WO2020000615A1 - Metal composite material - Google Patents

Metal composite material Download PDF

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Publication number
WO2020000615A1
WO2020000615A1 PCT/CN2018/101941 CN2018101941W WO2020000615A1 WO 2020000615 A1 WO2020000615 A1 WO 2020000615A1 CN 2018101941 W CN2018101941 W CN 2018101941W WO 2020000615 A1 WO2020000615 A1 WO 2020000615A1
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Prior art keywords
ball milling
mixed powder
powder
metal composite
ball
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PCT/CN2018/101941
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French (fr)
Chinese (zh)
Inventor
樊璠
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樊璠
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Application filed by 樊璠 filed Critical 樊璠
Priority to US16/765,180 priority Critical patent/US20200347482A1/en
Priority to US16/560,962 priority patent/US20200002786A1/en
Publication of WO2020000615A1 publication Critical patent/WO2020000615A1/en

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
    • 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
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0408—Light metal alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/10—Alloys containing non-metals
    • C22C1/1084—Alloys containing non-metals by mechanical alloying (blending, milling)
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0084—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ carbon or graphite as the main non-metallic constituent
    • 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
    • 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
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/05—Light metals
    • B22F2301/058—Magnesium
    • 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
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/40—Carbon, graphite
    • 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
    • B22F2302/00—Metal Compound, non-Metallic compound or non-metal composition of the powder or its coating
    • B22F2302/40—Carbon, graphite
    • B22F2302/403—Carbon nanotube
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
    • C22C2026/002—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties
    • C22C2202/04—Hydrogen absorbing

Definitions

  • the invention relates to the technical field of new energy materials, in particular to a green metal composite material.
  • the amount of adsorption is also relatively low, between about 3-6 wt%, and the conditions are harsh, the temperature is 78K, and the pressure is 40bars.
  • activated carbon is cheap and easily available. If proper methods can be used to improve its performance, it has great application prospects.
  • the activated carbon is treated with nitric acid or NaOCl, and its hydrogen absorption amount and discharge amount when used as an electrode are significantly improved.
  • the reason why carbon nanotubes and nano-carbon fibers have become a popular hydrogen storage material is that their large hydrogen storage capacity generally reaches 10% by weight, and some even reach more than 60% by weight. But some scientists have tested this before, but it ended in failure.
  • the purpose of the present invention is to provide a green metal composite material, thereby overcoming the disadvantages of the prior art.
  • the present invention provides a green metal composite material, which is characterized in that the green metal composite material is prepared by the following method: providing Mg, Mo, Al, Ni, and Ti powder; according to a predetermined chemical formula, the Mg, Mo, Al, Ni, and Ti powders were weighed; Mg, Mo, Al, Ni, and Ti powders were weighed first to obtain a first mixed powder; and the first mixed powder was vacuum smelted to obtain a Mg-based alloy Ingots; crushing Mg-based alloy ingots; providing carbon nanotubes and graphene powders; surface modification of carbon nanotubes and graphene powders; crushing Mg-based alloy ingots and surface-modified carbon nanotubes and The graphene powder is mixed and subjected to a second ball milling to obtain a second mixed powder; the second mixed powder is subjected to a first heat treatment to obtain a third mixed powder; and the third mixed powder is subjected to a second hot-press sintering.
  • the first ball milling of Mg, Mo, Al, Ni, and Ti powders after the symmetrical weighting is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 1500-1800r / min, and the ball milling time is 10- In 20h, the ball-to-material ratio is 8: 1-9: 1.
  • the ball milling atmosphere is an argon atmosphere
  • the ball milling speed is 1500-1800r / min
  • the ball milling time is 10-
  • the ball-to-material ratio is 8: 1-9: 1.
  • each ball is milled for 60-70min, and the ball milling is suspended for 4-5min.
  • the temperature in the ball mill tank is controlled below 600 ° C.
  • the vacuum melting of the first mixed powder is specifically: the vacuum degree is lower than 0.01 Pa, the melting time is 80-100 min, and the alloy ingot is inverted once every 200-250 s during the melting process.
  • the surface modification of the carbon nanotubes and the graphene powder is specifically: disposing an organic solvent of a silane coupling agent, wherein the weight percentage of the silane coupling agent is 2-3 wt%; And the graphene powder are placed in an organic solution of a silane coupling agent and stirred, the stirring time is 50-70 min, and the stirring temperature is 70-80 ° C.
  • the second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 500-600r / min, the ball milling time is 5-8h, and the ball-to-material ratio is 4: 1-5: 1.
  • the ball milling atmosphere is an argon atmosphere
  • the ball milling speed is 500-600r / min
  • the ball milling time is 5-8h
  • the ball-to-material ratio is 4: 1-5: 1.
  • each ball is milled for 30-40 minutes, and the ball milling is suspended for 4-5 minutes.
  • the temperature in the ball mill tank is controlled below 300 ° C.
  • the second mixed powder 100-120 parts of Mg-based alloy ingots after crushing, 10-20 parts of carbon nanotubes after surface modification, and surface modification are included in terms of parts by weight.
  • the latter graphene powder accounts for 3-5 parts.
  • the first heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is hydrogen, the heat treatment temperature is 600-650 ° C, the heat treatment time is 10-20min, and the heating rate is 10-20 ° C / min.
  • the second hot-pressing sintering of the third mixed powder is specifically: the hot-pressing air pressure is lower than 0.03Pa, the hot-pressing temperature is 700-780 ° C, the hot-pressing pressure is 5-10MPa, and the hot-pressing time For 5-10min.
  • Mg-based hydrogen storage materials Compared with coordinated hydride hydrogen storage materials, Mg-based hydrogen storage materials have more stable chemical properties, can adapt to more severe use environments, and have more material storage requirements. Loose, lower storage costs. Compared with rare-earth hydrogen storage materials, Mg-based hydrogen storage materials do not include important rare-earth elements, and they have a wide range of raw materials and are not easily controlled by other countries. However, for Mg-based hydrogen storage materials, the biggest problem is that the hydrogen storage capacity is weak. At the same time, the modification of Mg-based hydrogen storage materials and the improvement of hydrogen storage capacity by doping metal elements have actually reached the theory. At the limit, hydrogen storage capacity can no longer be improved by simple composition design.
  • the process of the present invention well solves the problem of poor compatibility of non-metal particles and metal substrates, easy segregation, With the problem of unstable nature, a hydrogen storage material with stable properties, strong hydrogen storage capacity, and suitable for industrial production was prepared at a lower cost.
  • Green metal composite materials are prepared by the following methods: providing Mg, Mo, Al, Ni, and Ti powder; weighing Mg, Mo, Al, Ni, and Ti powder according to a predetermined chemical formula; Mg, Mo, and Al, Ni, and Ti powders are subjected to a first ball milling to obtain a first mixed powder; the first mixed powder is vacuum smelted to obtain an Mg-based alloy ingot; the Mg-based alloy ingot is crushed; carbon nanotubes and graphene powder are provided; Carbon nanotubes and graphene powders are subjected to surface modification; the broken Mg-based alloy ingots and surface-modified carbon nanotubes and graphene powders are mixed and subjected to a second ball milling to obtain a second mixed powder; The mixed powder is subjected to a first heat treatment to obtain a third mixed powder; the third mixed powder is subjected to a second hot-pressing sintering.
  • the first ball milling of Mg, Mo, Al, Ni, and Ti powders after symmetrical weighting is as follows: the ball milling atmosphere is argon, the ball milling speed is 1500r / min, the ball milling time is 10h, and the ball-to-material ratio is 8: 1. In the process, each ball was milled for 60 minutes, and the ball milling was suspended for 4 minutes. During the ball milling, the temperature in the ball mill tank was controlled below 600 ° C.
  • the vacuum melting of the first mixed powder is specifically: the vacuum degree is less than 0.01 Pa, and the melting time is 80 min. In the melting process, the alloy ingot is inverted once every 200 s of melting.
  • the surface modification of the carbon nanotubes and graphene powder is specifically: disposing an organic solvent of a silane coupling agent, wherein the weight percentage of the silane coupling agent is 2% by weight; placing the carbon nanotubes and graphene powder on the silane coupling agent And stir in the organic solution, the stirring time is 50 min, and the stirring temperature is 70 ° C.
  • the second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 500 r / min, the ball milling time is 5 h, the ball-to-material ratio is 4: 1, during the ball milling process, each ball milling is 30 minutes, and the ball milling is suspended for 4 minutes.
  • the temperature in the tank was below 300 ° C.
  • 100 parts by weight of the broken Mg-based alloy ingot, 10 parts by surface-modified carbon nanotubes, and 3 parts by surface-modified graphene powder are calculated in terms of parts by weight.
  • Green metal composite materials are prepared by the following methods: providing Mg, Mo, Al, Ni, and Ti powder; weighing Mg, Mo, Al, Ni, and Ti powder according to a predetermined chemical formula; Mg, Mo, and Al, Ni, and Ti powders are subjected to a first ball milling to obtain a first mixed powder; the first mixed powder is vacuum smelted to obtain an Mg-based alloy ingot; the Mg-based alloy ingot is crushed; carbon nanotubes and graphene powder are provided; Carbon nanotubes and graphene powders are subjected to surface modification; the broken Mg-based alloy ingots and surface-modified carbon nanotubes and graphene powders are mixed and subjected to a second ball milling to obtain a second mixed powder; The mixed powder is subjected to a first heat treatment to obtain a third mixed powder; the third mixed powder is subjected to a second hot-pressing sintering.
  • the first ball milling of Mg, Mo, Al, Ni, and Ti powders after symmetrical weighting is as follows: the ball milling atmosphere is argon, the ball milling speed is 1800r / min, the ball milling time is 20h, and the ball-to-material ratio is 9: 1.
  • each ball was milled for 70 minutes, and the milling was suspended for 5 minutes.
  • the temperature in the ball mill tank was controlled below 600 ° C.
  • the vacuum melting of the first mixed powder is specifically: the vacuum degree is less than 0.01 Pa, and the melting time is 100 minutes. In the melting process, the alloy ingot is inverted once every 250 s of melting.
  • the surface modification of carbon nanotubes and graphene powder is specifically: disposing an organic solvent of a silane coupling agent, wherein the weight percentage of the silane coupling agent is 3% by weight; placing the carbon nanotubes and graphene powder on the silane coupling agent The organic solution was stirred in the organic solution for 70 minutes, and the stirring temperature was 80 ° C.
  • the second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 600r / min, the ball milling time is 8h, the ball-to-material ratio is 5: 1, during the ball milling process, each ball milling is 40min, the ball milling is suspended for 5min, and the ball milling process is controlled
  • the temperature in the tank was below 300 ° C.
  • the first heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is hydrogen, the heat treatment temperature is 650 ° C., the heat treatment time is 20 minutes, and the heating rate is 20 ° C./min.
  • the second hot-pressing sintering of the third mixed powder is specifically: the hot-pressing air pressure is less than 0.03 Pa, the hot-pressing temperature is 780 ° C., the hot-pressing pressure is 10 MPa, and the hot-pressing time is 10 min.
  • the green metal composite is prepared by the following methods: providing Mg, Mo, Al, Ni, and Ti powder; weighing Mg, Mo, Al, Ni, and Ti powder according to a predetermined chemical formula; Mg, Mo, and Al, Ni, and Ti powders are subjected to a first ball milling to obtain a first mixed powder; the first mixed powder is vacuum smelted to obtain an Mg-based alloy ingot; the Mg-based alloy ingot is crushed; carbon nanotubes and graphene powder are provided; Carbon nanotubes and graphene powders are subjected to surface modification; the broken Mg-based alloy ingots and surface-modified carbon nanotubes and graphene powders are mixed and subjected to a second ball milling to obtain a second mixed powder; The mixed powder is subjected to a first heat treatment to obtain a third mixed powder; the third mixed powder is subjected to a second hot-pressing sintering.
  • the first ball milling of Mg, Mo, Al, Ni, and Ti powders after symmetrical weighting is as follows: the ball milling atmosphere is argon, the ball milling speed is 1600r / min, the ball milling time is 15h, and the ball-to-material ratio is 8.5: 1.
  • each ball was milled for 65 minutes, and the ball mill was suspended for 4.5 minutes.
  • the temperature in the ball mill tank was controlled below 600 ° C.
  • the vacuum melting of the first mixed powder is specifically: the vacuum degree is less than 0.01 Pa, and the melting time is 90 minutes. During the melting process, the alloy ingot is inverted once every 220 s of melting.
  • the surface modification of carbon nanotubes and graphene powder is specifically: disposing an organic solvent of a silane coupling agent, wherein the weight percentage of the silane coupling agent is 2.5% by weight; placing the carbon nanotubes and graphene powder in a silane coupling The organic solution of the agent was stirred, and the stirring time was 60 min, and the stirring temperature was 75 ° C.
  • the second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 550r / min, the ball milling time is 6h, the ball-to-material ratio is 4.5: 1, during the ball milling process, each ball milling is 35min, the ball milling is suspended for 4.5min, and the ball milling process is controlled
  • the temperature in the ball mill tank is below 300 ° C.
  • the first heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is hydrogen, the heat treatment temperature is 620 ° C., the heat treatment time is 15 minutes, and the heating rate is 15 ° C./min.
  • the second hot-pressing sintering of the third mixed powder is specifically: the hot-pressing air pressure is lower than 0.03 Pa, the hot-pressing temperature is 730 ° C, the hot-pressing pressure is 8 MPa, and the hot-pressing time is 8 min.
  • Green metal composite materials are prepared by the following methods: providing Mg, Mo, Al, Ni, and Ti powder; weighing Mg, Mo, Al, Ni, and Ti powder according to a predetermined chemical formula; Mg, Mo, and Al, Ni, and Ti powders are subjected to a first ball milling to obtain a first mixed powder; the first mixed powder is vacuum smelted to obtain an Mg-based alloy ingot; the Mg-based alloy ingot is crushed; carbon nanotubes and graphene powder are provided; Carbon nanotubes and graphene powders are subjected to surface modification; the broken Mg-based alloy ingots and surface-modified carbon nanotubes and graphene powders are mixed and subjected to a second ball milling to obtain a second mixed powder; The mixed powder is subjected to a first heat treatment to obtain a third mixed powder; the third mixed powder is subjected to a second hot-pressing sintering.
  • the first ball milling of Mg, Mo, Al, Ni, and Ti powder after symmetrical weighting is as follows: the ball milling atmosphere is argon, the ball milling speed is 2000r / min, the ball milling time is 25h, and the ball-to-material ratio is 10: 1. In the process, each ball was milled for 80 minutes, and the ball milling was suspended for 10 minutes. During the ball milling, the temperature in the ball mill tank was controlled below 600 ° C.
  • the vacuum melting of the first mixed powder is specifically: the vacuum degree is less than 0.01 Pa, and the melting time is 90 minutes. During the melting process, the alloy ingot is inverted once every 220 s of melting.
  • the surface modification of carbon nanotubes and graphene powder is specifically: disposing an organic solvent of a silane coupling agent, wherein the weight percentage of the silane coupling agent is 2.5% by weight; placing the carbon nanotubes and graphene powder in a silane coupling The organic solution of the agent was stirred, and the stirring time was 60 min, and the stirring temperature was 75 ° C.
  • the second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 550r / min, the ball milling time is 6h, the ball-to-material ratio is 4.5: 1, during the ball milling process, each ball milling is 35min, the ball milling is suspended for 4.5min, and the ball milling process is controlled
  • the temperature in the ball mill tank is below 300 ° C.
  • the first heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is hydrogen, the heat treatment temperature is 620 ° C., the heat treatment time is 15 minutes, and the heating rate is 15 ° C./min.
  • the second hot-pressing sintering of the third mixed powder is specifically: the hot-pressing air pressure is lower than 0.03 Pa, the hot-pressing temperature is 730 ° C., the hot-pressing pressure is 8 MPa, and the hot-pressing time is 8 min.
  • Green metal composite materials are prepared by the following methods: providing Mg, Mo, Al, Ni, and Ti powder; weighing Mg, Mo, Al, Ni, and Ti powder according to a predetermined chemical formula; Mg, Mo, and Al, Ni, and Ti powders are subjected to a first ball milling to obtain a first mixed powder; the first mixed powder is vacuum smelted to obtain an Mg-based alloy ingot; the Mg-based alloy ingot is crushed; carbon nanotubes and graphene powder are provided; Carbon nanotubes and graphene powders are subjected to surface modification; the broken Mg-based alloy ingots and surface-modified carbon nanotubes and graphene powders are mixed and subjected to a second ball milling to obtain a second mixed powder; The mixed powder is subjected to a first heat treatment to obtain a third mixed powder; the third mixed powder is subjected to a second hot-pressing sintering.
  • the first ball milling of Mg, Mo, Al, Ni, and Ti powders after symmetrical weighting is as follows: the ball milling atmosphere is argon, the ball milling speed is 1600r / min, the ball milling time is 15h, and the ball-to-material ratio is 8.5: 1.
  • each ball was milled for 65 minutes, and the ball mill was suspended for 4.5 minutes.
  • the temperature in the ball mill tank was controlled below 600 ° C.
  • the vacuum melting of the first mixed powder is specifically: the vacuum degree is less than 0.01 Pa, and the melting time is 200 min. In the melting process, the alloy ingot is inverted once every 500 s of melting.
  • the surface modification of carbon nanotubes and graphene powder is specifically: disposing an organic solvent of a silane coupling agent, wherein the weight percentage of the silane coupling agent is 5 wt%; placing the carbon nanotubes and graphene powder on the silane coupling agent The organic solution was stirred in the organic solution for 10 minutes, and the stirring temperature was 20 ° C.
  • the second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 700 r / min, the ball milling time is 10 hours, and the ball-to-material ratio is 8: 1. During the ball milling process, each ball milling is performed for 50 minutes, and the ball milling is suspended for 8 minutes. The temperature in the tank was below 300 ° C. In the second mixed powder, 110 parts by weight of the crushed Mg-based alloy ingots, 15 parts by surface-modified carbon nanotubes, and 4 parts by surface-modified graphene powder.
  • the first heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is hydrogen, the heat treatment temperature is 620 ° C., the heat treatment time is 15 minutes, and the heating rate is 15 ° C./min.
  • the second hot-pressing sintering of the third mixed powder is specifically: the hot-pressing air pressure is lower than 0.03 Pa, the hot-pressing temperature is 730 ° C., the hot-pressing pressure is 8 MPa, and the hot-pressing time is 8 min.
  • Green metal composite materials are prepared by the following methods: providing Mg, Mo, Al, Ni, and Ti powder; weighing Mg, Mo, Al, Ni, and Ti powder according to a predetermined chemical formula; Mg, Mo, and Al, Ni, and Ti powders are subjected to a first ball milling to obtain a first mixed powder; the first mixed powder is vacuum smelted to obtain an Mg-based alloy ingot; the Mg-based alloy ingot is crushed; carbon nanotubes and graphene powder are provided; Carbon nanotubes and graphene powders are subjected to surface modification; the broken Mg-based alloy ingots and surface-modified carbon nanotubes and graphene powders are mixed and subjected to a second ball milling to obtain a second mixed powder; The mixed powder is subjected to a first heat treatment to obtain a third mixed powder; the third mixed powder is subjected to a second hot-pressing sintering.
  • the first ball milling of Mg, Mo, Al, Ni, and Ti powders after symmetrical weighting is as follows: the ball milling atmosphere is argon, the ball milling speed is 1600r / min, the ball milling time is 15h, and the ball-to-material ratio is 8.5: 1.
  • each ball was milled for 65 minutes, and the ball mill was suspended for 4.5 minutes.
  • the temperature in the ball mill tank was controlled below 600 ° C.
  • the vacuum melting of the first mixed powder is specifically: the vacuum degree is less than 0.01 Pa, and the melting time is 90 minutes. During the melting process, the alloy ingot is inverted once every 220 s of melting.
  • the surface modification of carbon nanotubes and graphene powder is specifically: disposing an organic solvent of a silane coupling agent, wherein the weight percentage of the silane coupling agent is 2.5% by weight; placing the carbon nanotubes and graphene powder in a silane coupling The organic solution of the agent was stirred, and the stirring time was 60 min, and the stirring temperature was 75 ° C.
  • the second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 550r / min, the ball milling time is 6h, the ball-to-material ratio is 4.5: 1, during the ball milling process, each ball milling is 35min, the ball milling is suspended for 4.5min, and the ball milling process is controlled
  • the temperature in the ball mill tank is below 300 ° C.
  • the second mixed powder 150 parts by weight of the crushed Mg-based alloy ingot, 5 parts by surface-modified carbon nanotubes, and 1 part by surface-modified graphene powder.
  • the first heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is hydrogen, the heat treatment temperature is 620 ° C., the heat treatment time is 15 minutes, and the heating rate is 15 ° C./min.
  • the second hot-pressing sintering of the third mixed powder is specifically: the hot-pressing air pressure is lower than 0.03 Pa, the hot-pressing temperature is 730 ° C., the hot-pressing pressure is 8 MPa, and the hot-pressing time is 8 min.
  • Green metal composite materials are prepared by the following methods: providing Mg, Mo, Al, Ni, and Ti powder; weighing Mg, Mo, Al, Ni, and Ti powder according to a predetermined chemical formula; Mg, Mo, and Al, Ni, and Ti powders are subjected to a first ball milling to obtain a first mixed powder; the first mixed powder is vacuum smelted to obtain an Mg-based alloy ingot; the Mg-based alloy ingot is crushed; carbon nanotubes and graphene powder are provided; Carbon nanotubes and graphene powders are subjected to surface modification; the broken Mg-based alloy ingots and surface-modified carbon nanotubes and graphene powders are mixed and subjected to a second ball milling to obtain a second mixed powder; The mixed powder is subjected to a first heat treatment to obtain a third mixed powder; the third mixed powder is subjected to a second hot-pressing sintering.
  • the first ball milling of Mg, Mo, Al, Ni, and Ti powders after symmetrical weighting is as follows: the ball milling atmosphere is argon, the ball milling speed is 1600r / min, the ball milling time is 15h, and the ball-to-material ratio is 8.5: 1.
  • each ball was milled for 65 minutes, and the ball mill was suspended for 4.5 minutes.
  • the temperature in the ball mill tank was controlled below 600 ° C.
  • the vacuum melting of the first mixed powder is specifically: the vacuum degree is less than 0.01 Pa, and the melting time is 90 minutes. During the melting process, the alloy ingot is inverted once every 220 s of melting.
  • the surface modification of carbon nanotubes and graphene powder is specifically: disposing an organic solvent of a silane coupling agent, wherein the weight percentage of the silane coupling agent is 2.5% by weight; placing the carbon nanotubes and graphene powder in a silane coupling The organic solution of the agent was stirred, and the stirring time was 60 min, and the stirring temperature was 75 ° C.
  • the second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 550r / min, the ball milling time is 6h, the ball-to-material ratio is 4.5: 1, during the ball milling process, each ball milling is 35min, the ball milling is suspended for 4.5min, and the ball milling process is controlled
  • the temperature in the ball mill tank is below 300 ° C.
  • the first heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is hydrogen, the heat treatment temperature is 700 ° C., the heat treatment time is 25 minutes, and the heating rate is 30 ° C./min.
  • the second hot-pressing sintering of the third mixed powder is specifically: the hot-pressing air pressure is less than 0.03 Pa, the hot-pressing temperature is 820 ° C., the hot-pressing pressure is 20 MPa, and the hot-pressing time is 4 min.

Abstract

A metal composite material. The metal composite material is prepared by the following method: providing Mg, Mo, Al, Ni and Ti powder; weighing the Mg, Mo, Al, Ni and Ti powder according to a predetermined chemical formula; performing first-time ball-milling on the weighed Mg, Mo, Al, Ni and Ti powder to obtain first mixed powder; performing vacuum smelting on the first mixed powder to obtain an Mg based alloy ingot; crushing the Mg based alloy ingot; providing a carbon nano tube and graphene powder; performing surface modification on the carbon nano tube and the graphene powder; mixing the crushed Mg based alloy ingot with the surface-modified carbon nano tube and the graphene powder, and performing second-time ball-milling to obtain second mixed powder; performing first-time thermal treatment on the second mixed powder to obtain third mixed powder; and performing second-time hot-pressing sintering on the third mixed powder. The process solves the problems of poor compatibility, easy segregation and unstable properties between nonmetal particles and metal matrix, and prepares a hydrogen storage material which is stable in property, strong in hydrogen storage capacity and suitable for industrial production.

Description

[根据细则37.2由ISA制定的发明名称]　金属复合材料[Name of invention made by ISA according to Rule 37.2] Metal composite 技术领域Technical field
本发明涉及新能源材料技术领域，特别涉及一种绿色金属复合材料。The invention relates to the technical field of new energy materials, in particular to a green metal composite material.
背景技术Background technique
对碳系列储氢材料的研究是近些年兴起的一个热门课题。大家知道，由于碳的多孔结构和碳原子对气体分子的特殊吸引作用，碳对几乎所有的气体都存在或大或小的吸附作用。所以把它作为一种储氢材料来研究也就是自然而然的事。目前对碳系列储氢材料的研究主要是集中在石墨、活性碳、纳米碳管和纳米碳纤维等方面，下面将对这些材料的研究做一简单的介绍，特别是有关纳米碳管和纳米碳纤维的研究。活性碳对H 2的吸附能力不太明显。吸附量也相对较低，大约3-6wt％之间，且条件苛刻，温度为78K，压力为40bars。但活性碳便宜且很容易获得。假如采用适当方法可以改善其性能的话，当有很大的应用前途。现有技术采用硝酸或NaOCl处理活性碳，其吸氢量以及作为电极时的放电量就有了明显的改善。纳米碳管和纳米碳纤维之所以成为一种热门的储氢材料，一是它们的储氢量大，一般也达到10wt％，有的甚至达到60wt％以上。但此前曾有科学工作者对此进行检验，却以失败告终。然其储氢量比储氢合金高却是不争的事实。再就是其质量相对较轻，便于携带。但由于其合成非常困难，条件苛刻，要消耗大量能量：合成之后又要经过化学处理和提纯才能应用；最重要的一点是，其储氢性质和储氢机理至今还处在争论的行列，故仍未得到广泛的应用。 The research on carbon series hydrogen storage materials has been a hot topic in recent years. It is known that due to the porous structure of carbon and the special attraction of carbon atoms to gas molecules, carbon has a large or small adsorption effect on almost all gases. So it is natural to study it as a kind of hydrogen storage material. The current research on carbon series hydrogen storage materials is mainly focused on graphite, activated carbon, nano-carbon tubes, and nano-carbon fibers. The following will briefly introduce the research of these materials, especially about the carbon nanotubes and nano-carbon fibers. the study. The adsorption capacity of activated carbon for H 2 is less obvious. The amount of adsorption is also relatively low, between about 3-6 wt%, and the conditions are harsh, the temperature is 78K, and the pressure is 40bars. But activated carbon is cheap and easily available. If proper methods can be used to improve its performance, it has great application prospects. In the prior art, the activated carbon is treated with nitric acid or NaOCl, and its hydrogen absorption amount and discharge amount when used as an electrode are significantly improved. The reason why carbon nanotubes and nano-carbon fibers have become a popular hydrogen storage material is that their large hydrogen storage capacity generally reaches 10% by weight, and some even reach more than 60% by weight. But some scientists have tested this before, but it ended in failure. However, it is an indisputable fact that its hydrogen storage capacity is higher than that of hydrogen storage alloys. Then it is relatively light and easy to carry. However, because its synthesis is very difficult and harsh conditions, it requires a lot of energy: after synthesis, it must be chemically treated and purified before it can be applied; the most important point is that its hydrogen storage properties and hydrogen storage mechanism are still in the ranks of debate, so Has not been widely used.
公开于该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不应当被视为承认或以任何形式暗示该信息构成已为本领域一般技术人员所公知的现有技术。The information disclosed in this Background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that the information constitutes prior art that is already known to a person of ordinary skill in the art.
发明内容Summary of the invention
本发明的目的在于提供一种绿色金属复合材料，从而克服现有技术的缺点。The purpose of the present invention is to provide a green metal composite material, thereby overcoming the disadvantages of the prior art.
为实现上述目的，本发明提供了一种绿色金属复合材料，其特征在于：绿色金属复合材料是由如下方法制备的：提供Mg、Mo、Al、Ni以及Ti粉；按照预定化学式，对Mg、Mo、Al、Ni以及Ti粉进行称重；对称重之后的Mg、Mo、Al、Ni以及Ti粉进行第一球磨，得到第一混合粉；对第一混合粉进行真空熔炼，得到Mg基合金锭；对Mg基合金锭进行破碎；提供碳纳米管和石墨烯粉末；对碳纳米管和石墨烯粉末进行表面改性；将破碎之后的Mg基合金锭以及表面改性后的碳纳米管和石墨烯粉末混合，并进行第二球磨，得到第二混合粉；对第二混合粉进行第一热处理，得到第三混合粉；对第三混合粉进行第二热压烧结。To achieve the above object, the present invention provides a green metal composite material, which is characterized in that the green metal composite material is prepared by the following method: providing Mg, Mo, Al, Ni, and Ti powder; according to a predetermined chemical formula, the Mg, Mo, Al, Ni, and Ti powders were weighed; Mg, Mo, Al, Ni, and Ti powders were weighed first to obtain a first mixed powder; and the first mixed powder was vacuum smelted to obtain a Mg-based alloy Ingots; crushing Mg-based alloy ingots; providing carbon nanotubes and graphene powders; surface modification of carbon nanotubes and graphene powders; crushing Mg-based alloy ingots and surface-modified carbon nanotubes and The graphene powder is mixed and subjected to a second ball milling to obtain a second mixed powder; the second mixed powder is subjected to a first heat treatment to obtain a third mixed powder; and the third mixed powder is subjected to a second hot-press sintering.
优选地，上述技术方案中，其中，预定化学式为：Mg 100-x-y-z-aMo xAl yNi zTi a，其中，x＝0.5-1.5，y＝2-3，z＝10-12，a＝1-3。 Preferably, in the above technical solution, wherein the predetermined chemical formula is: Mg 100-xyza Mo x Al y Ni z Ti a , wherein x = 0.5-1.5, y = 2-3, z = 10-12, a = 1 -3.
优选地，上述技术方案中，对称重之后的Mg、Mo、Al、Ni以及Ti粉进行第一球磨具体为：球磨气氛为氩气气氛，球磨速度为1500-1800r/min，球磨时间为10-20h，球料比为8:1-9:1，在球磨过程中每球磨60-70min，暂停球磨4-5min，球磨过程中控制球磨罐中的温度低于600℃。Preferably, in the above technical solution, the first ball milling of Mg, Mo, Al, Ni, and Ti powders after the symmetrical weighting is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 1500-1800r / min, and the ball milling time is 10- In 20h, the ball-to-material ratio is 8: 1-9: 1. During the ball milling process, each ball is milled for 60-70min, and the ball milling is suspended for 4-5min. During the ball milling process, the temperature in the ball mill tank is controlled below 600 ° C.
优选地，上述技术方案中，对第一混合粉进行真空熔炼具体为：真空度低于0.01Pa，熔炼时间为80-100min，在熔炼过程中，每熔炼200-250s将合金锭进行一次翻转。Preferably, in the above technical solution, the vacuum melting of the first mixed powder is specifically: the vacuum degree is lower than 0.01 Pa, the melting time is 80-100 min, and the alloy ingot is inverted once every 200-250 s during the melting process.
优选地，上述技术方案中，对碳纳米管和石墨烯粉末进行表面改性具体为：配置硅烷偶联剂有机溶剂，其中，硅烷偶联剂的重量百分数为2-3wt％；将碳纳米管和石墨烯粉末置于硅烷偶联剂的有机溶液中并进行搅拌，搅拌时间为50-70min，搅拌温度为70-80℃。Preferably, in the above technical solution, the surface modification of the carbon nanotubes and the graphene powder is specifically: disposing an organic solvent of a silane coupling agent, wherein the weight percentage of the silane coupling agent is 2-3 wt%; And the graphene powder are placed in an organic solution of a silane coupling agent and stirred, the stirring time is 50-70 min, and the stirring temperature is 70-80 ° C.
优选地，上述技术方案中，第二球磨具体为：球磨气氛为氩气气氛，球磨速度为500-600r/min，球磨时间为5-8h，球料比为4:1-5:1，在球磨过程中 每球磨30-40min，暂停球磨4-5min，球磨过程中控制球磨罐中的温度低于300℃。Preferably, in the above technical solution, the second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 500-600r / min, the ball milling time is 5-8h, and the ball-to-material ratio is 4: 1-5: 1. During the ball milling process, each ball is milled for 30-40 minutes, and the ball milling is suspended for 4-5 minutes. During the ball milling process, the temperature in the ball mill tank is controlled below 300 ° C.
优选地，上述技术方案中，在第二混合粉中，以重量份计，破碎之后的Mg基合金锭占100-120份，表面改性后的碳纳米管占10-20份和表面改性后的石墨烯粉末占3-5份。Preferably, in the above technical solution, in the second mixed powder, 100-120 parts of Mg-based alloy ingots after crushing, 10-20 parts of carbon nanotubes after surface modification, and surface modification are included in terms of parts by weight. The latter graphene powder accounts for 3-5 parts.
优选地，上述技术方案中，对第二混合粉进行第一热处理具体为：热处理气氛为氢气，热处理温度为600-650℃，热处理时间为10-20min，升温速率为10-20℃/min。Preferably, in the above technical solution, the first heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is hydrogen, the heat treatment temperature is 600-650 ° C, the heat treatment time is 10-20min, and the heating rate is 10-20 ° C / min.
优选地，上述技术方案中，对第三混合粉进行第二热压烧结具体为：热压气压低于0.03Pa，热压温度为700-780℃，热压压力为5-10MPa，热压时间为5-10min。Preferably, in the above technical solution, the second hot-pressing sintering of the third mixed powder is specifically: the hot-pressing air pressure is lower than 0.03Pa, the hot-pressing temperature is 700-780 ° C, the hot-pressing pressure is 5-10MPa, and the hot-pressing time For 5-10min.
与现有技术相比，本发明具有如下有益效果：相比于配位氢化物储氢材料，Mg系储氢材料的化学性质更稳定，能够适应更为严酷的使用环境，并且材料保存要求更宽松，保存成本更低。而相比于稀土系储氢材料，Mg系储氢材料中不包括重要的稀土元素，原料来源广泛，不易受到其它国家的控制。但是目前对于Mg系储氢材料而言，最大的问题在于：储氢能力较弱，同时，通过掺杂金属元素的方法对Mg系储氢材料进行改性、提高储氢能力实际上已经达到理论极限，通过简单的成分设计已经不能继续提高储氢能力。为了能够继续提高材料的储氢能力，目前可行的方法有以下几种：1、改变材料的制备方法，通过可控的改变材料的微观结构仍然有望继续提高材料的储氢能力，但是由于材料的微观结构与储氢能力之间的关系尚不清楚，所以这种方法设计成本高，设计之后实现又极为困难。2、掺杂非金属元素，但是这种方法由于非金属元素与金属元素之间相容性的问题，导致合金性能不稳定。为了克服现有技术的缺陷，本发明提出了一种掺杂碳纳米管和石墨烯粉末储氢材料，本发明的工艺很好的解决了非金属颗粒与金属基体相容性差、易偏聚、性质不稳定的问题，以较低的成本制备得到了性质稳定、储氢能力强并且适于工业生产的储氢材料。Compared with the prior art, the present invention has the following beneficial effects: Compared with coordinated hydride hydrogen storage materials, Mg-based hydrogen storage materials have more stable chemical properties, can adapt to more severe use environments, and have more material storage requirements. Loose, lower storage costs. Compared with rare-earth hydrogen storage materials, Mg-based hydrogen storage materials do not include important rare-earth elements, and they have a wide range of raw materials and are not easily controlled by other countries. However, for Mg-based hydrogen storage materials, the biggest problem is that the hydrogen storage capacity is weak. At the same time, the modification of Mg-based hydrogen storage materials and the improvement of hydrogen storage capacity by doping metal elements have actually reached the theory. At the limit, hydrogen storage capacity can no longer be improved by simple composition design. In order to continue to improve the hydrogen storage capacity of the material, there are currently available methods: 1. Change the preparation method of the material, and it is expected to continue to improve the hydrogen storage capacity of the material by controlling the microstructure of the material. The relationship between the microstructure and the hydrogen storage capacity is unclear, so this method is costly to design and extremely difficult to implement after design. 2. Non-metallic elements are doped, but this method results in unstable alloy properties due to compatibility issues between non-metallic elements and metallic elements. In order to overcome the shortcomings of the prior art, the present invention proposes a doped carbon nanotube and graphene powder hydrogen storage material. The process of the present invention well solves the problem of poor compatibility of non-metal particles and metal substrates, easy segregation, With the problem of unstable nature, a hydrogen storage material with stable properties, strong hydrogen storage capacity, and suitable for industrial production was prepared at a lower cost.
具体实施方式detailed description
提供以下实施方式是为了能够更透彻地理解本公开，并且能够将本公开的范围完整的传达给本领域的技术人员。The following embodiments are provided to enable a more thorough understanding of the present disclosure, and to fully convey the scope of the present disclosure to those skilled in the art.
实施例1Example 1
绿色金属复合材料是由如下方法制备的：提供Mg、Mo、Al、Ni以及Ti粉；按照预定化学式，对Mg、Mo、Al、Ni以及Ti粉进行称重；对称重之后的Mg、Mo、Al、Ni以及Ti粉进行第一球磨，得到第一混合粉；对第一混合粉进行真空熔炼，得到Mg基合金锭；对Mg基合金锭进行破碎；提供碳纳米管和石墨烯粉末；对碳纳米管和石墨烯粉末进行表面改性；将破碎之后的Mg基合金锭以及表面改性后的碳纳米管和石墨烯粉末混合，并进行第二球磨，得到第二混合粉；对第二混合粉进行第一热处理，得到第三混合粉；对第三混合粉进行第二热压烧结。其中，预定化学式为：Mg 100-x-y-z-aMo xAl yNi zTi a，其中，x＝0.5，y＝2，z＝10，a＝1。对称重之后的Mg、Mo、Al、Ni以及Ti粉进行第一球磨具体为：球磨气氛为氩气气氛，球磨速度为1500r/min，球磨时间为10h，球料比为8:1，在球磨过程中每球磨60min，暂停球磨4min，球磨过程中控制球磨罐中的温度低于600℃。对第一混合粉进行真空熔炼具体为：真空度低于0.01Pa，熔炼时间为80min，在熔炼过程中，每熔炼200s将合金锭进行一次翻转。对碳纳米管和石墨烯粉末进行表面改性具体为：配置硅烷偶联剂有机溶剂，其中，硅烷偶联剂的重量百分数为2wt％；将碳纳米管和石墨烯粉末置于硅烷偶联剂的有机溶液中并进行搅拌，搅拌时间为50min，搅拌温度为70℃。第二球磨具体为：球磨气氛为氩气气氛，球磨速度为500r/min，球磨时间为5h，球料比为4:1，在球磨过程中每球磨30min，暂停球磨4min，球磨过程中控制球磨罐中的温度低于300℃。在第二混合粉中，以重量份计，破碎之后的Mg基合金锭占100份，表面改性后的碳纳米管占10份和表面改性后的石墨烯粉末占3份。对第二混合粉进行第一热处理具体为：热处理气氛为氢气，热处理温度为600℃，热处理时间为10min，升温速率为10℃/min。对第三混合粉进行第二热压烧结具体为：热压气压低于0.03Pa，热压温度为 700℃，热压压力为5MPa，热压时间为5min。 Green metal composite materials are prepared by the following methods: providing Mg, Mo, Al, Ni, and Ti powder; weighing Mg, Mo, Al, Ni, and Ti powder according to a predetermined chemical formula; Mg, Mo, and Al, Ni, and Ti powders are subjected to a first ball milling to obtain a first mixed powder; the first mixed powder is vacuum smelted to obtain an Mg-based alloy ingot; the Mg-based alloy ingot is crushed; carbon nanotubes and graphene powder are provided; Carbon nanotubes and graphene powders are subjected to surface modification; the broken Mg-based alloy ingots and surface-modified carbon nanotubes and graphene powders are mixed and subjected to a second ball milling to obtain a second mixed powder; The mixed powder is subjected to a first heat treatment to obtain a third mixed powder; the third mixed powder is subjected to a second hot-pressing sintering. Wherein, the predetermined chemical formula is: Mg 100-xyza Mo x Al y Ni z Ti a , where x = 0.5, y = 2, z = 10, a = 1. The first ball milling of Mg, Mo, Al, Ni, and Ti powders after symmetrical weighting is as follows: the ball milling atmosphere is argon, the ball milling speed is 1500r / min, the ball milling time is 10h, and the ball-to-material ratio is 8: 1. In the process, each ball was milled for 60 minutes, and the ball milling was suspended for 4 minutes. During the ball milling, the temperature in the ball mill tank was controlled below 600 ° C. The vacuum melting of the first mixed powder is specifically: the vacuum degree is less than 0.01 Pa, and the melting time is 80 min. In the melting process, the alloy ingot is inverted once every 200 s of melting. The surface modification of the carbon nanotubes and graphene powder is specifically: disposing an organic solvent of a silane coupling agent, wherein the weight percentage of the silane coupling agent is 2% by weight; placing the carbon nanotubes and graphene powder on the silane coupling agent And stir in the organic solution, the stirring time is 50 min, and the stirring temperature is 70 ° C. The second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 500 r / min, the ball milling time is 5 h, the ball-to-material ratio is 4: 1, during the ball milling process, each ball milling is 30 minutes, and the ball milling is suspended for 4 minutes. The temperature in the tank was below 300 ° C. In the second mixed powder, 100 parts by weight of the broken Mg-based alloy ingot, 10 parts by surface-modified carbon nanotubes, and 3 parts by surface-modified graphene powder are calculated in terms of parts by weight. The first heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is hydrogen, the heat treatment temperature is 600 ° C., the heat treatment time is 10 minutes, and the heating rate is 10 ° C./min. The second hot-pressing sintering of the third mixed powder is specifically: the hot-pressing air pressure is less than 0.03 Pa, the hot-pressing temperature is 700 ° C., the hot-pressing pressure is 5 MPa, and the hot-pressing time is 5 min.
实施例2Example 2
绿色金属复合材料是由如下方法制备的：提供Mg、Mo、Al、Ni以及Ti粉；按照预定化学式，对Mg、Mo、Al、Ni以及Ti粉进行称重；对称重之后的Mg、Mo、Al、Ni以及Ti粉进行第一球磨，得到第一混合粉；对第一混合粉进行真空熔炼，得到Mg基合金锭；对Mg基合金锭进行破碎；提供碳纳米管和石墨烯粉末；对碳纳米管和石墨烯粉末进行表面改性；将破碎之后的Mg基合金锭以及表面改性后的碳纳米管和石墨烯粉末混合，并进行第二球磨，得到第二混合粉；对第二混合粉进行第一热处理，得到第三混合粉；对第三混合粉进行第二热压烧结。其中，预定化学式为：Mg 100-x-y-z-aMo xAl yNi zTi a，其中，x＝1.5，y＝3，z＝12，a＝3。对称重之后的Mg、Mo、Al、Ni以及Ti粉进行第一球磨具体为：球磨气氛为氩气气氛，球磨速度为1800r/min，球磨时间为20h，球料比为9:1，在球磨过程中每球磨70min，暂停球磨5min，球磨过程中控制球磨罐中的温度低于600℃。对第一混合粉进行真空熔炼具体为：真空度低于0.01Pa，熔炼时间为100min，在熔炼过程中，每熔炼250s将合金锭进行一次翻转。对碳纳米管和石墨烯粉末进行表面改性具体为：配置硅烷偶联剂有机溶剂，其中，硅烷偶联剂的重量百分数为3wt％；将碳纳米管和石墨烯粉末置于硅烷偶联剂的有机溶液中并进行搅拌，搅拌时间为70min，搅拌温度为80℃。第二球磨具体为：球磨气氛为氩气气氛，球磨速度为600r/min，球磨时间为8h，球料比为5:1，在球磨过程中每球磨40min，暂停球磨5min，球磨过程中控制球磨罐中的温度低于300℃。在第二混合粉中，以重量份计，破碎之后的Mg基合金锭占120份，表面改性后的碳纳米管占20份和表面改性后的石墨烯粉末占5份。对第二混合粉进行第一热处理具体为：热处理气氛为氢气，热处理温度为650℃，热处理时间为20min，升温速率为20℃/min。对第三混合粉进行第二热压烧结具体为：热压气压低于0.03Pa，热压温度为780℃，热压压力为10MPa，热压时间为10min。 Green metal composite materials are prepared by the following methods: providing Mg, Mo, Al, Ni, and Ti powder; weighing Mg, Mo, Al, Ni, and Ti powder according to a predetermined chemical formula; Mg, Mo, and Al, Ni, and Ti powders are subjected to a first ball milling to obtain a first mixed powder; the first mixed powder is vacuum smelted to obtain an Mg-based alloy ingot; the Mg-based alloy ingot is crushed; carbon nanotubes and graphene powder are provided; Carbon nanotubes and graphene powders are subjected to surface modification; the broken Mg-based alloy ingots and surface-modified carbon nanotubes and graphene powders are mixed and subjected to a second ball milling to obtain a second mixed powder; The mixed powder is subjected to a first heat treatment to obtain a third mixed powder; the third mixed powder is subjected to a second hot-pressing sintering. Wherein, the predetermined chemical formula is: Mg 100-xyza Mo x Al y Ni z Ti a , where x = 1.5, y = 3, z = 12, a = 3. The first ball milling of Mg, Mo, Al, Ni, and Ti powders after symmetrical weighting is as follows: the ball milling atmosphere is argon, the ball milling speed is 1800r / min, the ball milling time is 20h, and the ball-to-material ratio is 9: 1. During the milling process, each ball was milled for 70 minutes, and the milling was suspended for 5 minutes. During the milling process, the temperature in the ball mill tank was controlled below 600 ° C. The vacuum melting of the first mixed powder is specifically: the vacuum degree is less than 0.01 Pa, and the melting time is 100 minutes. In the melting process, the alloy ingot is inverted once every 250 s of melting. The surface modification of carbon nanotubes and graphene powder is specifically: disposing an organic solvent of a silane coupling agent, wherein the weight percentage of the silane coupling agent is 3% by weight; placing the carbon nanotubes and graphene powder on the silane coupling agent The organic solution was stirred in the organic solution for 70 minutes, and the stirring temperature was 80 ° C. The second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 600r / min, the ball milling time is 8h, the ball-to-material ratio is 5: 1, during the ball milling process, each ball milling is 40min, the ball milling is suspended for 5min, and the ball milling process is controlled The temperature in the tank was below 300 ° C. In the second mixed powder, 120 parts by weight of the broken Mg-based alloy ingots, 20 parts by surface-modified carbon nanotubes, and 5 parts by surface-modified graphene powders. The first heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is hydrogen, the heat treatment temperature is 650 ° C., the heat treatment time is 20 minutes, and the heating rate is 20 ° C./min. The second hot-pressing sintering of the third mixed powder is specifically: the hot-pressing air pressure is less than 0.03 Pa, the hot-pressing temperature is 780 ° C., the hot-pressing pressure is 10 MPa, and the hot-pressing time is 10 min.
实施例3Example 3
绿色金属复合材料是由如下方法制备的：提供Mg、Mo、Al、Ni以及Ti 粉；按照预定化学式，对Mg、Mo、Al、Ni以及Ti粉进行称重；对称重之后的Mg、Mo、Al、Ni以及Ti粉进行第一球磨，得到第一混合粉；对第一混合粉进行真空熔炼，得到Mg基合金锭；对Mg基合金锭进行破碎；提供碳纳米管和石墨烯粉末；对碳纳米管和石墨烯粉末进行表面改性；将破碎之后的Mg基合金锭以及表面改性后的碳纳米管和石墨烯粉末混合，并进行第二球磨，得到第二混合粉；对第二混合粉进行第一热处理，得到第三混合粉；对第三混合粉进行第二热压烧结。其中，预定化学式为：Mg 100-x-y-z-aMo xAl yNi zTi a，其中，x＝1，y＝2.5，z＝11，a＝2。对称重之后的Mg、Mo、Al、Ni以及Ti粉进行第一球磨具体为：球磨气氛为氩气气氛，球磨速度为1600r/min，球磨时间为15h，球料比为8.5:1，在球磨过程中每球磨65min，暂停球磨4.5min，球磨过程中控制球磨罐中的温度低于600℃。对第一混合粉进行真空熔炼具体为：真空度低于0.01Pa，熔炼时间为90min，在熔炼过程中，每熔炼220s将合金锭进行一次翻转。对碳纳米管和石墨烯粉末进行表面改性具体为：配置硅烷偶联剂有机溶剂，其中，硅烷偶联剂的重量百分数为2.5wt％；将碳纳米管和石墨烯粉末置于硅烷偶联剂的有机溶液中并进行搅拌，搅拌时间为60min，搅拌温度为75℃。第二球磨具体为：球磨气氛为氩气气氛，球磨速度为550r/min，球磨时间为6h，球料比为4.5:1，在球磨过程中每球磨35min，暂停球磨4.5min，球磨过程中控制球磨罐中的温度低于300℃。在第二混合粉中，以重量份计，破碎之后的Mg基合金锭占110份，表面改性后的碳纳米管占15份和表面改性后的石墨烯粉末占4份。对第二混合粉进行第一热处理具体为：热处理气氛为氢气，热处理温度为620℃，热处理时间为15min，升温速率为15℃/min。对第三混合粉进行第二热压烧结具体为：热压气压低于0.03Pa，热压温度为730℃，热压压力为8MPa，热压时间为8min。 The green metal composite is prepared by the following methods: providing Mg, Mo, Al, Ni, and Ti powder; weighing Mg, Mo, Al, Ni, and Ti powder according to a predetermined chemical formula; Mg, Mo, and Al, Ni, and Ti powders are subjected to a first ball milling to obtain a first mixed powder; the first mixed powder is vacuum smelted to obtain an Mg-based alloy ingot; the Mg-based alloy ingot is crushed; carbon nanotubes and graphene powder are provided; Carbon nanotubes and graphene powders are subjected to surface modification; the broken Mg-based alloy ingots and surface-modified carbon nanotubes and graphene powders are mixed and subjected to a second ball milling to obtain a second mixed powder; The mixed powder is subjected to a first heat treatment to obtain a third mixed powder; the third mixed powder is subjected to a second hot-pressing sintering. Wherein, the predetermined chemical formula is: Mg 100-xyza Mo x Al y Ni z Ti a , where x = 1, y = 2.5, z = 11, and a = 2. The first ball milling of Mg, Mo, Al, Ni, and Ti powders after symmetrical weighting is as follows: the ball milling atmosphere is argon, the ball milling speed is 1600r / min, the ball milling time is 15h, and the ball-to-material ratio is 8.5: 1. During the ball milling process, each ball was milled for 65 minutes, and the ball mill was suspended for 4.5 minutes. During the ball milling process, the temperature in the ball mill tank was controlled below 600 ° C. The vacuum melting of the first mixed powder is specifically: the vacuum degree is less than 0.01 Pa, and the melting time is 90 minutes. During the melting process, the alloy ingot is inverted once every 220 s of melting. The surface modification of carbon nanotubes and graphene powder is specifically: disposing an organic solvent of a silane coupling agent, wherein the weight percentage of the silane coupling agent is 2.5% by weight; placing the carbon nanotubes and graphene powder in a silane coupling The organic solution of the agent was stirred, and the stirring time was 60 min, and the stirring temperature was 75 ° C. The second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 550r / min, the ball milling time is 6h, the ball-to-material ratio is 4.5: 1, during the ball milling process, each ball milling is 35min, the ball milling is suspended for 4.5min, and the ball milling process is controlled The temperature in the ball mill tank is below 300 ° C. In the second mixed powder, 110 parts by weight of the crushed Mg-based alloy ingots, 15 parts by surface-modified carbon nanotubes, and 4 parts by surface-modified graphene powder. The first heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is hydrogen, the heat treatment temperature is 620 ° C., the heat treatment time is 15 minutes, and the heating rate is 15 ° C./min. The second hot-pressing sintering of the third mixed powder is specifically: the hot-pressing air pressure is lower than 0.03 Pa, the hot-pressing temperature is 730 ° C, the hot-pressing pressure is 8 MPa, and the hot-pressing time is 8 min.
实施例4Example 4
绿色金属复合材料是由如下方法制备的：提供Mg、Mo、Al、Ni以及Ti粉；按照预定化学式，对Mg、Mo、Al、Ni以及Ti粉进行称重；对称重之后的Mg、Mo、Al、Ni以及Ti粉进行第一球磨，得到第一混合粉；对第一混合粉进行真空熔炼，得到Mg基合金锭；对Mg基合金锭进行破碎；提供碳纳米 管和石墨烯粉末；对碳纳米管和石墨烯粉末进行表面改性；将破碎之后的Mg基合金锭以及表面改性后的碳纳米管和石墨烯粉末混合，并进行第二球磨，得到第二混合粉；对第二混合粉进行第一热处理，得到第三混合粉；对第三混合粉进行第二热压烧结。其中，预定化学式为：Mg 100-x-y-z-aMo xAl yNi zTi a，其中，x＝2，y＝1，z＝5，a＝0。对称重之后的Mg、Mo、Al、Ni以及Ti粉进行第一球磨具体为：球磨气氛为氩气气氛，球磨速度为2000r/min，球磨时间为25h，球料比为10:1，在球磨过程中每球磨80min，暂停球磨10min，球磨过程中控制球磨罐中的温度低于600℃。对第一混合粉进行真空熔炼具体为：真空度低于0.01Pa，熔炼时间为90min，在熔炼过程中，每熔炼220s将合金锭进行一次翻转。对碳纳米管和石墨烯粉末进行表面改性具体为：配置硅烷偶联剂有机溶剂，其中，硅烷偶联剂的重量百分数为2.5wt％；将碳纳米管和石墨烯粉末置于硅烷偶联剂的有机溶液中并进行搅拌，搅拌时间为60min，搅拌温度为75℃。第二球磨具体为：球磨气氛为氩气气氛，球磨速度为550r/min，球磨时间为6h，球料比为4.5:1，在球磨过程中每球磨35min，暂停球磨4.5min，球磨过程中控制球磨罐中的温度低于300℃。在第二混合粉中，以重量份计，破碎之后的Mg基合金锭占110份，表面改性后的碳纳米管占15份和表面改性后的石墨烯粉末占4份。对第二混合粉进行第一热处理具体为：热处理气氛为氢气，热处理温度为620℃，热处理时间为15min，升温速率为15℃/min。对第三混合粉进行第二热压烧结具体为：热压气压低于0.03Pa，热压温度为730℃，热压压力为8MPa，热压时间为8min。 Green metal composite materials are prepared by the following methods: providing Mg, Mo, Al, Ni, and Ti powder; weighing Mg, Mo, Al, Ni, and Ti powder according to a predetermined chemical formula; Mg, Mo, and Al, Ni, and Ti powders are subjected to a first ball milling to obtain a first mixed powder; the first mixed powder is vacuum smelted to obtain an Mg-based alloy ingot; the Mg-based alloy ingot is crushed; carbon nanotubes and graphene powder are provided; Carbon nanotubes and graphene powders are subjected to surface modification; the broken Mg-based alloy ingots and surface-modified carbon nanotubes and graphene powders are mixed and subjected to a second ball milling to obtain a second mixed powder; The mixed powder is subjected to a first heat treatment to obtain a third mixed powder; the third mixed powder is subjected to a second hot-pressing sintering. Wherein, the predetermined chemical formula is: Mg 100-xyza Mo x Al y Ni z Ti a , where x = 2, y = 1, z = 5, a = 0. The first ball milling of Mg, Mo, Al, Ni, and Ti powder after symmetrical weighting is as follows: the ball milling atmosphere is argon, the ball milling speed is 2000r / min, the ball milling time is 25h, and the ball-to-material ratio is 10: 1. In the process, each ball was milled for 80 minutes, and the ball milling was suspended for 10 minutes. During the ball milling, the temperature in the ball mill tank was controlled below 600 ° C. The vacuum melting of the first mixed powder is specifically: the vacuum degree is less than 0.01 Pa, and the melting time is 90 minutes. During the melting process, the alloy ingot is inverted once every 220 s of melting. The surface modification of carbon nanotubes and graphene powder is specifically: disposing an organic solvent of a silane coupling agent, wherein the weight percentage of the silane coupling agent is 2.5% by weight; placing the carbon nanotubes and graphene powder in a silane coupling The organic solution of the agent was stirred, and the stirring time was 60 min, and the stirring temperature was 75 ° C. The second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 550r / min, the ball milling time is 6h, the ball-to-material ratio is 4.5: 1, during the ball milling process, each ball milling is 35min, the ball milling is suspended for 4.5min, and the ball milling process is controlled The temperature in the ball mill tank is below 300 ° C. In the second mixed powder, 110 parts by weight of the crushed Mg-based alloy ingots, 15 parts by surface-modified carbon nanotubes, and 4 parts by surface-modified graphene powder. The first heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is hydrogen, the heat treatment temperature is 620 ° C., the heat treatment time is 15 minutes, and the heating rate is 15 ° C./min. The second hot-pressing sintering of the third mixed powder is specifically: the hot-pressing air pressure is lower than 0.03 Pa, the hot-pressing temperature is 730 ° C., the hot-pressing pressure is 8 MPa, and the hot-pressing time is 8 min.
实施例5Example 5
绿色金属复合材料是由如下方法制备的：提供Mg、Mo、Al、Ni以及Ti粉；按照预定化学式，对Mg、Mo、Al、Ni以及Ti粉进行称重；对称重之后的Mg、Mo、Al、Ni以及Ti粉进行第一球磨，得到第一混合粉；对第一混合粉进行真空熔炼，得到Mg基合金锭；对Mg基合金锭进行破碎；提供碳纳米管和石墨烯粉末；对碳纳米管和石墨烯粉末进行表面改性；将破碎之后的Mg基合金锭以及表面改性后的碳纳米管和石墨烯粉末混合，并进行第二球磨，得到第二混合粉；对第二混合粉进行第一热处理，得到第三混合粉；对第三 混合粉进行第二热压烧结。其中，预定化学式为：Mg 100-x-y-z-aMo xAl yNi zTi a，其中，x＝1，y＝2.5，z＝11，a＝2。对称重之后的Mg、Mo、Al、Ni以及Ti粉进行第一球磨具体为：球磨气氛为氩气气氛，球磨速度为1600r/min，球磨时间为15h，球料比为8.5:1，在球磨过程中每球磨65min，暂停球磨4.5min，球磨过程中控制球磨罐中的温度低于600℃。对第一混合粉进行真空熔炼具体为：真空度低于0.01Pa，熔炼时间为200min，在熔炼过程中，每熔炼500s将合金锭进行一次翻转。对碳纳米管和石墨烯粉末进行表面改性具体为：配置硅烷偶联剂有机溶剂，其中，硅烷偶联剂的重量百分数为5wt％；将碳纳米管和石墨烯粉末置于硅烷偶联剂的有机溶液中并进行搅拌，搅拌时间为10min，搅拌温度为20℃。第二球磨具体为：球磨气氛为氩气气氛，球磨速度为700r/min，球磨时间为10h，球料比为8:1，在球磨过程中每球磨50min，暂停球磨8min，球磨过程中控制球磨罐中的温度低于300℃。在第二混合粉中，以重量份计，破碎之后的Mg基合金锭占110份，表面改性后的碳纳米管占15份和表面改性后的石墨烯粉末占4份。对第二混合粉进行第一热处理具体为：热处理气氛为氢气，热处理温度为620℃，热处理时间为15min，升温速率为15℃/min。对第三混合粉进行第二热压烧结具体为：热压气压低于0.03Pa，热压温度为730℃，热压压力为8MPa，热压时间为8min。 Green metal composite materials are prepared by the following methods: providing Mg, Mo, Al, Ni, and Ti powder; weighing Mg, Mo, Al, Ni, and Ti powder according to a predetermined chemical formula; Mg, Mo, and Al, Ni, and Ti powders are subjected to a first ball milling to obtain a first mixed powder; the first mixed powder is vacuum smelted to obtain an Mg-based alloy ingot; the Mg-based alloy ingot is crushed; carbon nanotubes and graphene powder are provided; Carbon nanotubes and graphene powders are subjected to surface modification; the broken Mg-based alloy ingots and surface-modified carbon nanotubes and graphene powders are mixed and subjected to a second ball milling to obtain a second mixed powder; The mixed powder is subjected to a first heat treatment to obtain a third mixed powder; the third mixed powder is subjected to a second hot-pressing sintering. Wherein, the predetermined chemical formula is: Mg 100-xyza Mo x Al y Ni z Ti a , where x = 1, y = 2.5, z = 11, and a = 2. The first ball milling of Mg, Mo, Al, Ni, and Ti powders after symmetrical weighting is as follows: the ball milling atmosphere is argon, the ball milling speed is 1600r / min, the ball milling time is 15h, and the ball-to-material ratio is 8.5: 1. During the ball milling process, each ball was milled for 65 minutes, and the ball mill was suspended for 4.5 minutes. During the ball milling process, the temperature in the ball mill tank was controlled below 600 ° C. The vacuum melting of the first mixed powder is specifically: the vacuum degree is less than 0.01 Pa, and the melting time is 200 min. In the melting process, the alloy ingot is inverted once every 500 s of melting. The surface modification of carbon nanotubes and graphene powder is specifically: disposing an organic solvent of a silane coupling agent, wherein the weight percentage of the silane coupling agent is 5 wt%; placing the carbon nanotubes and graphene powder on the silane coupling agent The organic solution was stirred in the organic solution for 10 minutes, and the stirring temperature was 20 ° C. The second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 700 r / min, the ball milling time is 10 hours, and the ball-to-material ratio is 8: 1. During the ball milling process, each ball milling is performed for 50 minutes, and the ball milling is suspended for 8 minutes. The temperature in the tank was below 300 ° C. In the second mixed powder, 110 parts by weight of the crushed Mg-based alloy ingots, 15 parts by surface-modified carbon nanotubes, and 4 parts by surface-modified graphene powder. The first heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is hydrogen, the heat treatment temperature is 620 ° C., the heat treatment time is 15 minutes, and the heating rate is 15 ° C./min. The second hot-pressing sintering of the third mixed powder is specifically: the hot-pressing air pressure is lower than 0.03 Pa, the hot-pressing temperature is 730 ° C., the hot-pressing pressure is 8 MPa, and the hot-pressing time is 8 min.
实施例6Example 6
绿色金属复合材料是由如下方法制备的：提供Mg、Mo、Al、Ni以及Ti粉；按照预定化学式，对Mg、Mo、Al、Ni以及Ti粉进行称重；对称重之后的Mg、Mo、Al、Ni以及Ti粉进行第一球磨，得到第一混合粉；对第一混合粉进行真空熔炼，得到Mg基合金锭；对Mg基合金锭进行破碎；提供碳纳米管和石墨烯粉末；对碳纳米管和石墨烯粉末进行表面改性；将破碎之后的Mg基合金锭以及表面改性后的碳纳米管和石墨烯粉末混合，并进行第二球磨，得到第二混合粉；对第二混合粉进行第一热处理，得到第三混合粉；对第三混合粉进行第二热压烧结。其中，预定化学式为：Mg 100-x-y-z-aMo xAl yNi zTi a，其中，x＝1，y＝2.5，z＝11，a＝2。对称重之后的Mg、Mo、Al、Ni以及Ti粉进行第一球磨具体为：球磨气氛为氩气气氛，球磨速度为1600r/min，球磨时间 为15h，球料比为8.5:1，在球磨过程中每球磨65min，暂停球磨4.5min，球磨过程中控制球磨罐中的温度低于600℃。对第一混合粉进行真空熔炼具体为：真空度低于0.01Pa，熔炼时间为90min，在熔炼过程中，每熔炼220s将合金锭进行一次翻转。对碳纳米管和石墨烯粉末进行表面改性具体为：配置硅烷偶联剂有机溶剂，其中，硅烷偶联剂的重量百分数为2.5wt％；将碳纳米管和石墨烯粉末置于硅烷偶联剂的有机溶液中并进行搅拌，搅拌时间为60min，搅拌温度为75℃。第二球磨具体为：球磨气氛为氩气气氛，球磨速度为550r/min，球磨时间为6h，球料比为4.5:1，在球磨过程中每球磨35min，暂停球磨4.5min，球磨过程中控制球磨罐中的温度低于300℃。在第二混合粉中，以重量份计，破碎之后的Mg基合金锭占150份，表面改性后的碳纳米管占5份和表面改性后的石墨烯粉末占1份。对第二混合粉进行第一热处理具体为：热处理气氛为氢气，热处理温度为620℃，热处理时间为15min，升温速率为15℃/min。对第三混合粉进行第二热压烧结具体为：热压气压低于0.03Pa，热压温度为730℃，热压压力为8MPa，热压时间为8min。 Green metal composite materials are prepared by the following methods: providing Mg, Mo, Al, Ni, and Ti powder; weighing Mg, Mo, Al, Ni, and Ti powder according to a predetermined chemical formula; Mg, Mo, and Al, Ni, and Ti powders are subjected to a first ball milling to obtain a first mixed powder; the first mixed powder is vacuum smelted to obtain an Mg-based alloy ingot; the Mg-based alloy ingot is crushed; carbon nanotubes and graphene powder are provided; Carbon nanotubes and graphene powders are subjected to surface modification; the broken Mg-based alloy ingots and surface-modified carbon nanotubes and graphene powders are mixed and subjected to a second ball milling to obtain a second mixed powder; The mixed powder is subjected to a first heat treatment to obtain a third mixed powder; the third mixed powder is subjected to a second hot-pressing sintering. Wherein, the predetermined chemical formula is: Mg 100-xyza Mo x Al y Ni z Ti a , where x = 1, y = 2.5, z = 11, and a = 2. The first ball milling of Mg, Mo, Al, Ni, and Ti powders after symmetrical weighting is as follows: the ball milling atmosphere is argon, the ball milling speed is 1600r / min, the ball milling time is 15h, and the ball-to-material ratio is 8.5: 1. During the ball milling process, each ball was milled for 65 minutes, and the ball mill was suspended for 4.5 minutes. During the ball milling process, the temperature in the ball mill tank was controlled below 600 ° C. The vacuum melting of the first mixed powder is specifically: the vacuum degree is less than 0.01 Pa, and the melting time is 90 minutes. During the melting process, the alloy ingot is inverted once every 220 s of melting. The surface modification of carbon nanotubes and graphene powder is specifically: disposing an organic solvent of a silane coupling agent, wherein the weight percentage of the silane coupling agent is 2.5% by weight; placing the carbon nanotubes and graphene powder in a silane coupling The organic solution of the agent was stirred, and the stirring time was 60 min, and the stirring temperature was 75 ° C. The second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 550r / min, the ball milling time is 6h, the ball-to-material ratio is 4.5: 1, during the ball milling process, each ball milling is 35min, the ball milling is suspended for 4.5min, and the ball milling process is controlled The temperature in the ball mill tank is below 300 ° C. In the second mixed powder, 150 parts by weight of the crushed Mg-based alloy ingot, 5 parts by surface-modified carbon nanotubes, and 1 part by surface-modified graphene powder. The first heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is hydrogen, the heat treatment temperature is 620 ° C., the heat treatment time is 15 minutes, and the heating rate is 15 ° C./min. The second hot-pressing sintering of the third mixed powder is specifically: the hot-pressing air pressure is lower than 0.03 Pa, the hot-pressing temperature is 730 ° C., the hot-pressing pressure is 8 MPa, and the hot-pressing time is 8 min.
实施例7Example 7
绿色金属复合材料是由如下方法制备的：提供Mg、Mo、Al、Ni以及Ti粉；按照预定化学式，对Mg、Mo、Al、Ni以及Ti粉进行称重；对称重之后的Mg、Mo、Al、Ni以及Ti粉进行第一球磨，得到第一混合粉；对第一混合粉进行真空熔炼，得到Mg基合金锭；对Mg基合金锭进行破碎；提供碳纳米管和石墨烯粉末；对碳纳米管和石墨烯粉末进行表面改性；将破碎之后的Mg基合金锭以及表面改性后的碳纳米管和石墨烯粉末混合，并进行第二球磨，得到第二混合粉；对第二混合粉进行第一热处理，得到第三混合粉；对第三混合粉进行第二热压烧结。其中，预定化学式为：Mg 100-x-y-z-aMo xAl yNi zTi a，其中，x＝1，y＝2.5，z＝11，a＝2。对称重之后的Mg、Mo、Al、Ni以及Ti粉进行第一球磨具体为：球磨气氛为氩气气氛，球磨速度为1600r/min，球磨时间为15h，球料比为8.5:1，在球磨过程中每球磨65min，暂停球磨4.5min，球磨过程中控制球磨罐中的温度低于600℃。对第一混合粉进行真空熔炼具体为：真空度低于0.01Pa，熔炼时间为90min，在熔炼过程中，每熔炼220s将合金 锭进行一次翻转。对碳纳米管和石墨烯粉末进行表面改性具体为：配置硅烷偶联剂有机溶剂，其中，硅烷偶联剂的重量百分数为2.5wt％；将碳纳米管和石墨烯粉末置于硅烷偶联剂的有机溶液中并进行搅拌，搅拌时间为60min，搅拌温度为75℃。第二球磨具体为：球磨气氛为氩气气氛，球磨速度为550r/min，球磨时间为6h，球料比为4.5:1，在球磨过程中每球磨35min，暂停球磨4.5min，球磨过程中控制球磨罐中的温度低于300℃。在第二混合粉中，以重量份计，破碎之后的Mg基合金锭占110份，表面改性后的碳纳米管占15份和表面改性后的石墨烯粉末占4份。对第二混合粉进行第一热处理具体为：热处理气氛为氢气，热处理温度为700℃，热处理时间为25min，升温速率为30℃/min。对第三混合粉进行第二热压烧结具体为：热压气压低于0.03Pa，热压温度为820℃，热压压力为20MPa，热压时间为4min。 Green metal composite materials are prepared by the following methods: providing Mg, Mo, Al, Ni, and Ti powder; weighing Mg, Mo, Al, Ni, and Ti powder according to a predetermined chemical formula; Mg, Mo, and Al, Ni, and Ti powders are subjected to a first ball milling to obtain a first mixed powder; the first mixed powder is vacuum smelted to obtain an Mg-based alloy ingot; the Mg-based alloy ingot is crushed; carbon nanotubes and graphene powder are provided; Carbon nanotubes and graphene powders are subjected to surface modification; the broken Mg-based alloy ingots and surface-modified carbon nanotubes and graphene powders are mixed and subjected to a second ball milling to obtain a second mixed powder; The mixed powder is subjected to a first heat treatment to obtain a third mixed powder; the third mixed powder is subjected to a second hot-pressing sintering. Wherein, the predetermined chemical formula is: Mg 100-xyza Mo x Al y Ni z Ti a , where x = 1, y = 2.5, z = 11, and a = 2. The first ball milling of Mg, Mo, Al, Ni, and Ti powders after symmetrical weighting is as follows: the ball milling atmosphere is argon, the ball milling speed is 1600r / min, the ball milling time is 15h, and the ball-to-material ratio is 8.5: 1. During the ball milling process, each ball was milled for 65 minutes, and the ball mill was suspended for 4.5 minutes. During the ball milling process, the temperature in the ball mill tank was controlled below 600 ° C. The vacuum melting of the first mixed powder is specifically: the vacuum degree is less than 0.01 Pa, and the melting time is 90 minutes. During the melting process, the alloy ingot is inverted once every 220 s of melting. The surface modification of carbon nanotubes and graphene powder is specifically: disposing an organic solvent of a silane coupling agent, wherein the weight percentage of the silane coupling agent is 2.5% by weight; placing the carbon nanotubes and graphene powder in a silane coupling The organic solution of the agent was stirred, and the stirring time was 60 min, and the stirring temperature was 75 ° C. The second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 550r / min, the ball milling time is 6h, the ball-to-material ratio is 4.5: 1, during the ball milling process, each ball milling is 35min, the ball milling is suspended for 4.5min, and the ball milling process is controlled The temperature in the ball mill tank is below 300 ° C. In the second mixed powder, 110 parts by weight of the crushed Mg-based alloy ingots, 15 parts by surface-modified carbon nanotubes, and 4 parts by surface-modified graphene powder. The first heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is hydrogen, the heat treatment temperature is 700 ° C., the heat treatment time is 25 minutes, and the heating rate is 30 ° C./min. The second hot-pressing sintering of the third mixed powder is specifically: the hot-pressing air pressure is less than 0.03 Pa, the hot-pressing temperature is 820 ° C., the hot-pressing pressure is 20 MPa, and the hot-pressing time is 4 min.
对实施例1-7进行吸氢质量百分数测试和30分钟吸氢质量百分数测试，测试方式是本领域公知的方式，测试结果基于实施例1进行归一化，测试结果列于表1。The hydrogen absorption percentage test and the 30-minute hydrogen absorption percentage test of Examples 1-7 were performed in a manner known in the art. The test results were normalized based on Example 1. The test results are shown in Table 1.
表1Table 1
 Zh 吸氢质量百分数Hydrogen absorption percentage 30分钟吸氢质量百分数30 minutes hydrogen absorption percentage
实施例1Example 1 100％100% 100％100%
实施例2Example 2 102％102% 101％101%
实施例3Example 3 102％102% 104％104%
实施例4Example 4 73％73% 59％59%
实施例5Example 5 69％69% 55％55%
实施例6Example 6 72％72% 51％51%
实施例7Example 7 73％73% 41％41%
前述对本发明的具体示例性实施方案的描述是为了说明和例证的目的。这些描述并非想将本发明限定为所公开的精确形式，并且很显然，根据上述 教导，可以进行很多改变和变化。对示例性实施例进行选择和描述的目的在于解释本发明的特定原理及其实际应用，从而使得本领域的技术人员能够实现并利用本发明的各种不同的示例性实施方案以及各种不同的选择和改变。本发明的范围意在由权利要求书及其等同形式所限定。The foregoing description of specific exemplary embodiments of the present invention has been provided for the purposes of illustration and illustration. These descriptions are not intended to limit the invention to the precise forms disclosed, and it is apparent that many changes and modifications can be made in light of the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical application, so that those skilled in the art can implement and utilize the various exemplary embodiments of the present invention and various different Choose and change. It is intended that the scope of the invention be defined by the Claims and their equivalents.

Claims (9)

  1. 一种绿色金属复合材料，其特征在于：所述绿色金属复合材料是由如下方法制备的：A green metal composite material, characterized in that the green metal composite material is prepared by the following method:
    提供Mg、Mo、Al、Ni以及Ti粉；Provide Mg, Mo, Al, Ni and Ti powder;
    按照预定化学式，对所述Mg、Mo、Al、Ni以及Ti粉进行称重；Weighing said Mg, Mo, Al, Ni and Ti powder according to a predetermined chemical formula;
    对称重之后的所述Mg、Mo、Al、Ni以及Ti粉进行第一球磨，得到第一混合粉；Performing the first ball milling on the Mg, Mo, Al, Ni, and Ti powders after being weighed to obtain a first mixed powder;
    对所述第一混合粉进行真空熔炼，得到Mg基合金锭；Vacuum melting the first mixed powder to obtain a Mg-based alloy ingot;
    对所述Mg基合金锭进行破碎；Crushing the Mg-based alloy ingot;
    提供碳纳米管和石墨烯粉末；Provide carbon nanotubes and graphene powder;
    对所述碳纳米管和石墨烯粉末进行表面改性；Performing surface modification on the carbon nanotubes and graphene powder;
    将破碎之后的Mg基合金锭以及表面改性后的碳纳米管和石墨烯粉末混合，并进行第二球磨，得到第二混合粉；Mixing the crushed Mg-based alloy ingot and the surface-modified carbon nanotubes and graphene powder, and performing a second ball milling to obtain a second mixed powder;
    对第二混合粉进行第一热处理，得到第三混合粉；Performing a first heat treatment on the second mixed powder to obtain a third mixed powder;
    对所述第三混合粉进行第二热压烧结。A second hot-pressing sintering is performed on the third mixed powder.
  2. 如权利要求1所述的绿色金属复合材料，其特征在于：其中，所述预定化学式为：Mg 100-x-y-z-aMo xAl yNi zTi a，其中，x＝0.5-1.5，y＝2-3，z＝10-12，a＝1-3。 The green metal composite material according to claim 1, wherein the predetermined chemical formula is: Mg 100-xyza Mo x Al y Ni z Ti a , where x = 0.5-1.5, y = 2-3 , Z = 10-12, a = 1-3.
  3. 如权利要求1所述的绿色金属复合材料，其特征在于：对称重之后的所述Mg、Mo、Al、Ni以及Ti粉进行第一球磨具体为：球磨气氛为氩气气氛，球磨速度为1500-1800r/min，球磨时间为10-20h，球料比为8:1-9:1，在球磨过程中每球磨60-70min，暂停球磨4-5min，球磨过程中控制球磨罐中的温度低于600℃。The green metal composite material according to claim 1, wherein the first ball milling of the Mg, Mo, Al, Ni, and Ti powders after the symmetrical weighting is specifically: the ball milling atmosphere is an argon atmosphere, and the ball milling speed is 1500. -1800r / min, ball milling time is 10-20h, ball-to-material ratio is 8: 1-9: 1, during ball milling, each ball is milled for 60-70min, ball milling is suspended for 4-5min, the temperature in the ball milling tank is controlled during the ball milling At 600 ° C.
  4. 如权利要求1所述的绿色金属复合材料，其特征在于：对所述第一混合粉进行真空熔炼具体为：真空度低于0.01Pa，熔炼时间为80-100min，在熔 炼过程中，每熔炼200-250s将合金锭进行一次翻转。The green metal composite material according to claim 1, characterized in that the vacuum melting of the first mixed powder is specifically: the vacuum degree is lower than 0.01 Pa, and the melting time is 80-100 min. 200-250s turn the alloy ingot once.
  5. 如权利要求1所述的绿色金属复合材料，其特征在于：对所述碳纳米管和石墨烯粉末进行表面改性具体为：The green metal composite material according to claim 1, wherein the surface modification of the carbon nanotubes and graphene powder is specifically:
    配置硅烷偶联剂有机溶剂，其中，所述硅烷偶联剂的重量百分数为2-3wt％；Configure a silane coupling agent organic solvent, wherein the weight percentage of the silane coupling agent is 2-3 wt%;
    将所述碳纳米管和石墨烯粉末置于所述硅烷偶联剂的有机溶液中并进行搅拌，搅拌时间为50-70min，搅拌温度为70-80℃。The carbon nanotubes and graphene powder are placed in an organic solution of the silane coupling agent and stirred, the stirring time is 50-70 min, and the stirring temperature is 70-80 ° C.
  6. 如权利要求1所述的绿色金属复合材料，其特征在于：第二球磨具体为：球磨气氛为氩气气氛，球磨速度为500-600r/min，球磨时间为5-8h，球料比为4:1-5:1，在球磨过程中每球磨30-40min，暂停球磨4-5min，球磨过程中控制球磨罐中的温度低于300℃。The green metal composite material according to claim 1, characterized in that the second ball milling is specifically: the ball milling atmosphere is an argon atmosphere, the ball milling speed is 500-600r / min, the ball milling time is 5-8h, and the ball-material ratio is 4 : 1-5: 1, during the ball milling process, each ball milling is 30-40min, the ball milling is suspended for 4-5min, and the temperature in the ball milling tank is controlled below 300 ° C during the ball milling process.
  7. 如权利要求1所述的绿色金属复合材料，其特征在于：在所述第二混合粉中，以重量份计，破碎之后的Mg基合金锭占100-120份，表面改性后的碳纳米管占10-20份和表面改性后的石墨烯粉末占3-5份。The green metal composite material according to claim 1, wherein in the second mixed powder, 100-120 parts of the Mg-based alloy ingot after the crushing are contained in parts by weight, and carbon nanometers after surface modification The tube accounts for 10-20 parts and the surface modified graphene powder accounts for 3-5 parts.
  8. 如权利要求1所述的绿色金属复合材料，其特征在于：对第二混合粉进行第一热处理具体为：热处理气氛为氢气，热处理温度为600-650℃，热处理时间为10-20min，升温速率为10-20℃/min。The green metal composite material according to claim 1, wherein the first heat treatment of the second mixed powder is specifically: the heat treatment atmosphere is hydrogen, the heat treatment temperature is 600-650 ° C, the heat treatment time is 10-20min, and the heating rate is 10-20 ° C / min.
  9. 如权利要求1所述的绿色金属复合材料，其特征在于：对所述第三混合粉进行第二热压烧结具体为：热压气压低于0.03Pa，热压温度为700-780℃，热压压力为5-10MPa，热压时间为5-10min。The green metal composite material according to claim 1, wherein the second hot-pressing sintering of the third mixed powder is: the hot-pressing air pressure is lower than 0.03Pa, the hot-pressing temperature is 700-780 ° C, The pressing pressure is 5-10MPa, and the hot pressing time is 5-10min.
PCT/CN2018/101941 2018-06-29 2018-08-23 Metal composite material WO2020000615A1 (en)

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