CN112024896B - Preparation method of CNTs-ZA27 zinc-aluminum-based composite bar with high C content - Google Patents

Preparation method of CNTs-ZA27 zinc-aluminum-based composite bar with high C content Download PDF

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CN112024896B
CN112024896B CN202011114468.5A CN202011114468A CN112024896B CN 112024896 B CN112024896 B CN 112024896B CN 202011114468 A CN202011114468 A CN 202011114468A CN 112024896 B CN112024896 B CN 112024896B
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ball milling
zinc
aluminum
powder
cnts
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CN112024896A (en
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刘洋
罗浩宇
孙天友
苗华磊
朱戴博
杨岳云
王兴
刘志伟
李萌萌
韩石磊
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Xiangtan University
Zhuzhou Smelter Group Co Ltd
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Xiangtan University
Zhuzhou Smelter Group Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
    • C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
    • C22C49/04—Light metals
    • C22C49/06—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/17—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging
    • B22F2003/175—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by forging by hot forging, below sintering temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

Abstract

A preparation method of a CNTs-ZA27 zinc-aluminum based composite bar with high C content relates to a preparation method of a ZA27 composite bar. The invention aims to solve the problems that the carbon nano tube in the carbon nano tube reinforced zinc-aluminum matrix composite prepared by the existing method is not uniformly dispersed, the strength and toughness of the carbon nano tube reinforced zinc-aluminum matrix composite are not obviously improved due to structural damage, and the deformability is poor. The method comprises the following steps: 1. mixing materials; 2. low-temperature high-speed ball milling; 3. performing low-speed ball milling; 4. warm-pressing and forming; 5. and (3) performing powder forging to obtain the CNTs-ZA27 zinc-aluminum-based composite bar with the diameter of 20-60 mm and the high C content. The CNTs-ZA27 zinc-aluminum-based composite bar with high C content prepared by the method has compact structure, and the wear resistance and the corrosion resistance are greatly improved compared with the conventional ZA 27. The invention can obtain the CNTs-ZA27 zinc-aluminum-based composite bar with high C content.

Description

Preparation method of CNTs-ZA27 zinc-aluminum-based composite bar with high C content
Technical Field
The invention relates to a preparation method of a ZA27 composite bar.
Background
In terms of mechanical properties, the ZA27 alloy has the characteristics of light weight, high strength, high hardness, good friction and wear properties, good bearing capacity, good ductility, no magnetism and no spark generation in collision, and has the advantages of low ZA27 raw material cost, simple forming process and lower smelting and processing cost in an economic angle. The ZA27 alloy is used to replace traditional copper alloy parts for making bearing bush, worm wheel, slide block and other wear-resisting parts, resulting in excellent economic and social benefits.
At present, the production process of the ZA27 alloy bar mainly comprises ingot casting and rolling deformation, molten zinc-aluminum alloy is poured into a casting mold, a solid ingot is obtained after cooling, a surface oxide layer is removed, and rolling deformation is carried out to obtain the zinc-aluminum alloy bar or plate.
The Carbon Nano Tubes (CNTs) are a nano material with a hollow structure, and have the characteristics of small density, high strength, large specific surface area, high-temperature stability, high electrical conductivity and thermal conductivity, low thermal expansion coefficient, strong acid, strong alkali and high-temperature oxidation resistance, however, the CNTs are easy to agglomerate, the dispersion effect of the traditional ball milling mixing process is extremely limited, the traditional ball milling mixing process has better dispersion effect by adopting a planetary ball mill and a horizontal stirring ball mill, but the output energy and the ball milling efficiency are higher, and the structural integrity damage of the CNTs is easy to cause.
Disclosure of Invention
The invention aims to solve the problems that the carbon nano tube in the carbon nano tube reinforced zinc-aluminum-based composite material prepared by the existing method is not uniformly dispersed, the strength and toughness of the carbon nano tube reinforced zinc-aluminum-based composite material are not obviously improved due to structural damage, and the deformability is poor, and provides the preparation method of the CNTs-ZA27 zinc-aluminum-based composite rod with high C content.
A preparation method of a CNTs-ZA27 zinc-aluminum based composite bar with high C content is completed according to the following steps:
1. uniformly mixing a mixture of zinc powder and aluminum powder with a carbon nano tube to obtain mixed powder; adding the grinding balls and the mixed powder into a ball milling tank, and sealing the ball milling tank;
the mass fraction of the carbon nano tubes in the mixed powder in the step one is 0.01-0.5%;
the mass ratio of the mixed powder to the grinding ball in the first step is 1 (5-15);
the mass fraction of the aluminum powder in the mixture of the zinc powder and the aluminum powder in the step one is 25-28%;
2. high-speed low-temperature ball milling:
vacuumizing the sealed ball-milling tank, injecting liquid nitrogen or liquid argon into the ball-milling tank with the vacuum degree of-0.07 to-0.09 MPa, and performing ball milling under the protection of the liquid nitrogen or the liquid argon to finish high-speed ball milling;
the ball milling rotating speed in the step two is 450 r/min-800 r/min;
3. low-speed ball milling:
firstly, standing a ball milling tank which finishes high-speed ball milling, then releasing pressure of the ball milling tank, opening the ball milling tank, adding a lubricant into the ball milling tank, sealing the ball milling tank, vacuumizing the sealed ball milling tank, and finally performing ball milling under the vacuum degree of-0.07 to-0.09 MPa to obtain mixed powder containing the lubricant;
the ball milling rotating speed in the third step is 50 r/min-200 r/min;
the mass ratio of the lubricant to the mixed powder in the ball milling tank in the third step is (1-5) to 100;
4. warm-pressing and forming:
firstly, injecting mixed powder containing a lubricant into a mold, then pressing at the temperature of 100-150 ℃ and the pressure of 450-650 MPa, and finally maintaining the pressure at the temperature of 100-150 ℃ to obtain a rod-shaped green body with the diameter of 15-45 mm;
5. powder forging:
carrying out vacuum sintering on the bar-shaped green body with the diameter of 15-45 mm in a vacuum furnace at the temperature of 420-480 ℃ for 120-480 min to obtain a vacuum sintered bar-shaped green body; heating the bar-shaped green body after vacuum sintering to 300-380 ℃, and then forging the bar-shaped green body under the argon atmosphere at the temperature of 300-380 ℃ to obtain the CNTs-ZA27 zinc-aluminum based composite bar with the high C content and the diameter of 20-60 mm.
The invention provides a preparation method of a CNTs-ZA27 zinc-aluminum based composite bar with high C content, which adopts low-temperature mechanical alloying, variable-speed ball milling, warm compaction and powder forging. Compared with the traditional Mg and Al-CNTs product preparation method, the method has the following advantages:
(1) The low-temperature mechanical alloying is a high-energy ball milling process, which is to ball mill the alloy powder in a low-temperature medium (such as liquid nitrogen, liquid argon and the like) or in a low-temperature environment. Meanwhile, the low temperature changes the characteristic of powder deformation dynamics, increases the microhardness of powder particles, strengthens the powder, reduces the ductility, makes the cold welding process more difficult, and improves the dispersion probability of CNTs in the alloy powder;
(2) The variable speed ball milling is to match the high speed ball milling with the low speed ball milling to uniformly disperse the CNTs into the matrix powder on the premise of not damaging the structural integrity of the CNTs, so that the final strengthening of the alloy tends to be ideal;
(3) Adding a lubricant into the mixed powder subjected to high-speed ball milling, then carrying out low-speed ball milling, and then carrying out warm-pressing forming, wherein the process enables the powder particles to be rearranged under the action of temperature and pressure, so that the plastic deformation of the powder particles is improved, compared with a cold pressing method, the method can greatly improve the densification degree of a powder metallurgy product, and the density can reach 98%; the problems that the ZA27 is hard and brittle and difficult to deform greatly after the CNTs reinforcement is added are solved;
(4) The powder forging is a method for forging and forming a prefabricated blank on a press at one time and realizing flash-free precision die forging, and the invention can forge a sintered body with 80 percent of theoretical density to nearly 100 percent of theoretical density;
(5) The CNTs-ZA27 zinc-aluminum-based composite bar with high C content prepared by the method has compact structure, and the wear resistance and the corrosion resistance are greatly improved compared with the conventional ZA 27.
Drawings
FIG. 1 is a flow chart of a process for preparing a high C content CNTs-ZA27 zinc-aluminum based composite rod according to the first embodiment;
FIG. 2 is an SEM photograph of a lubricant-containing mixed powder prepared at a high speed for a short time in one comparative example;
FIG. 3 is an SEM photograph of a mixed powder containing a lubricant prepared at a low speed and a long time in the second comparative example;
FIG. 4 is a low magnification SEM photograph of a mixed powder containing a lubricant prepared in step three of the first example;
fig. 5 is a high-magnification SEM image of the mixed powder containing the lubricant prepared in step three of example one.
Detailed Description
The following examples further illustrate the present invention but are not to be construed as limiting the invention. Modifications and substitutions to methods, procedures, or conditions of the invention may be made without departing from the spirit of the invention.
The first embodiment is as follows: the embodiment is a preparation method of a CNTs-ZA27 zinc-aluminum-based composite bar with high C content, which is completed according to the following steps:
1. uniformly mixing a mixture of zinc powder and aluminum powder with a carbon nano tube to obtain mixed powder; adding the grinding balls and the mixed powder into a ball milling tank, and sealing the ball milling tank;
the mass fraction of the carbon nano tubes in the mixed powder in the step one is 0.01-0.5%;
the mass ratio of the mixed powder to the grinding ball in the first step is 1 (5-15);
the mass fraction of the aluminum powder in the mixture of the zinc powder and the aluminum powder in the step one is 25-28%;
2. high-speed low-temperature ball milling:
vacuumizing the sealed ball-milling tank, injecting liquid nitrogen or liquid argon into the ball-milling tank with the vacuum degree of-0.07 to-0.09 MPa, and performing ball milling under the protection of the liquid nitrogen or the liquid argon to finish high-speed ball milling;
the ball milling rotating speed in the step two is 450 r/min-800 r/min;
3. low-speed ball milling:
firstly, standing a ball milling tank which finishes high-speed ball milling, then releasing pressure of the ball milling tank, opening the ball milling tank, adding a lubricant into the ball milling tank, sealing the ball milling tank, vacuumizing the sealed ball milling tank, and finally performing ball milling under the vacuum degree of-0.07 to-0.09 MPa to obtain mixed powder containing the lubricant;
the ball milling rotating speed in the third step is 50 r/min-200 r/min;
the mass ratio of the lubricant to the mixed powder in the ball milling tank in the third step is (1-5) to 100;
4. warm-pressing and forming:
firstly, injecting mixed powder containing a lubricant into a mold, then pressing at the temperature of 100-150 ℃ and the pressure of 450-650 MPa, and finally maintaining the pressure at the temperature of 100-150 ℃ to obtain a rod-shaped green body with the diameter of 15-45 mm;
5. powder forging:
carrying out vacuum sintering on the bar-shaped green body with the diameter of 15-45 mm in a vacuum furnace at the temperature of 420-480 ℃ for 120-480 min to obtain a vacuum sintered bar-shaped green body; heating the bar-shaped green body after vacuum sintering to 300-380 ℃, and then forging the bar-shaped green body in an argon atmosphere at the temperature of 300-380 ℃ to obtain the CNTs-ZA27 zinc-aluminum-based composite bar with the diameter of 20-60 mm and high C content.
The embodiment provides a preparation method of a CNTs-ZA27 zinc-aluminum-based composite bar with high C content, which adopts low-temperature mechanical alloying, variable-speed ball milling, warm compaction and powder forging. Compared with the traditional Mg and Al-CNTs product preparation method, the method has the following advantages:
(1) The low-temperature mechanical alloying is a high-energy ball milling process, which is to ball mill alloy powder in a low-temperature medium (such as liquid nitrogen, liquid argon and the like) or in a low-temperature environment. Meanwhile, the low temperature changes the characteristic of powder deformation dynamics, increases the microhardness of powder particles, strengthens the powder, reduces the ductility, makes the cold welding process more difficult, and improves the dispersion probability of CNTs in the alloy powder;
(2) The variable speed ball milling is to match the high speed ball milling with the low speed ball milling to uniformly disperse the CNTs into the matrix powder on the premise of not damaging the structural integrity of the CNTs, so that the final strengthening of the alloy tends to be ideal;
(3) Adding a lubricant into the mixed powder subjected to high-speed ball milling, then carrying out low-speed ball milling, and then carrying out warm-pressing forming, wherein the process enables the powder particles to be rearranged under the action of temperature and pressure, so that the plastic deformation of the powder particles is improved, compared with a cold pressing method, the implementation method can greatly improve the densification degree of the powder metallurgy product, and the density can reach 98%; the problems that the ZA27 is hard and brittle and difficult to deform greatly after the CNTs reinforcement is added are solved;
(4) The powder forging is a method for forging and forming a prefabricated blank on a press at one time and realizing flash-free precision die forging, and the embodiment can forge a sintered body with 80% of theoretical density to nearly 100% of theoretical density;
(5) The CNTs-ZA27 zinc-aluminum-based composite bar with high C content prepared by the embodiment has compact structure, and the wear resistance and the corrosion resistance are greatly improved compared with the conventional ZA 27.
The mixture of zinc powder and aluminum powder in the first step of this embodiment is formed by mixing pure zinc powder and pure aluminum powder.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: in the mixture of the zinc powder and the aluminum powder in the step one, the particle size of the zinc powder is 200-500 meshes, and the particle size of the aluminum powder is 200-500 meshes. Other steps are the same as in the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the grinding ball in the step one is a hard alloy ball. The other steps are the same as in the first or second embodiment.
The fourth concrete implementation mode is as follows: the difference between this embodiment and one of the first to third embodiments is as follows: the ball milling time in the step two is 15 min-60 min. The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and the first to the fourth embodiments is: the ball milling time in the third step is 240-540 min. The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: the standing time in the third step is 2 min-5 min. The other steps are the same as those in the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and the first to sixth embodiments is: the loading speed of the pressing in the fourth step is 2-40 mm/s, and the pressure maintaining time is 60-180 s. The other steps are the same as those in the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: the lubricant in the third step is one or a mixture of several of polyamide, polyimide, polyether imide, polyether, polysulfone, cellulose ester, thermoplastic phenolic resin, polyethylene glycol and polyvinyl alcohol. The other steps are the same as those in the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: in the fourth step, the mixed powder containing the lubricant is firstly injected into a mould, then the mould is pressed at the temperature of 100-120 ℃ and the pressure of 500-600 MPa, and finally the pressure is maintained at the temperature of 100-120 ℃ to obtain the rod-shaped green body with the diameter of 15-45 mm. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: step five, performing vacuum sintering on the bar-shaped green body with the diameter of 15-45 mm in a vacuum furnace at the temperature of 460-480 ℃ for 360-420 min to obtain a vacuum sintered bar-shaped green body; heating the bar-shaped green body after vacuum sintering to 300-380 ℃, and then forging the bar-shaped green body in an argon atmosphere at the temperature of 300-380 ℃ to obtain the CNTs-ZA27 zinc-aluminum-based composite bar with the diameter of 20-60 mm and high C content. The other steps are the same as those in the first to ninth embodiments.
The present invention will be described in detail below with reference to the drawings and examples.
The first embodiment is as follows: a preparation method of a CNTs-ZA27 zinc-aluminum based composite bar with high C content is completed according to the following steps:
1. uniformly mixing a mixture of zinc powder and aluminum powder with a carbon nano tube to obtain mixed powder; adding the grinding balls and the mixed powder into a ball milling tank, and sealing the ball milling tank;
in the mixture of the zinc powder and the aluminum powder in the step one, the particle size of the zinc powder is 400 meshes, and the particle size of the aluminum powder is 400 meshes;
the grinding ball in the step one is a hard alloy ball;
the mass fraction of the carbon nano tubes in the mixed powder in the step one is 0.05 percent;
the mass ratio of the mixed powder to the grinding balls in the step one is 1:7;
the mass fraction of the aluminum powder in the mixture of the zinc powder and the aluminum powder in the step one is 27%;
2. high-speed low-temperature ball milling:
vacuumizing the sealed ball-milling tank, injecting liquid nitrogen into the ball-milling tank with the vacuum degree of-0.09 MPa, and performing ball milling under the protection of the liquid nitrogen to finish high-speed ball milling;
the ball milling rotating speed in the step two is 500r/min; the ball milling time in the step two is 30min;
3. low-speed ball milling:
firstly, standing a ball milling tank which finishes high-speed ball milling, then releasing pressure of the ball milling tank, opening the ball milling tank, adding a lubricant into the ball milling tank, sealing the ball milling tank, vacuumizing the sealed ball milling tank, and finally performing ball milling under the vacuum degree of-0.09 MPa to obtain mixed powder containing the lubricant;
the ball milling rotating speed in the third step is 150r/min; the ball milling time in the third step is 300min;
the mass ratio of the lubricant to the mixed powder in the ball milling tank in the third step is 1;
the standing time in the third step is 2 min-5 min;
the lubricant in the third step is a mixture of polyamide and thermoplastic phenolic resin; the mass ratio of the polyamide to the thermoplastic phenolic resin in the lubricant is 1:1;
4. warm-pressing and forming:
firstly, injecting mixed powder containing a lubricant into a die, then pressing at the temperature of 120 ℃, the pressing loading speed of 30mm/s and the pressure of 500MPa, and finally maintaining the pressure at the temperature of 120 ℃ to obtain a rod-shaped green body with the diameter of 15 mm;
the pressure maintaining time in the fourth step is 120s;
5. powder forging:
carrying out vacuum sintering on the bar-shaped green body with the diameter of 15mm in a vacuum furnace, wherein the temperature of the vacuum sintering is 460 ℃, and the time of the vacuum sintering is 360min, so as to obtain the bar-shaped green body after the vacuum sintering; heating the bar-shaped green body after vacuum sintering to 380 ℃, and then forging the bar-shaped green body at the temperature of 350 ℃ in an argon atmosphere to obtain the CNTs-ZA27 zinc-aluminum-based composite bar with the diameter of 20mm and high C content.
FIG. 1 is a flow chart of a process for preparing a high C content CNTs-ZA27 zinc-aluminum based composite rod as described in example one.
The properties of the CNTs-ZA27 zinc-aluminum based composite rod with high C content and the diameter of 20mm prepared in the first embodiment are shown in Table 1.
TABLE 1
Tensile strength (MPa) 482
Yield strength (MPa) 406
Elongation after rupture (%) 27.3
Wear Rate (. Times.10) -5 mm 3 N -1 m -1 ) 2.73
Comparative example one: the high-speed short-time preparation of mixed powder containing lubricant is completed according to the following steps:
1. uniformly mixing a mixture of zinc powder and aluminum powder with a carbon nano tube to obtain mixed powder; adding the grinding balls and the mixed powder into a ball milling tank;
in the mixture of the zinc powder and the aluminum powder in the step one, the particle size of the zinc powder is 400 meshes, and the particle size of the aluminum powder is 400 meshes;
the grinding ball in the step one is a hard alloy ball;
the mass fraction of the carbon nano tubes in the mixed powder in the step one is 0.05 percent;
the mass ratio of the mixed powder to the grinding balls in the step one is 1:7;
the mass fraction of the aluminum powder in the mixture of the zinc powder and the aluminum powder in the step one is 27%;
2. adding a lubricant into the ball milling tank, sealing the ball milling tank, vacuumizing the sealed ball milling tank, and finally performing ball milling under the vacuum degree of-0.07 to-0.09 MPa to obtain mixed powder containing the lubricant;
the ball milling rotating speed in the step two is 500r/min; the ball milling time in the step two is 30min;
the lubricant in the second step is a mixture of polyamide and thermoplastic phenolic resin; the mass ratio of polyamide to phenolic resin in the lubricant is 1:1.
Comparative example two: the preparation of the mixed powder containing the lubricant at low speed and long time is completed according to the following steps:
1. uniformly mixing a mixture of zinc powder and aluminum powder with a carbon nano tube to obtain mixed powder; adding the grinding balls and the mixed powder into a ball milling tank;
in the mixture of the zinc powder and the aluminum powder in the step one, the particle size of the zinc powder is 400 meshes, and the particle size of the aluminum powder is 400 meshes;
the grinding ball in the step one is a hard alloy ball;
the mass fraction of the carbon nano tubes in the mixed powder in the step one is 0.05 percent;
the mass ratio of the mixed powder to the grinding balls in the step one is 1:7;
the mass fraction of the aluminum powder in the mixture of the zinc powder and the aluminum powder in the step one is 27%;
2. adding a lubricant into the ball milling tank, sealing the ball milling tank, vacuumizing the sealed ball milling tank, and finally performing ball milling under the vacuum degree of-0.07 to-0.09 MPa to obtain mixed powder containing the lubricant;
the ball milling rotating speed in the step two is 200r/min; the ball milling time in the step two is 6 hours;
the lubricant in the second step is a mixture of polyamide and thermoplastic phenolic resin; the mass ratio of polyamide to phenolic resin in the lubricant is 1:1.
FIG. 2 is an SEM photograph of a lubricant-containing mixed powder prepared at a high speed for a short time in one comparative example;
FIG. 3 is an SEM photograph of a mixed powder containing a lubricant prepared at a low speed and a long time in the second comparative example;
FIG. 4 is a low-magnification SEM image of a mixed powder containing a lubricant prepared in step three of example one;
FIG. 5 is a high magnification SEM image of a lubricant-containing mixed powder prepared in step three of example one;
as can be seen from FIG. 2, when the ball milling time is short, the deformation of the metal matrix powder is small, and it is difficult to reliably bond CNTs.
As can be seen from fig. 3, when the ball milling rotation speed is insufficient, the CNTs are not broken into aggregates and are not uniformly dispersed in the metal matrix powder.
As can be seen from FIG. 4 and FIG. 5, in the first embodiment, CNTs aggregates are broken up by high-speed low-temperature ball milling and are uniformly dispersed in metal matrix powder, and then the metal matrix powder is pressed into sheets by low-speed long-time ball milling and is mechanically welded, so that the CNTs on the surface of the metal matrix powder are more tightly combined with metal, and the action of re-agglomeration of the CNTs in the operations of taking out the powder and the like is prevented.
Example two: a preparation method of a CNTs-ZA27 zinc-aluminum based composite bar with high C content is completed according to the following steps:
1. uniformly mixing a mixture of zinc powder and aluminum powder with a carbon nano tube to obtain mixed powder; adding the grinding balls and the mixed powder into a ball milling tank, and sealing the ball milling tank;
in the mixture of the zinc powder and the aluminum powder in the step one, the particle size of the zinc powder is 400 meshes, and the particle size of the aluminum powder is 400 meshes;
the grinding ball in the step one is a hard alloy ball;
the mass fraction of the carbon nano tubes in the mixed powder in the step one is 0.15%;
the mass ratio of the mixed powder to the grinding balls in the step one is 1;
the mass fraction of the aluminum powder in the mixture of the zinc powder and the aluminum powder in the step one is 27%;
2. high-speed low-temperature ball milling:
vacuumizing the sealed ball milling tank, injecting liquid nitrogen into the ball milling tank with the vacuum degree of-0.09 MPa, and performing ball milling under the protection of liquid nitrogen to finish high-speed ball milling;
the ball milling rotating speed in the step two is 750r/min; the ball milling time in the step two is 15min;
3. low-speed ball milling:
firstly, standing a ball milling tank which finishes high-speed ball milling, then releasing pressure of the ball milling tank, opening the ball milling tank, adding a lubricant into the ball milling tank, sealing the ball milling tank, vacuumizing the sealed ball milling tank, and finally performing ball milling under the vacuum degree of-0.09 MPa to obtain mixed powder containing the lubricant;
the ball milling rotating speed in the third step is 100r/min; the ball milling time in the third step is 360min;
the mass ratio of the lubricant to the mixed powder in the ball milling tank in the third step is 2:100, respectively;
the standing time in the third step is 3min;
the lubricant in the third step is thermoplastic phenolic resin;
4. warm-pressing and forming:
firstly, injecting mixed powder containing a lubricant into a die, then pressing at the temperature of 120 ℃, the pressing loading speed of 30mm/s and the pressure of 600MPa, and finally maintaining the pressure at the temperature of 120 ℃ to obtain a rod-shaped green body with the diameter of 25 mm;
the pressure maintaining time in the fourth step is 60s;
5. powder forging:
carrying out vacuum sintering on the bar-shaped green body with the diameter of 25mm in a vacuum furnace, wherein the temperature of the vacuum sintering is 480 ℃, and the time of the vacuum sintering is 420min, so as to obtain the bar-shaped green body after the vacuum sintering; heating the rod-shaped green body after vacuum sintering to 360 ℃, and then forging the rod-shaped green body at the temperature of 330 ℃ in an argon atmosphere to obtain the CNTs-ZA27 zinc-aluminum-based composite rod with the diameter of 30mm and high C content.
The properties of the CNTs-ZA27 zinc-aluminum based composite rods with high C content and 20mm diameter prepared in the second embodiment are shown in Table 2.
TABLE 2
Tensile strength (MPa) 502
Yield strength (MPa) 417
Elongation after rupture (%) 25.9
Wear Rate (. Times.10) -5 mm 3 N -1 m -1 ) 2.29
Example three: a preparation method of a CNTs-ZA27 zinc-aluminum based composite bar with high C content is completed according to the following steps:
1. uniformly mixing a mixture of zinc powder and aluminum powder with a carbon nano tube to obtain mixed powder; adding the grinding balls and the mixed powder into a ball milling tank, and sealing the ball milling tank;
in the mixture of the zinc powder and the aluminum powder in the step one, the particle size of the zinc powder is 400 meshes, and the particle size of the aluminum powder is 400 meshes;
the grinding ball in the step one is a hard alloy ball;
the mass fraction of the carbon nano tubes in the mixed powder in the step one is 0.15%;
the mass ratio of the mixed powder to the grinding balls in the step one is 1:7;
the mass fraction of the aluminum powder in the mixture of the zinc powder and the aluminum powder in the step one is 27%;
2. high-speed low-temperature ball milling:
vacuumizing the sealed ball milling tank, injecting liquid nitrogen into the ball milling tank with the vacuum degree of-0.09 MPa, and performing ball milling under the protection of liquid nitrogen to finish high-speed ball milling;
the ball milling rotating speed in the step two is 600r/min; the ball milling time in the step two is 30min;
3. low-speed ball milling:
firstly, standing a ball milling tank which finishes high-speed ball milling, then releasing pressure of the ball milling tank, opening the ball milling tank, adding a lubricant into the ball milling tank, sealing the ball milling tank, vacuumizing the sealed ball milling tank, and finally performing ball milling under the vacuum degree of-0.09 MPa to obtain mixed powder containing the lubricant;
the ball milling rotating speed in the third step is 200r/min; the ball milling time in the third step is 360min;
the mass ratio of the lubricant to the mixed powder in the ball milling tank in the third step is 1;
the standing time in the third step is 5min;
the lubricant in the third step is thermoplastic phenolic resin;
4. warm-pressing and forming:
firstly, injecting mixed powder containing a lubricant into a die, then pressing at the temperature of 120 ℃, the pressing loading speed of 30mm/s and the pressure of 600MPa, and finally maintaining the pressure at the temperature of 120 ℃ to obtain a rod-shaped green body with the diameter of 30 mm;
the pressure maintaining time in the step four is 180s;
5. powder forging:
carrying out vacuum sintering on the bar-shaped green body with the diameter of 30mm in a vacuum furnace, wherein the temperature of the vacuum sintering is 460 ℃, and the time of the vacuum sintering is 360min, so as to obtain the bar-shaped green body after the vacuum sintering; heating the bar-shaped green body after vacuum sintering to 350 ℃, and then forging the bar-shaped green body at the temperature of 320 ℃ in an argon atmosphere to obtain the CNTs-ZA27 zinc-aluminum-based composite bar with the diameter of 35mm and high C content.
The properties of the CNTs-ZA27 zinc-aluminum based composite rod with high C content and the diameter of 20mm prepared by the third preparation method are listed in Table 3.
TABLE 3
Tensile strength (MPa) 514
Yield strength (MPa) 425
Elongation after rupture (%) 24.7
Wear Rate (. Times.10) -5 mm 3 N -1 m -1 ) 1.96

Claims (6)

1. A preparation method of a CNTs-ZA27 zinc-aluminum-based composite bar with high C content is characterized in that the preparation method of the CNTs-ZA27 zinc-aluminum-based composite bar with high C content is completed according to the following steps:
1. uniformly mixing a mixture of zinc powder and aluminum powder with a carbon nano tube to obtain mixed powder; adding the grinding balls and the mixed powder into a ball milling tank, and sealing the ball milling tank;
the mass fraction of the carbon nano tubes in the mixed powder in the step one is 0.01-0.5%;
the mass ratio of the mixed powder to the grinding ball in the first step is 1 (5-15);
the mass fraction of the aluminum powder in the mixture of the zinc powder and the aluminum powder in the step one is 25-28%;
2. high-speed low-temperature ball milling:
vacuumizing the sealed ball-milling tank, injecting liquid nitrogen or liquid argon into the ball-milling tank with the vacuum degree of-0.07 to-0.09 MPa, and performing ball milling under the protection of the liquid nitrogen or the liquid argon to finish high-speed ball milling;
the ball milling rotating speed in the step two is 500 r/min-800 r/min;
the ball milling time in the step two is 15 min-60 min;
3. low-speed ball milling:
firstly, standing a ball milling tank which finishes high-speed ball milling, then releasing pressure of the ball milling tank, opening the ball milling tank, adding a lubricant into the ball milling tank, sealing the ball milling tank, vacuumizing the sealed ball milling tank, and finally performing ball milling under the vacuum degree of-0.07 to-0.09 MPa to obtain mixed powder containing the lubricant;
the ball milling rotating speed in the third step is 50 r/min-200 r/min;
the ball milling time in the third step is 240 min-540 min;
the mass ratio of the lubricant to the mixed powder in the ball milling tank in the third step is (1-5) to 100;
the lubricant in the third step is one or a mixture of several of polyamide, polyimide, polyether imide, polyether, polysulfone, cellulose ester, thermoplastic phenolic resin, polyethylene glycol and polyvinyl alcohol;
4. warm-pressing and forming:
firstly, injecting mixed powder containing a lubricant into a mold, then pressing at 100-150 ℃ and 450-650 MPa, and finally maintaining the pressure at 100-150 ℃ to obtain a rod-shaped green body with the diameter of 15-45 mm;
the loading speed of the pressing in the step four is 2-40 mm/s, and the pressure maintaining time is 60-180 s;
5. powder forging:
carrying out vacuum sintering on the rod-shaped blank with the diameter of 15-45 mm in a vacuum furnace at the temperature of 420-480 ℃ for 120-480 min to obtain a vacuum sintered rod-shaped blank; heating the bar-shaped green body after vacuum sintering to 300-380 ℃, and then forging the bar-shaped green body in an argon atmosphere at the temperature of 300-380 ℃ to obtain the CNTs-ZA27 zinc-aluminum-based composite bar with the diameter of 20-60 mm and high C content.
2. The method of claim 1, wherein the mixture of zinc powder and aluminum powder in step one has a particle size of 200-500 mesh, and the aluminum powder has a particle size of 200-500 mesh.
3. The method for preparing a high-C content CNTs-ZA27 zinc-aluminum based composite bar according to claim 1, characterized in that the grinding balls in step one are cemented carbide balls.
4. The method for preparing the CNTs-ZA27 zinc-aluminum based composite bar with high C content according to claim 1, wherein the standing time in the third step is 2min to 5min.
5. The method for preparing the CNTs-ZA27 zinc-aluminum based composite bar with high C content according to claim 1, wherein the step four is to inject the mixed powder containing the lubricant into the mold, then to press at 100-120 ℃ and 500-600 MPa, finally to maintain the pressure at 100-120 ℃ to obtain the bar-shaped green body with the diameter of 15-45 mm.
6. The method for preparing the CNTs-ZA27 zinc-aluminum based composite bar with high C content according to claim 1, wherein in the fifth step, a bar-shaped green body with a diameter of 15mm to 45mm is subjected to vacuum sintering in a vacuum furnace, the temperature of the vacuum sintering is 460 ℃ to 480 ℃, and the time of the vacuum sintering is 360min to 420min, so as to obtain a bar-shaped green body after the vacuum sintering; heating the bar-shaped green body after vacuum sintering to 300-380 ℃, and then forging the bar-shaped green body in an argon atmosphere at the temperature of 300-380 ℃ to obtain the CNTs-ZA27 zinc-aluminum-based composite bar with the diameter of 20-60 mm and high C content.
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