strengthens Cu-base composites | |
| CN101831622B (en) | Grapheme foam and preparation method thereof | |
| CN102942177B (en) | Method for preparing graphene sheet | |
| CN105645375A (en) | Method for direct growth of porous carbon nanotubes on nano-porous copper | |
| CN104528683B (en) | A kind of preparation method of bamboo-like carbon nano tubes | |
| CN110148760B (en) | Porous carbon-carbon nanotube composite material and preparation method and application thereof | |
| CN113831131B (en) | Carbon foam in-situ growth carbon nanotube composite electromagnetic shielding material and preparation method thereof | |
| KR101591454B1 (en) | Manufacturing method for Metal and Oxide hybrid coated Nano Carbon | |
| CN102092670B (en) | Carbon nano-tube composite structure and preparation method thereof | |
| CN101857460A (en) | Preparation method of carbon nano tube array for spinning | |
| CN102658153B (en) | Preparation method of copper substrate surface growth fullerene doped porous carbon nanofibers | |
| CN102320590B (en) | Method for directly growing single and double-spiral nano carbon fibers on copper matrix | |
| CN110451465B (en) | Sea urchin-shaped boron nitride nanosphere-nanotube hierarchical structure and preparation method thereof | |
| CN101139092B (en) | Method for preparing nanometer carbon tube on the aluminum foil | |
| CN110697695A (en) | Preparation method of graphene reinforced metal matrix foam framework structure composite material | |
| US8475761B2 (en) | Method for producing carbon nanocoils | |
| Zhao et al. | Carbon nanotube growth in the pores of expanded graphite by chemical vapor deposition | |
| CN104310371A (en) | Method for growing carbon nano tube in situ on surface of fiber | |
| CN105645376A (en) | Method for direct growth of porous carbon nanotube graphene hybrid on nano-porous copper | |
| CN102351164B (en) | Method for directly growing vertical nano carbon fiber arrays on copper matrix | |
| CN107857250B (en) | Melamine foam in-situ growth carbon nanotube composite super-hydrophobic material and preparation method thereof | |
| Wu et al. | Nitrogen-doped multilayered nanographene derived from Ni 3 C with efficient electron field emission | |
| CN109665516A (en) | A kind of simple method for preparing upright graphene nano chip arrays | |
| CN103993475B (en) | A kind of preparation method at carbon fiber surface coated Si/C nano wire |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130123 Termination date: 20210622 |