CN112548107A - Preparation method of carbon nano tube coated oxide dispersion strengthened steel composite powder - Google Patents

Preparation method of carbon nano tube coated oxide dispersion strengthened steel composite powder Download PDF

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CN112548107A
CN112548107A CN202011313009.XA CN202011313009A CN112548107A CN 112548107 A CN112548107 A CN 112548107A CN 202011313009 A CN202011313009 A CN 202011313009A CN 112548107 A CN112548107 A CN 112548107A
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powder
gas
carbon source
source precursor
strengthened steel
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李少夫
崔景毅
杨亚锋
胡超权
王宇枭
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Institute of Process Engineering of CAS
Nanjing Green Manufacturing Industry Innovation Research Institute of Process Engineering of CAS
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Institute of Process Engineering of CAS
Nanjing Green Manufacturing Industry Innovation Research Institute of Process Engineering of CAS
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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
    • B22F1/0007—
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • 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
    • C22C32/001—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 with only oxides
    • C22C32/0015—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 with only oxides with only single oxides as main non-metallic constituents
    • C22C32/0026—Matrix based on Ni, Co, Cr or alloys thereof
    • 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
    • B22F2301/35—Iron
    • 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
    • B22F2302/25—Oxide
    • 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

Abstract

The invention relates to a preparation method of carbon nano tube coated oxide dispersion strengthened steel composite powder, which comprises the following steps: adding oxide dispersion strengthened steel powder into a fluidized bed, removing air, heating to a set temperature, introducing mixed gas consisting of a carbon source precursor and protective gas, stopping introducing the carbon source precursor after preset reaction time is reached, only introducing the protective gas to remove residual carbon source precursor, and cooling to obtain the carbon nanotube-coated oxide dispersion strengthened steel composite powder. The preparation method provided by the invention realizes the composite powder with the core-shell structure by adopting the specific raw materials and the redesigned preparation process, and has the advantages of simple process, short production flow, low cost, good industrialization prospect and the like.

Description

Preparation method of carbon nano tube coated oxide dispersion strengthened steel composite powder
Technical Field
The invention relates to the field of nuclear reactor cladding materials, and relates to a preparation method of carbon nano tube coated oxide dispersion strengthened steel powder.
Background
The supercritical water reactor is a fourth-generation reactor developed based on a water-cooled reactor technology and a supercritical thermal power technology, has the advantages of high safety, economy, continuity and the like, and becomes a key candidate reactor type for future development of nuclear power technology in China. However, the supercritical water reactor needs to operate in high-pressure (more than 25MPa), high-temperature (more than 500 ℃) and strong neutron irradiation environments, and the extreme operating conditions cause that the cladding tube material of the conventional pressurized water reactor cannot meet the requirement of the cladding tube material of the supercritical water reactor in terms of high-temperature mechanical property and corrosion resistance, so that the problem of material selection becomes a main obstacle for restricting the development of the supercritical water reactor.
Compared with other traditional structural materials of the nuclear reactor cladding tube, such as austenitic stainless steel, ferrite/martensitic stainless steel and nickel-based alloy, the oxide dispersion strengthened steel is an important candidate structural material of a supercritical water reactor due to excellent creep strength resistance and neutron irradiation resistance under high-temperature conditions. However, the mechanical properties of the oxide dispersion strengthened steel still do not reach the theoretical strength equivalent to the nano oxide strengthening phase after years of development, and when the addition amount reaches more than 1%, the room temperature strength is only improved by less than 300MPa compared with the commercial stainless steel. The main reason is that the oxide dispersion strengthened steel structure prepared by the powder metallurgy technology presents the grain size bimodal distribution characteristic, wherein fine grains inhibit the grain growth because the grain boundary is pinned by nano oxide particles in the sintering process, so a large amount of second phase particles are dispersed in the fine grains and the grain boundary; however, the number density of nano oxide particles distributed in the large-size crystal grains and on the grain boundary is very low, the pinning strengthening effect is very weak, and the nonuniformity of the structure and the performance of the oxide dispersion strengthened steel is directly caused, so that the service performance of the oxide dispersion strengthened steel cannot achieve the expected effect.
Although the mechanical ball milling mixing technique in the prior art is the most common technique for introducing CNTs in a metal matrix, for example, CN101550523A discloses a nickel aluminide intermetallic-carbon nanotube composite material consisting of a nickel aluminide intermetallic compound and nickel-plated carbon nanotubes; wherein: the composite material comprises the following components in percentage by weight: 2-9% of nickel-plated carbon nano tube, and the balance of nickel-aluminide intermetallic compound. The composite material is prepared by preparing Ni by using a mechanical alloying method3Al nano powder, chemical nickel plating on the surface of carbon nanotube, mechanical ball milling method to synthesize Ni3The Al-carbon nano tube composite powder is prepared by performing cold pressing and preforming on the composite powder and then performing hot pressing and sintering. The prepared composite material has high compression strength and fracture toughness and good corrosion resistance, can be applied to turbine blades of aero-engines, and has potential application prospects in the fields of atomic energy industry, catalytic industry, electronic technology and the like.
CN108754205A discloses a preparation method of a carbon nanotube reinforced metal matrix composite material mixed with homologous microdroplets, which can solve the problems that the carbon nanotubes are easy to agglomerate, have low density and are not easy to mix into metal melt in the preparation process of the metal matrix composite material at present. The method comprises the following steps: putting the same spherical metal powder and carbon nano tube powder in a certain ratio into a ball milling tank for ball milling method mixing, wherein the spherical metal powder and the carbon nano tube powder can form local high temperature and compressive stress action on the powder surface in the ball milling process, and the spherical metal powder with the carbon nano tube bonded on the surface is obtained. Adding the obtained metal powder with the carbon nano tube adhered on the surface into the metal melt, and slightly stirring the metal melt in the adding process. The same spherical metal powder is melted at high temperature, the carbon nano tubes are uniformly and dispersedly distributed in the metal melt, the reinforced metal matrix composite material with the carbon nano tubes uniformly distributed in the metal matrix is prepared, and the whole preparation process is simple, efficient and convenient to operate. However, in order to overcome the problem of CNT agglomeration caused by van der waals forces, high energy input is often required, the structural components and structural integrity of CNTs are damaged, the high temperature stability of CNTs is damaged, and alloying elements such as Fe, Ni, Ti, and the like react with CNTs during sintering of CNT-oxide dispersion strengthened steel mixed powder, so that CNTs cannot be retained in oxide dispersion strengthened steel. In addition, a large amount of impurities such as oxygen, nitrogen and the like are often introduced in the ball milling process, so that the two-phase interface is very fragile, and the structure stability and the service performance of the oxide dispersion strengthened steel are damaged.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a preparation method of carbon nanotube-coated oxide dispersion-strengthened steel composite powder, the composite powder with a core-shell structure can be prepared by the preparation method, and the preparation method has the advantages of simple process, short production flow, low cost, good industrialization prospect and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of carbon nano tube coated oxide dispersion strengthened steel composite powder, which comprises the following steps: adding oxide dispersion strengthened steel powder into a fluidized bed, removing air, heating to a set temperature, introducing mixed gas consisting of a carbon source precursor and protective gas, stopping introducing the carbon source precursor after preset reaction time is reached, only introducing the protective gas to remove residual carbon source precursor, and cooling to obtain the carbon nanotube-coated oxide dispersion strengthened steel composite powder.
The preparation method provided by the invention realizes the composite powder with the core-shell structure by adopting the specific raw materials and the redesigned preparation process, and has the advantages of simple process, short production flow, low cost, good industrialization prospect and the like.
As a preferred technical scheme of the invention, the oxide dispersion strengthened steel powder is obtained by carrying out high-energy ball milling on gas atomized pre-alloy powder and rare earth oxide powder.
Preferably, the rare earth oxide powder in the high energy ball milled powder is 0.1-2% by mass, and the rest is gas atomized pre-alloyed powder, such as 0.1%, 0.5%, 1%, 1.5% or 2%, but not limited to the recited values, and other values not recited in the range are also applicable.
Preferably, the gas atomized prealloyed powder comprises the following components in percentage by mass: fe 45-95.5%, and the balance being alloying elements, for example, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, or 95.5%, etc., but not limited to the recited values, and other values not recited in this range are also applicable.
Preferably, the alloying elements comprise 1 or a combination of at least 2 of Cr, Ni, Mo, W, Ti, Zr, or Hf.
Preferably, the particles in the gas atomized pre-alloyed powder are spherical in shape.
Preferably, the purity of the gas atomized pre-alloyed powder is > 98%, and may be, for example, 98.2%, 98.5%, 98.7%, 99%, 99.2%, 99.6%, 99.8%, etc., but is not limited to the recited values, and other values not recited within this range are equally applicable.
Preferably, the particle size of the gas atomized pre-alloyed powder is < 150 μm, and may be, for example, 149 μm, 147 μm, 145 μm, 142 μm, 140 μm, 135 μm, 130 μm, 125 μm, 120 μm, 115 μm, 110 μm or 105 μm, but is not limited to the values recited, and other values not recited within this range are equally applicable.
As a preferred embodiment of the present invention, the rare earth oxide powder includes yttrium oxide powder.
Preferably, the rare earth oxide has a particle size of < 500nm, which may be, for example, 498nm, 496nm, 494nm, 492nm, 490nm, 488nm, 486nm, 484nm, 482nm, 480nm, 478nm, 476nm, 474nm, 472nm, 470nm, 450nm, 420nm, 400nm, 350nm, or 300nm, and the like, but is not limited to the recited values, and other values not recited in this range are equally applicable.
Preferably, the rare earth oxide has a purity of > 97%, and may be, for example, 97%, 97.5%, 98%, 98.2%, 98.5%, 98.7%, 99%, 99.2%, 99.6%, or 99.8%, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
In the invention, other control parameters in the high-energy ball milling are all realized by adopting the prior art, and the details are not repeated in the invention.
As a preferred embodiment of the present invention, the carbon source precursor includes 1 or a combination of at least 2 of methane, ethane, propane, ethylene, propylene, acetylene, propyne, or carbon monoxide.
Preferably, the purity of the carbon source precursor is > 99.99%, for example, 99.991%, 99.992%, 99.993%, 99.994%, 99.995%, 99.996%, 99.997%, 99.998%, 99.999% and the like, but is not limited to the recited values, and other values not recited in the range are also applicable.
As a preferred technical scheme of the invention, the protective gas comprises nitrogen and/or inert gas.
In the present invention, the inert gas includes helium, neon, argon, or the like.
Preferably, the shielding gas has a purity of > 99.99%, and may be, for example, 99.991%, 99.992%, 99.993%, 99.994%, 99.995%, 99.996%, 99.997%, 99.998%, 99.999%, etc., but is not limited to the recited values, and other values not recited in the range are also applicable.
In a preferred embodiment of the present invention, the set temperature is 500-850 ℃, and may be, for example, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, or 800 ℃, but is not limited to the values listed, and other values not listed in the range are also applicable.
In a preferred embodiment of the present invention, the volume ratio of the carbon source precursor to the shielding gas in the mixed gas is (1-10): (2-100), and may be, for example, 1:1, 1:2, 1:10, 1:20, 1:40, 1:60, 1:80, 1:100, 2:1, 5:2, 8:10, 7:20, 3:40, 9:60, 9:80, or 9:100, but is not limited to the above-mentioned values, and other values not listed in this range are also applicable.
As a preferred embodiment of the present invention, the flow rate of the mixed gas is 0.1 to 2m/min, and may be, for example, 0.1m/min, 0.2m/min, 0.4m/min, 0.6m/min, 0.8m/min, 1m/min, 1.2m/min, 1.4m/min, 1.6m/min, 1.8m/min or 2m/min, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are also applicable.
In a preferred embodiment of the present invention, the predetermined reaction time is 2 to 120min, and may be, for example, 2min, 5min, 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min or 120min, but is not limited to the above-mentioned values, and other values not listed in the above range are also applicable.
As a preferred technical solution of the present invention, the preparation method comprises: adding oxide dispersion strengthened steel powder into a fluidized bed, removing air, heating to a set temperature, introducing mixed gas consisting of a carbon source precursor and protective gas, stopping introducing the carbon source precursor after preset reaction time is reached, only introducing the protective gas to remove residual carbon source precursor, and cooling to obtain the carbon nanotube-coated oxide dispersion strengthened steel composite powder;
the set temperature is 500-850 ℃; the volume ratio of the carbon source precursor to the protective gas in the mixed gas is (1-10) to (2-100); the flow rate of the mixed gas is 0.1-2 m/min.
The fluidized bed comprises high-purity quartz or stainless steel, the purity of the high-purity quartz is more than or equal to 99.5%, the fluidized bed consists of a conical fluidized bed inner tube and an original cylindrical sleeve, the conical angle of the conical fluidized bed inner tube is 20-50 degrees, the diameter of the conical fluidized bed inner tube is 20-70mm, the distribution plate is a quartz sintered plate and the like, the diameter of the cylindrical sleeve is 40-80mm, and the diameter of the air inlet and the air outlet is 2-15 mm. The cooling after the reaction is finished can adopt air cooling or furnace cooling.
Compared with the prior art, the invention at least has the following beneficial effects:
(1) the preparation method provided by the invention realizes the composite powder with the core-shell structure by adopting the specific raw materials and the redesigned preparation process, and has the advantages of simple process, short production flow, low cost, good industrialization prospect and the like.
(2) The prepared CNT coated on the surface of the powder has the advantages of adjustable mass fraction, length-diameter ratio and coating layer thickness, high uniformity, good structural integrity and the like, wherein the content of the CNT coated on the surface of the powder is between 0.05 and 5.0 wt.%, and the length-diameter ratio is more than 5.
Drawings
FIG. 1 is an SEM image of carbon nanotube-coated oxide dispersion-strengthened steel composite powder obtained in example 1 of the present invention;
FIG. 2 is a high magnification photograph of the carbon nanotube-coated oxide dispersion strengthened steel composite powder obtained in example 1 of the present invention;
FIG. 3 is an SEM image of the carbon nanotube-coated oxide dispersion-strengthened steel composite powder obtained in example 2 of the present invention;
FIG. 4 is a high magnification photograph of the carbon nanotube-coated oxide dispersion-strengthened steel composite powder obtained in example 2 of the present invention.
The present invention is described in further detail below. The following examples are merely illustrative of the present invention and do not represent or limit the scope of the claims, which are defined by the claims.
Detailed Description
To better illustrate the invention and to facilitate the understanding of the technical solutions thereof, typical but non-limiting examples of the invention are as follows:
example 1
The embodiment provides a preparation method of carbon nanotube coated oxide dispersion strengthened steel composite powder, which comprises the following steps:
1. argon atomized 13Cr-2W-0.5Ti-Fe pre-alloy powder is selected as a raw material, the purity is 98.5 percent, and the particle size is-325 meshes; the yttrium oxide nano powder is selected as a raw material, the grain size is less than 100nm, and the purity is 97.6%.
2. Pre-mixing the pre-alloyed powder and yttrium oxide nano powder according to a mass ratio of 99.6:0.4, then putting the pre-alloyed powder and yttrium oxide nano powder into a stainless steel ball-milling tank for high-energy ball milling, wherein the ball-material ratio is 10:1, the ball-milling rotation speed is 380rpm under the protection of argon, the ball-milling time is 30 hours, and performing batch ball milling.
3. The fluidized bed reactor is made of high-purity quartz and consists of a conical fluidized bed inner tube and an original cylindrical sleeve, the cone angle of the conical fluidized bed inner tube is 20 degrees, the diameter of the conical fluidized bed inner tube is 30mm, the distribution plate is a quartz sintered plate, the diameter of the cylindrical sleeve is 50mm, and the diameter of the air inlet and the diameter of the air outlet are 6 mm.
4. Weighing 100g of oxide dispersion strengthened steel powder after ball milling, adding the oxide dispersion strengthened steel powder into a fluidized bed, connecting a gas circuit through a silicone tube, introducing high-purity argon gas to discharge air in the fluidized bed, wherein the gas speed is 0.5m/min, and the time is 30 min.
5. A high-temperature resistance furnace is used as a heating device, the resistance furnace is cylindrical, the height of the resistance furnace is 50cm, round openings with the size of 15cm are formed in the upper end and the lower end of the resistance furnace, the fluidized bed reactor is placed into the resistance furnace, the temperature is raised to 600 ℃, the stabilization is carried out for 5min, the volume ratio of acetylene to argon is controlled to be 1:4, the flow rate of mixed gas is 0.5m/min, and the chemical vapor deposition reaction is carried out for 15 min.
Stopping introducing acetylene and increasing the gas velocity of argon to 0.5m/min, taking out the fluidized bed after 5min of stabilization, air-cooling the fluidized bed to room temperature, and taking out the powder to obtain the composite powder for preparing the CNT-assisted reinforced oxide dispersion-strengthened steel, wherein the CNT content is 3.5 wt%, and SEM pictures are shown in figures 1 and 2.
Example 2
The embodiment provides a preparation method of carbon nanotube coated oxide dispersion strengthened steel composite powder, which comprises the following steps:
1. argon atomized 316L-4Al prealloying powder is selected as a raw material, the purity is 98.5 percent, and the particle size is 325 meshes below zero; the yttrium oxide nano powder is selected as a raw material, the grain size is less than 100nm, and the purity is 97.6%.
2. Pre-mixing the pre-alloyed powder and yttrium oxide nano powder according to a mass ratio of 99:1, then putting the pre-alloyed powder and yttrium oxide nano powder into a stainless steel ball-milling tank for high-energy ball milling, wherein the ball-material ratio is 10:1, the ball-milling rotation speed is 380rpm, the ball-milling time is 30h, and the ball-milling is carried out in an intermittent ball-milling mode.
3. The fluidized bed reactor is made of high-purity quartz and consists of a conical fluidized bed inner tube and an original cylindrical sleeve, the cone angle of the conical fluidized bed inner tube is 20 degrees, the diameter of the conical fluidized bed inner tube is 30mm, the distribution plate is a quartz sintered plate, the diameter of the cylindrical sleeve is 50mm, and the diameter of the air inlet and the diameter of the air outlet are 6 mm.
4. Weighing 100g of oxide dispersion strengthened steel powder after ball milling, adding the oxide dispersion strengthened steel powder into a fluidized bed, connecting a gas circuit through a silicone tube, introducing high-purity argon gas to discharge air in the fluidized bed, wherein the gas speed is 0.5m/min, and the time is 30 min.
5. A high-temperature resistance furnace is used as a heating device, the resistance furnace is cylindrical, the height of the resistance furnace is 50cm, round openings with the size of 15cm are formed in the upper end and the lower end of the resistance furnace, the fluidized bed reactor is placed into the resistance furnace, the temperature is raised to 600 ℃, the stabilization is carried out for 5min, the ratio of acetylene to argon in mixed gas is controlled to be 1:4, the flow rate of the mixed gas is 0.5m/min, and chemical vapor deposition reaction is carried out for 15 min.
Stopping introducing acetylene and increasing the gas velocity of argon to 0.5m/min, taking out the fluidized bed after 5min of stabilization, air-cooling the fluidized bed to room temperature, and taking out the powder to obtain the composite powder for preparing the CNT-assisted reinforced oxide dispersion-strengthened steel, wherein the CNT content is 0.5 wt%, and SEM pictures are shown in figures 3 and 4.
Example 3
The embodiment provides a preparation method of carbon nanotube coated oxide dispersion strengthened steel composite powder, which comprises the following steps: the difference from example 1 is that the set temperature is lowered to 500 ℃ from 600 ℃ and the reaction time is increased from 15min to 30 min. The composite powder for preparing the CNT-assisted reinforced oxide dispersion-strengthened steel is obtained, the content of the CNT is 5 wt.%, the CNT is still uniformly coated on the surface of the powder, the number density of the CNT is reduced, the length of the CNT is increased, and the reduction of the reaction temperature influences the nucleation number of the CNT, but the increase of the reaction time can improve the growth aging of the CNT, so that the coating amount, the mass fraction and the uniformity of the CNT are not obviously reduced.
Comparative example 1
The only difference from example 1 is that the set temperature was 400 ℃ and no coated CNT was found on the surface of the powder.
Comparative example 2
The difference from example 1 is only that the set temperature is 950 ℃, the powder surface is coated with a small amount of CNT, the CNT content is 1 wt.%, but at the same time, a lot of flocculent amorphous carbon exists, the coating content and distribution uniformity of the CNT are damaged, because at such a high temperature, the pyrolysis behavior of the carbon source precursor is dramatically improved, a lot of amorphous carbon is deposited on the powder surface, and the CNT generation is inhibited.
Comparative example 3
The difference from example 1 is only that the volume ratio of the carbon source precursor to the shielding gas in the mixed gas is 1:200, and no CNT is generated on the surface of the powder, because the carbon source concentration is too low, the number of deposited carbon atoms is too small, and is lower than the solubility of the metal element in the oxide dispersion-strengthened steel powder to the carbon element, so that all the deposited carbon atoms are dissolved into the metal powder in a solid state, and no CNT can be formed.
Comparative example 4
The difference from the embodiment 1 is only that the volume ratio of the carbon source precursor to the protective gas in the mixed gas is 10:1, the surface of the powder is not coated with the CNT, but a large amount of carbon is deposited to form a carbon layer, because the carbon source precursor concentration is too high, the speed of the CNT growing through catalytic nucleation is far lower than the speed of the carbon source pyrolysis to form amorphous carbon, the surface of the powder is quickly and completely covered by the amorphous carbon, and then the CNT cannot be synthesized.
According to the results of the embodiment and the comparative example, the preparation method provided by the invention realizes the composite powder with the core-shell structure by adopting the specific raw materials and the redesigned preparation process, and has the advantages of simple process, short production flow, low cost, good industrialization prospect and the like.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. A preparation method of carbon nano tube coated oxide dispersion strengthened steel composite powder is characterized by comprising the following steps: adding oxide dispersion strengthened steel powder into a fluidized bed, removing air, heating to a set temperature, introducing mixed gas consisting of a carbon source precursor and protective gas, stopping introducing the carbon source precursor after preset reaction time is reached, only introducing the protective gas to remove residual carbon source precursor, and cooling to obtain the carbon nanotube-coated oxide dispersion strengthened steel composite powder.
2. The method according to claim 1, wherein the oxide-dispersion strengthened steel powder is obtained by subjecting gas atomized pre-alloyed powder and rare earth oxide powder to high energy ball milling;
preferably, the rare earth oxide powder in the high-energy ball-milled powder accounts for 0.1-2% by mass, and the balance is gas atomized pre-alloy powder;
preferably, the gas atomized prealloyed powder comprises the following components in percentage by mass: 45-95.5% of Fe and the balance of alloy elements;
preferably, the alloying elements comprise 1 or a combination of at least 2 of Cr, Ni, Mo, W, Ti, Zr, or Hf;
preferably, the particles in the gas atomized pre-alloyed powder are spherical in shape;
preferably, the purity of the gas atomized prealloyed powder is > 98%;
preferably, the particle size of the gas atomized pre-alloyed powder is < 150 μm.
3. The method of claim 2, wherein the rare earth oxide powder comprises yttrium oxide powder;
preferably, the rare earth oxide has a particle size < 500 nm;
preferably, the rare earth oxide has a purity of > 97%.
4. The production method according to any one of claims 1 to 3, wherein the carbon source precursor includes 1 or a combination of at least 2 of methane, ethane, propane, ethylene, propylene, acetylene, propyne, or carbon monoxide;
preferably, the purity of the carbon source precursor is > 99.99%.
5. The method according to any one of claims 1 to 4, wherein the shielding gas comprises nitrogen and/or an inert gas;
preferably, the purity of the shielding gas is > 99.99%.
6. The method according to any one of claims 1-5, wherein the set temperature is 500-850 ℃.
7. The production method according to any one of claims 1 to 6, wherein the volume ratio of the carbon source precursor and the shielding gas in the mixed gas is (1-10) to (2-100).
8. The production method according to any one of claims 1 to 7, wherein the flow rate of the mixed gas is 0.1 to 2 m/min.
9. The method of any one of claims 1 to 8, wherein the predetermined reaction time is 2 to 120 min.
10. The method of any one of claims 1-9, comprising: adding oxide dispersion strengthened steel powder into a fluidized bed, removing air, heating to a set temperature, introducing mixed gas consisting of a carbon source precursor and protective gas, stopping introducing the carbon source precursor after preset reaction time is reached, only introducing the protective gas to remove residual carbon source precursor, and cooling to obtain the carbon nanotube-coated oxide dispersion strengthened steel composite powder;
the set temperature is 500-850 ℃; the volume ratio of the carbon source precursor to the protective gas in the mixed gas is (1-10) to (2-100); the flow rate of the mixed gas is 0.1-2 m/min.
CN202011313009.XA 2020-11-20 2020-11-20 Preparation method of carbon nano tube coated oxide dispersion strengthened steel composite powder Pending CN112548107A (en)

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