CN112501468B - Smelting process of carbon nano tube reinforced aluminum-based composite material - Google Patents

Smelting process of carbon nano tube reinforced aluminum-based composite material Download PDF

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CN112501468B
CN112501468B CN202010443495.0A CN202010443495A CN112501468B CN 112501468 B CN112501468 B CN 112501468B CN 202010443495 A CN202010443495 A CN 202010443495A CN 112501468 B CN112501468 B CN 112501468B
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aluminum
carbon nano
smelting
nano tube
carbon
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CN112501468A (en
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蔡炜
何卫
王利民
闻集群
李辛庚
宗立君
汤超
吴昊
卢才璇
陈胜男
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Wuhan Nanrui Electric Power Engineering Technology Equipment Co ltd
Wuhan NARI Ltd
Electric Power Research Institute of State Grid Shandong Electric Power Co Ltd
State Grid Shandong Electric Power Co Ltd
State Grid Electric Power Research Institute
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Wuhan Nanrui Electric Power Engineering Technology Equipment Co ltd
Wuhan NARI Ltd
Electric Power Research Institute of State Grid Shandong Electric Power Co Ltd
State Grid Shandong Electric Power Co Ltd
State Grid Electric Power Research Institute
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/10Alloys containing non-metals
    • C22C1/1036Alloys containing non-metals starting from a melt
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/06Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/10Alloys containing non-metals
    • C22C1/1005Pretreatment of the non-metallic additives
    • C22C1/1015Pretreatment of the non-metallic additives by preparing or treating a non-metallic additive preform
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/10Alloys containing non-metals
    • C22C1/1036Alloys containing non-metals starting from a melt
    • C22C1/1047Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C21/00Alloys based on aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C26/00Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C26/00Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C22C2026/002Carbon nanotubes

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Abstract

The invention provides a smelting process of a carbon nano tube reinforced aluminum-based composite material, which comprises the steps of carrying out ball milling, mixing and dispersing on a smelting auxiliary agent, carbon nano tubes and aluminum/aluminum alloy powder in a planetary ball mill to obtain mixed powder; putting the mixed powder into a die for cold pressing to obtain a carbon nano tube-aluminum/aluminum alloy prefabricated block; pressing the carbon nano tube-aluminum/aluminum alloy prefabricated block into molten aluminum through a bell jar, smelting under stirring, standing and then casting for forming, wherein the smelting auxiliary agent is potassium boroaluminate (KBF)4) Potassium titanium fluoroaluminate (K)2TiF6) Potassium fluoroaluminate (K)3AlF6) Or sodium fluoroaluminate (Na)3AlF6) Any one of them. The smelting process of the carbon nanotube reinforced aluminum matrix composite material adopts the smelting process to prepare the carbon nanotube reinforced aluminum matrix composite material, realizes the high-efficiency dispersion of the carbon nanotubes in the smelting process, can continue to use the traditional metal smelting equipment, has the characteristics of simple process, less investment, high product strength and the like, and is suitable for industrial batch production.

Description

Smelting process of carbon nano tube reinforced aluminum-based composite material
Technical Field
The invention relates to the technical field of aluminum alloy preparation, in particular to a smelting process of a carbon nano tube reinforced aluminum matrix composite.
Background
Carbon nanotubes are considered to be one of the most suitable reinforcements for composite materials because of their excellent physicochemical properties, mechanical properties and stable structure. The carbon nano tube is dispersed in the aluminum or aluminum alloy matrix to prepare the carbon nano tube reinforced aluminum matrix composite material with high specific strength and high specific modulus, and the carbon nano tube reinforced aluminum matrix composite material has great application value in the fields of aerospace, automobile manufacturing, power grids and the like. In general, in the existing research, the powder metallurgy method is mostly adopted to prepare the aluminum matrix composite, mainly because the carbon nanotubes are more easily dispersed by high energy ball milling, and the research report for the smelting method is relatively rare. Smelting is a very effective processing mode, an aluminum alloy matrix is in a molten state and is mixed with carbon nanotubes to form a new composite material, but the existing smelting process still has a plurality of problems: the untreated carbon nanotubes float upward and cannot be directly and effectively added and dispersed; the infiltration is difficult due to the large property difference between the carbon nano tube and the aluminum liquid, and the interface combination between the carbon nano tube and the aluminum liquid is weak; the higher melting temperature results in a severe chemical reaction between the carbon nanotubes and aluminum.
The physical or chemical plating on the surface of the carbon nano tube is an important means for improving the dispersibility and the compatibility with the metal melt, and patent 201510563653.5 shows that under the casting process condition, the blank carbon nano tube plated with a Ni or Cu metal layer has an influence on the performance of the aluminum matrix composite material, and the carbon nano tube after coating treatment has a more obvious reinforcing effect. However, the chemical plating method is generally low in efficiency and difficult in waste liquid treatment, and a simple and efficient composite material preparation process suitable for mass production needs to be provided.
Disclosure of Invention
The invention aims to provide a smelting process of a carbon nanotube reinforced aluminum matrix composite, which adopts the smelting process to prepare the carbon nanotube reinforced aluminum matrix composite, realizes the high-efficiency dispersion of carbon nanotubes in the smelting process, can continue to use the traditional metal smelting equipment, has the characteristics of simple process, less investment, high product strength and the like, and is suitable for industrial batch production.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a smelting process of a carbon nano tube reinforced aluminum matrix composite material comprises the following steps:
(1) carrying out ball milling, mixing and dispersing on the smelting auxiliary agent, the carbon nano tube and the aluminum/aluminum alloy powder in a planetary ball mill to obtain mixed powder;
(2) putting the mixed powder into a die for cold pressing to obtain a carbon nano tube-aluminum/aluminum alloy prefabricated block;
(3) and pressing the carbon nano tube-aluminum/aluminum alloy prefabricated block into the molten aluminum through a bell jar, smelting under stirring, standing and then casting and forming.
According to the scheme, the smelting auxiliary agent is KBF4、K2TiF6、K3AlF6Or Na3AlF6Any one of the carbon nanotubes and the aluminum/aluminum alloy powder is subjected to ball milling and mixing according to the mass ratio of 1:1: 8.
According to the scheme, the medium used for ball milling is steel balls or agate balls, the rotating speed is 200-500 r/min, and the ball milling time is 3-8 h.
According to the scheme, the pressing force during cold pressing is 100-300 MPa.
According to the scheme, auxiliary mechanical stirring or electromagnetic stirring is adopted for stirring, the rotating speed is 40-80 r/min, the prefabricated block is melted, and the carbon nano tubes enter the aluminum melt.
According to the scheme, the smelting temperature is 600-800 ℃, and the time is 10-30 min; the standing time is 10-30 min.
According to the scheme, the mass ratio of the carbon nanotubes in the carbon nanotube reinforced aluminum matrix composite is 1-3 wt.%.
The invention has the beneficial effects that:
1) the invention adopts potassium fluoroaluminate and the like as smelting aids, and prepares the carbon nano tube reinforced aluminum matrix composite by a bell jar briquetting casting method after ball milling and mixing with the carbon nano tube and the aluminum powder. The carbon nano tube is embedded into the aluminum particles in advance, so that the problem of floating of the carbon nano tube caused by property difference between the carbon nano tube and the aluminum particles is solved, and meanwhile, the potassium fluoroaluminate can improve the surface tension of the carbon nano tube, eliminate an existing oxide film and improve the wettability of the carbon nano tube and the interface bonding strength between the carbon nano tube and an aluminum base;
2) the smelting process of the invention realizes the high-efficiency dispersion of the carbon nano-tubes in the smelting process, can continue to use the traditional metal smelting equipment, has the characteristics of simple process, low investment, high product strength and the like, and is suitable for industrial batch production.
Drawings
FIG. 1 is a SEM photograph of a carbon nanotube-aluminum mixed powder of example 1 of the present invention;
fig. 2 is a true stress-strain curve of the carbon nanotube-reinforced aluminum matrix composite of example 1 of the present invention.
Detailed Description
The technical solution of the present invention is described below with reference to the accompanying drawings and examples.
Example 1, see fig. 1-2:
the invention provides a smelting process of a carbon nano tube reinforced aluminum matrix composite, which comprises the following steps:
(1) weighing a certain amount of 50g K3AlF650g of carbon nano tubes and 400g of aluminum powder are subjected to ball milling, mixing and dispersing for 5 hours in a planetary ball mill, wherein a ball milling medium is agate balls, and the rotating speed is 400r/min, so that carbon nano tube-aluminum mixed powder with the mass fraction of the carbon nano tubes of 10 wt.% is obtained;
(2) putting the mixed powder into a mould, and cold-pressing and molding under the pressure of 200MPa to obtain a prefabricated block with the diameter of 60mm multiplied by 20mm, thereby obtaining a carbon nano tube-aluminum prefabricated block;
(3) pressing the carbon nano tube-aluminum precast block into the molten aluminum through a bell jar, slowly stirring the molten aluminum (60 r/min), and smelting at 700 ℃ for 10min in a heat preservation manner, so that the precast block is dissolved and enters the molten aluminum; and standing the melt for 10min after stirring is finished, removing scum and oxides on the liquid surface, and quickly casting the melt into a preheated metal mold to obtain an aluminum-based composite material ingot with the mass fraction of the carbon nano tubes being 1 wt.%.
The materials in this example were characterized and the results are shown in fig. 1-2. The SEM image of the carbon nanotube-aluminum mixed powder prepared in step (1) is shown in FIG. 1, and it can be seen from FIG. 1 that the smelting auxiliary K3AlF6(KBF4、K2TiF6Or Na3AlF6) Under the impact, friction and shearing action of the ball milling medium, the aluminum alloy particles are subjected to deformation, cold welding, crushing and other processes, so that the carbon nanotubes are fully dispersed and embedded into the deformed aluminum alloy particles. The obtained carbon nanotube-aluminum mixed powder is pressed into a block, pressed into an aluminum melt through a graphite bell jar and assisted with mechanical stirring. The true stress-strain curve of the prepared carbon nanotube reinforced aluminum matrix composite is shown in figure 2, at K3AlF6Under the action of the smelting auxiliary agent, the oxide film on the interface of the carbon nano tube and the aluminum melt is stretched and widened, so that the dissociation and dissolution of the aluminum oxide film are promoted, and then the aluminum melt infiltrates into the aluminum particles through the capillary tube to form strong interface combination, thereby playing an effective mutual lapping and strengthening role between crystal grains. Compared with the method without adopting potassium fluoroaluminate, the potassium fluoroaluminate improves the tensile strength of the carbon nanotube reinforced aluminum matrix composite material by more than 30 percent, and maintains better shaping.
Example 2:
the invention provides a smelting process of a carbon nano tube reinforced aluminum matrix composite, which comprises the following steps:
(1) weighing a certain amount of 50g Na3AlF650g of carbon nano tubes and 400g of aluminum powder are subjected to ball milling, mixing and dispersing for 5 hours in a planetary ball mill, wherein a ball milling medium is agate balls, and the rotating speed is 400r/min, so that carbon nano tube-aluminum mixed powder with the mass fraction of the carbon nano tubes of 10 wt.% is obtained;
(2) putting the mixed powder into a mould, and cold-pressing and molding under the pressure of 200MPa to obtain a prefabricated block with the diameter of 60mm multiplied by 40mm, thereby obtaining a carbon nano tube-aluminum prefabricated block;
(3) pressing the carbon nano tube-aluminum precast block into the molten aluminum through a bell jar, slowly stirring the molten aluminum (60 r/min), and smelting at 750 ℃ for 10min in a heat preservation manner to dissolve the precast block and enter the molten aluminum; and standing the melt for 10min after stirring is finished, removing scum and oxides on the liquid surface, and quickly casting the melt into a preheated metal mold to obtain an aluminum-based composite material ingot with the mass fraction of the carbon nano tubes being 2 wt.%.
Example 3:
the invention provides a smelting process of a carbon nanotube reinforced aluminum matrix composite, which is basically the same as that in example 1, and is characterized in that: the smelting auxiliary agent is KBF4
Example 4:
the invention provides a smelting process of a carbon nanotube reinforced aluminum matrix composite, which is basically the same as that in example 1, and is characterized in that: the aluminum matrix is 6061 aluminum alloy.
The above embodiments are only used for illustrating but not limiting the technical solutions of the present invention, and although the above embodiments describe the present invention in detail, those skilled in the art should understand that: modifications and equivalents may be made thereto without departing from the spirit and scope of the invention and any modifications and equivalents may fall within the scope of the claims.

Claims (6)

1. A smelting process of a carbon nano tube reinforced aluminum matrix composite is characterized by comprising the following steps:
(1) carrying out ball milling, mixing and dispersing on the smelting auxiliary agent, the carbon nano tube and the aluminum/aluminum alloy powder in a planetary ball mill to obtain mixed powder;
(2) putting the mixed powder into a die for cold pressing to obtain a carbon nano tube-aluminum/aluminum alloy prefabricated block;
(3) pressing the carbon nano tube-aluminum/aluminum alloy prefabricated block into molten aluminum through a bell jar, smelting under stirring, standing and then casting and forming;
the smelting auxiliary agent is KBF4、K2TiF6、K3AlF6Or Na3AlF6Any one of the carbon nanotubes and the aluminum/aluminum alloy powder is subjected to ball milling and mixing according to the mass ratio of 1:1: 8.
2. The melting process of the carbon nanotube reinforced aluminum matrix composite according to claim 1, wherein the medium during ball milling is steel balls or agate balls, the rotating speed is 200-500 r/min, and the ball milling time is 3-8 h.
3. The melting process of the carbon nanotube reinforced aluminum matrix composite according to claim 1, wherein the pressing force during cold pressing is 100-300 MPa.
4. The melting process of the carbon nanotube reinforced aluminum matrix composite according to claim 1, wherein the stirring is assisted by mechanical stirring or electromagnetic stirring, and the rotating speed is 40-80 r/min.
5. The melting process of the carbon nanotube reinforced aluminum matrix composite according to claim 1, wherein the melting temperature is 600-800 ℃ and the time is 10-30 min; the standing time is 10-30 min.
6. The melting process of the carbon nanotube-reinforced aluminum-based composite material according to claim 1, wherein the mass ratio of the carbon nanotubes in the carbon nanotube-reinforced aluminum-based composite material is 1 to 3 wt.%.
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CN113444906B (en) * 2021-06-10 2023-06-16 湘潭大学 Method for preparing carbon nano tube reinforced light aluminum-based alloy
CN114318042A (en) * 2021-12-28 2022-04-12 贵阳华恒机械制造有限公司 Carbon nano tube reinforced cast ZL105 alloy material and preparation method thereof
CN115415516A (en) * 2022-07-06 2022-12-02 湖南文昌新材科技股份有限公司 Carbon nano tube reinforced aluminum matrix composite precursor preparation device

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CN105568034A (en) * 2015-12-17 2016-05-11 华南理工大学 Granular mixed reinforced aluminum-based composite material and method for preparing same
CN110229969A (en) * 2019-07-05 2019-09-13 西安交通大学 A kind of the nano-TiC particle reinforced aluminum matrix composites and method of melting-reaction method preparation

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