CN100400688C - Vapor depositing in-situ reaction process for preparing carbon nanotube reinforced copper-base composite material - Google Patents
Vapor depositing in-situ reaction process for preparing carbon nanotube reinforced copper-base composite material Download PDFInfo
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- CN100400688C CN100400688C CNB2006100147834A CN200610014783A CN100400688C CN 100400688 C CN100400688 C CN 100400688C CN B2006100147834 A CNB2006100147834 A CN B2006100147834A CN 200610014783 A CN200610014783 A CN 200610014783A CN 100400688 C CN100400688 C CN 100400688C
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Abstract
The present invention is preparation process of carbon nanotube reinforced copper-base composite material with high strength and high conductivity, and belongs to the field of copper-base composite material preparing technology. The preparation process includes the following steps: adding nickel nitrate hexahydrate, yttrium nitrate hexahydrate and ethanol soaked copper powder in certain weight proportion into distilled water to obtain nickel nitrate solution; dropping sodium hydroxide solution to the nickel nitrate solution to produce neutralizing reaction obtaining ternary Ni(OH)2/Y(OH)3/Cu colloid; washing, filtering, drying, grinding and calcining to obtain Ni/Y/Cu catalyst precursor; setting the precursor into reaction furnace, introducing H2 to reduce, and introducing N2 and reaction gas for catalytic cracking reaction to obtain composite carbon nanotube/Cu powder; initially pressing the composite powder, sintering and re-pressing to obtain carbon nanotube in-situ reinforced copper-base composite material.
Description
Technical field
The present invention relates to the preparation method that a kind of carbon nanotube reinforced copper-base prepares the Cu-base composites of high-strength highly-conductive, belong to the technology of preparing of Cu-base composites.
Background technology
It is that a class has the good comprehensive physicals and the functional materials of mechanical property that the high strength height is led copper-based material.It had both had high intensity and good plasticity, has good conductivity (specific conductivity and heat conductance) again, therefore the contact, the ring header of engine, armature, rotor, the empty frame lead of electric power train that are widely used in the lead frame of unicircuit, various welding electrode, electric works switch, and in the blast-furnace tuyere in the metallurgical industry, continuous cast mold, the first-class demanding conductive and heat-conductive environment of oxygen lance spraying.
Carbon nanotube has got most of the attention with its unique and potential structural performance, electrology characteristic and mechanical characteristics since 1991 are found.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.In addition, can make its electroconductibility be metal, semi-metal or semiconductive by grid structure and the diameter that changes in the carbon nanotube, as conductor, the electroconductibility of carbon nanotube can be better than copper, and carbon nanotube itself has high-wearing feature and self lubricity and high thermostability, therefore, prepare the performance requriements that Cu-base composites estimates to reach high-strength highly-conductive with carbon nanotube as strengthening body.
At present, in using carbon nano-tube reinforced metal-matrix composite material, complex method is generally rapid solidification method and powder metallurgic method.The research of carrying out comprises CNTs/Fe, CNTs/Al, CNTs/Ni, CNTs/Cu etc.But present existing studies show that, most of metal-base composites are making little progress aspect the raising mechanical property, this may be in the matrix material of preparation between carbon nanotube and the metal interface bond strength low due to, simultaneously also may be relevant with the size of carbon nanotube, purity, interpolation recombining process etc.Recently, employing molecular mixing methods such as Seung I.Cha have prepared carbon nanotube reinforced copper-base composite material, preferably resolve the dispersion problem of carbon nanotube, but this method also needs carbon nanotube is carried out complicated purifying, process such as surface-functionalized, destroy the original performance of carbon nanotube, and failed to obtain simultaneously having the over-all properties of high-strength high conductivity.
Summary of the invention
The object of the invention is to provide a kind of carbon nanotube reinforced copper-base to prepare the preparation method of the Cu-base composites of high-strength highly-conductive, and it is simple that this method has process, and the Cu-base composites of preparation has the over-all properties of high-strength high conductivity.
The present invention is achieved by the following technical solutions, and a kind of carbon nanotube reinforced copper-base prepares the preparation method of the Cu-base composites of high-strength highly-conductive, it is characterized in that comprising following process:
1) preparation Ni/Y/Cu catalyst precursor
At first copper powder is handled through soaked in absolute ethyl alcohol in advance, with six water nickelous nitrates, six water Yttrium trinitrates and the copper powder after soaking be that 1-8: 0.1-4: 98.9-88 joins that to obtain nickelous nitrate concentration in the deionized water be 0.05-0.1mol/L solution by mass ratio Ni: Y: Cu, adding naoh concentration under the mol ratio stirring in 1: 3 by six water nickelous nitrates and sodium hydroxide mol ratio 1: 2 and six water Yttrium trinitrates and sodium hydroxide in this solution is that 0.05-0.25mol/L solution to neutralization reaction finishes, and obtains Ni (OH)
2/ Y (OH)
3/ Cu ternary colloid.The ternary colloid adopts vacuum drying oven to dehydrate under 80-150 ℃ after washing, filtration, grinds with agate mortar, and at 300 ℃ of-500 ℃ of temperature lower calcinations, obtains the Ni/Y/Cu catalyst precursor of corresponding weight score.
2) preparation carbon nanotube/Cu composite powder
Get step 1) gained Ni/Y/Cu catalyst precursor, be layered in the quartz boat, quartz boat is placed flat-temperature zone, crystal reaction tube middle part; Under nitrogen protection, be warming up to 400 ℃-600 ℃; feeding flow velocity carried out reduction reaction 1.5-4 hour for 80-200mL/min hydrogen; feed nitrogen again; temperature is transferred to 500 ℃-700 ℃; volume ratio by nitrogen and reactant gases is that 1-7 feeds nitrogen and reactant gases methane or acetylene then, and the flow velocity of mixed gas is that 200-480mL/min carries out catalytic cracking reaction, reaction 0.25h-4h; under nitrogen atmosphere, furnace temperature is reduced to room temperature, obtain carbon nanotube/Cu composite powder.
3) preparation carbon nanotube/Cu matrix material
To step 2) preparation composite powder through 400～600MPa first pressing, 30～60s, be that 15～20 ℃/min rises to 900～1000 ℃ with temperature rise rate again, sintering 1.5～2.5h presses 30～60s again at 0.8～1.2GPa at last, obtains the carbon nanotube original position and strengthens Cu-base composites.
The present invention has the following advantages:
The present invention is by in-situ growing carbon nano tube on the copper powder matrix, solved the scattering problem of carbon nanotube in matrix material well, carbon nanotube is not reunited in composite powder, disperse to open very much, thereby the mechanical property and the thermal characteristics of material material under the prerequisite that keeps good electrical properties are greatly enhanced, can satisfy the technical requirements of contemporary microelectronics development, that is: the tensile strength 〉=600MPa of material, electric conductivity 〉=80%IACS (Intemational Annealed Copper Standard one I.A.C.S.), high temperature resistance softening temperature 〉=800K.
Description of drawings
Fig. 1 makes the TEM photo of composite powder for adopting the inventive method.
Fig. 2 makes the HRTEM photo of carbon pipe in the composite powder for adopting the inventive method.
Embodiment
Embodiment one
Use the 30mL soaked in absolute ethyl alcohol after a few hours the 18g electrolytic copper powder, be mixed with the 363mL aqueous solution with 7.926g six water nickelous nitrates and 1.723g six water Yttrium trinitrates, then 2.721g sodium hydroxide is mixed with the 272mL aqueous solution, under magnetic agitation, dropwise is added drop-wise in the above-mentioned solution, obtain Ni (OH)
2/ Y (OH)
3/ Cu ternary colloid; The ternary colloid is washed, filters, adopt vacuum drying oven under 80 ℃, to dehydrate, grind with agate mortar, and under 400 ℃ of nitrogen protections, calcine 2h, obtain the Ni/Y/Cu catalyst precursor.Get the 2gNi/Y/Cu catalyst precursor then, be warming up to 500 ℃ under the nitrogen protection, stop nitrogen, feed hydrogen and reduce, hydrogen flow rate is 80mL/min.After keeping 4h, turn off hydrogen, open nitrogen and continue to be warming up to 550 ℃; feed nitrogen and methane blended gas (nitrogen flow rate 300mL/min then; methane flow rate is 100mL/min) reaction 0.5h turn off gas mixture, furnace temperature is chilled to room temperature under the nitrogen protection, obtains the CNTs-Cu composite powder.Composite powder after the pressurize 60s first pressing, is that 20 ℃/min rises to 975 ℃ with temperature rise rate through 500MPa again, and sintering 1.5h obtains the CNTs/Cu matrix material at last after the multiple pressure that through the 1GPa dwell time is 60s.
Embodiment two
Use the 30mL soaked in absolute ethyl alcohol after a few hours the 38g electrolytic copper powder, be mixed with the 363mL aqueous solution with 7.926g six water nickelous nitrates and 1.723g six water Yttrium trinitrates, then 2.721g sodium hydroxide is mixed with the 272mL aqueous solution, under magnetic agitation, dropwise is added drop-wise in the above-mentioned solution, obtain Ni (OH)
2/ Y (OH)
3/ Cu ternary colloid; The ternary colloid is washed, filters, adopt vacuum drying oven under 150 ℃, to dehydrate, grind with agate mortar, and under 400 ℃ of nitrogen protections, calcine 2h, obtain the Ni/Y/Cu catalyst precursor.Get the 2gNi/Y/Cu catalyst precursor then, be warming up to 500 ℃ under the nitrogen protection, stop nitrogen, feed hydrogen and reduce, hydrogen flow rate is 200mL/min.After keeping 1.5h, turn off hydrogen, open nitrogen and continue to be warming up to 700 ℃; feed nitrogen and methane blended gas (nitrogen flow rate 300mL/min then; methane flow rate is 100mL/min) reaction 1h turn off gas mixture, furnace temperature is chilled to room temperature under the nitrogen protection, obtains the CNTs-Cu composite powder.Composite powder after the pressurize 60s first pressing, is that 20 ℃/min rises to 1000 ℃ with temperature rise rate through 400MPa again, and sintering 1.5h obtains the CNTs/Cu matrix material at last after the multiple pressure that through the 0.8GPa dwell time is 60s.
Embodiment three
Use the 30mL soaked in absolute ethyl alcohol after a few hours the 38g electrolytic copper powder, be mixed with the 363mL aqueous solution with 7.926g six water nickelous nitrates and 1.723g six water Yttrium trinitrates, then 2.721g sodium hydroxide is mixed with the 272mL aqueous solution, under magnetic agitation, dropwise is added drop-wise in the above-mentioned solution, obtain Ni (OH)
2/ Y (OH)
3/ Cu ternary colloid; The ternary colloid is washed, filters, adopt vacuum drying oven under 100 ℃, to dehydrate, grind with agate mortar, and under 400 ℃ of nitrogen protections, calcine 2h, obtain the Ni/Y/Cu catalyst precursor.Get the 2gNi/Y/Cu catalyst precursor then, be warming up to 400 ℃ under the nitrogen protection, stop nitrogen, feed hydrogen and reduce, hydrogen flow rate is 100mL/min.After keeping 4h, turn off that hydrogen feeds nitrogen and methane blended gas (nitrogen flow rate 420mL/min, methane flow rate is 60mL/min) reaction 1h turns off gas mixture, furnace temperature is chilled to room temperature under the nitrogen protection, obtains the CNTs-Cu composite powder.Composite powder after the pressurize 60s first pressing, is that 20 ℃/min rises to 900 ℃ with temperature rise rate through 600MPa again, and sintering 2.5h obtains the CNTs/Cu matrix material at last after the multiple pressure that through the 1.2GPa dwell time is 60s.
Embodiment four
Use the 30mL soaked in absolute ethyl alcohol after a few hours the 78g electrolytic copper powder, be mixed with the 363mL aqueous solution with 3.963g six water nickelous nitrates and 0.862g six water Yttrium trinitrates, then 1.361g sodium hydroxide is mixed with the 272mL aqueous solution, under magnetic agitation, dropwise is added drop-wise in the above-mentioned solution, obtain Ni (OH)
2/ Y (OH)
3/ Cu ternary colloid; The ternary colloid is washed, filters, adopt vacuum drying oven under 100 ℃, to dehydrate, grind with agate mortar, and under 500 ℃ of nitrogen protections, calcine 2h, obtain the Ni/Y/Cu catalyst precursor.Get the 2gNi/Y/Cu catalyst precursor then, be warming up to 500 ℃ under the nitrogen protection, stop nitrogen, feed hydrogen and reduce, hydrogen flow rate is 100mL/min.After keeping 2h, turn off that hydrogen feeds nitrogen and methane blended gas (nitrogen flow rate 100mL/min, methane flow rate is 100mL/min) reaction 1h turns off gas mixture, furnace temperature is chilled to room temperature under the nitrogen protection, obtains the CNTs-Cu composite powder.Composite powder after the pressurize 60s first pressing, is that 20 ℃/min rises to 975 ℃ with temperature rise rate through 500MPa again, and sintering 1.5h obtains the CNTs/Cu matrix material at last after the multiple pressure that through the 1GPa dwell time is 60s.
Embodiment five
Use the 30mL soaked in absolute ethyl alcohol after a few hours the 18.9g electrolytic copper powder, be mixed with the 340mL aqueous solution with 4.654g six water nickelous nitrates and 0.431g six water Yttrium trinitrates, then 1.498g sodium hydroxide is mixed with the 374mL aqueous solution, under magnetic agitation, dropwise is added drop-wise in the above-mentioned solution, obtain Ni (OH)
2/ Y (OH)
3/ Cu ternary colloid; The ternary colloid is washed, filters; adopt vacuum drying oven under 100 ℃, to dehydrate; grind with agate mortar, under nitrogen protection, powder is warming up to 400 ℃ of calcining 2h 300 ℃ of follow-up continuing of insulation 2h earlier then, obtain the Ni/Y/Cu catalyst precursor.Get the 2gNi/Y/Cu catalyst precursor then, be warming up to 500 ℃ under the nitrogen protection, stop nitrogen, feed hydrogen and reduce, hydrogen flow rate is 100mL/min.After keeping 2h, turn off that hydrogen feeds nitrogen and methane blended gas (nitrogen flow rate 300mL/min, methane flow rate is 100mL/min) reaction 1h turns off gas mixture, furnace temperature is chilled to room temperature under the nitrogen protection, obtains the CNTs-Cu composite powder.Composite powder after the pressurize 60s first pressing, is that 20 ℃/min rises to 975 ℃ with temperature rise rate through 500MPa again, and sintering 1.5h obtains the CNTs/Cu matrix material at last after the multiple pressure that through the 1GPa dwell time is 60s.
Claims (1)
1. a carbon nanotube reinforced copper-base prepares the preparation method of the Cu-base composites of high-strength highly-conductive, it is characterized in that comprising following process:
1) preparation Ni/Y/Cu catalyst precursor
At first copper powder is handled through soaked in absolute ethyl alcohol in advance, with six water nickelous nitrates, six water Yttrium trinitrates and the copper powder after soaking be that 1-8: 0.1-4: 98.9-88 joins that to obtain nickelous nitrate concentration in the deionized water be 0.05-0.1mol/L solution by mass ratio Ni: Y: Cu, adding naoh concentration under the mol ratio stirring in 1: 3 by six water nickelous nitrates and sodium hydroxide mol ratio 1: 2 and six water Yttrium trinitrates and sodium hydroxide in this solution is that 0.05-0.25mol/L solution to neutralization reaction finishes, and obtains Ni (OH)
2/ Y (OH)
3/ Cu ternary colloid, the ternary colloid adopts vacuum drying oven to dehydrate under 80-150 ℃ after washing, filtration, grinds with agate mortar, and at 300 ℃ of-500 ℃ of temperature lower calcinations, obtains the Ni/Y/Cu catalyst precursor of corresponding weight score;
2) preparation carbon nanotube/Cu composite powder
Get step 1) gained Ni/Y/Cu catalyst precursor, be layered in the quartz boat, quartz boat is placed flat-temperature zone, crystal reaction tube middle part, under nitrogen protection, be warming up to 400 ℃-600 ℃, feeding flow velocity carried out reduction reaction 1.5-4 hour for 80-200mL/min hydrogen, feed nitrogen again, temperature is transferred to 500 ℃-700 ℃, volume ratio by nitrogen and reactant gases is that 1-7 feeds nitrogen and reactant gases methane or acetylene then, the flow velocity of mixed gas is that 200-480mL/min carries out catalytic cracking reaction, reaction 0.25h-4h reduces to room temperature with furnace temperature under nitrogen atmosphere, obtain carbon nanotube/Cu composite powder;
3) preparation carbon nanotube/Cu matrix material
To step 2) preparation composite powder through 400～600MPa first pressing, 30～60s, be that 15～20 ℃/min rises to 900～1000 ℃ with temperature rise rate again, sintering 1.5～2.5h presses 30～60s again at 0.8～1.2GPa at last, obtains the carbon nanotube original position and strengthens Cu-base composites.
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| CN100443223C (en) * | 2007-02-01 | 2008-12-17 | 天津大学 | Method of producing composite material of carbon nanometer pipe/ nickel/ aluminum improving and toughening alumina radicel |
| CN100400689C (en) * | 2007-04-10 | 2008-07-09 | 天津大学 | Method for producing nano-diamond reinforced copper-base composite material by chemical codeposition |
| CN100463745C (en) * | 2007-06-13 | 2009-02-25 | 湖南大学 | Method for preparing copper-base composite particles of internal carbon-inlaid nano pipe |
| CN102324335B (en) * | 2011-06-07 | 2013-10-23 | 天津工业大学 | Method for preparing compound electrical contact material |
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| CN103128284B (en) * | 2013-03-15 | 2014-11-05 | 南昌航空大学 | Reinforced method of carbon nanotubes (CNTs) of laser-induced composite fused deposition gradient content for copper matrix composite materials |
| 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 |
| US9973062B2 (en) * | 2014-06-30 | 2018-05-15 | GM Global Technology Operations LLC | Method of synthesizing aluminum carbon nanotube materials for structural and conductor applications |
| CN105441711B (en) * | 2015-12-28 | 2017-07-28 | 哈尔滨工业大学 | A kind of preparation method of three-dimensional structure CNTs Reinforced Cu-Base Composites |
| CN108611520B (en) * | 2018-05-08 | 2019-05-31 | 上海理工大学 | A kind of copper-based in-situ composite material and preparation method thereof |
| CN108611510B (en) * | 2018-05-08 | 2019-05-28 | 上海理工大学 | A kind of CNTs/Cu composite material and preparation method |
| CN108611511B (en) * | 2018-05-08 | 2019-08-09 | 上海理工大学 | A kind of three-dimensional intercommunication CNTs/Cu composite material and preparation method |
| CN109338168B (en) * | 2018-11-02 | 2020-10-13 | 昆明理工大学 | Preparation method of complex-phase reinforced aluminum-based composite material |
| 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 |
| CN111020525A (en) * | 2020-01-07 | 2020-04-17 | 中国科学院过程工程研究所 | Preparation method of composite powder with carbon nano tube coated with metal matrix |
| CN114101662A (en) * | 2021-12-06 | 2022-03-01 | 赵玉荣 | Copper alloy carbon nanotube composite powder and preparation method and application thereof |
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| WO2004011178A1 (en) * | 2002-07-26 | 2004-02-05 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Synthesis of metal nanoparticle compositions from metallic and ethynyl compounds |
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| WO2004011178A1 (en) * | 2002-07-26 | 2004-02-05 | The Government Of The United States Of America, As Represented By The Secretary Of The Navy | Synthesis of metal nanoparticle compositions from metallic and ethynyl compounds |
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