CN112974795B - Composite powder for additive manufacturing and remanufacturing and preparation method thereof, and metal-based composite forming layer and preparation method thereof - Google Patents

Composite powder for additive manufacturing and remanufacturing and preparation method thereof, and metal-based composite forming layer and preparation method thereof Download PDF

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CN112974795B
CN112974795B CN202110161964.4A CN202110161964A CN112974795B CN 112974795 B CN112974795 B CN 112974795B CN 202110161964 A CN202110161964 A CN 202110161964A CN 112974795 B CN112974795 B CN 112974795B
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powder
metal
nitrate
composite
treatment
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CN112974795A (en
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于鹤龙
吉小超
王红美
尹艳丽
宋占永
周新远
魏敏
史佩京
张伟
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Hebei Jing Jin Ji Remanufacturing Industry Technology Research Co ltd
Academy of Armored Forces of PLA
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Hebei Jing Jin Ji Remanufacturing Industry Technology Research Co ltd
Academy of Armored Forces of PLA
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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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4417—Methods specially adapted for coating powder
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Abstract

The invention provides composite powder for additive manufacturing and remanufacturing and a preparation method thereof, and a metal matrix composite forming layer and a preparation method thereof. The invention provides a preparation method of composite powder for additive manufacturing, which comprises the following steps: a) carrying out acid treatment on the metal powder by using a nitrate solution to obtain acid-treated powder; b) carrying out chemical vapor deposition treatment on the acid-treated powder in a mixed gas environment of hydrocarbon gas, hydrogen and inert gas to obtain carbon nanotube-metal composite powder; the nitrate in the nitrate solution is selected from one or more of ferric nitrate, nickel nitrate and magnesium nitrate. The method comprises the steps of firstly carrying out acid treatment on metal powder by using nitrate solution, and then carrying out chemical vapor deposition treatment in a hydrocarbon-containing gas environment, so that the metal powder forms a carbon nano tube layer in situ, and the metal powder coated by the carbon nano tube is obtained. The composite powder can be used for preparing a composite forming layer on the surface of metal and is applied to the fields of additive manufacturing and remanufacturing.

Description

Composite powder for additive manufacturing and remanufacturing and preparation method thereof, and metal-based composite forming layer and preparation method thereof
Technical Field
The invention relates to the technical field of surface engineering and remanufacturing, in particular to composite powder for additive manufacturing and remanufacturing and a preparation method thereof, and a metal matrix composite forming layer and a preparation method thereof.
Background
With the continuous development of additive manufacturing and additive remanufacturing technologies, research and application of preparing metal matrix composites by using a 3D printing technology are increasing, and particularly, carbon nanotubes or in-situ carbide ceramic reinforced metal matrix composites have become a focus of research and attention in the field due to high chemical stability and excellent mechanical properties.
Currently, raw materials for preparing carbon nanotube or in-situ carbide ceramic reinforced metal matrix composites are mainly obtained by the following traditional methods: the method comprises the steps of mechanically mixing metal powder and carbon nano tubes by means of a ball milling dispersion method, carrying out ultrasonic liquid phase dispersion mixing by using an ultrasonic cleaning machine, mixing by using a liquid phase chemical method, and preparing agglomerated powder by using a binder in combination with ball milling dispersion. The above method has the following problems: 1) impurity elements are easily introduced in the ball milling process, metal oxidation is easily caused, and the carbon nano tubes are agglomerated and unevenly distributed, so that the reinforcement in the composite material is oversized or irregularly distributed; 2) the content of the carbon nano tube coated by the ultrasonic dispersion or liquid phase chemical method is limited, the utilization rate of the carbon nano tube is low, and the content of a carbon nano tube reinforcement or a carbide ceramic particle reinforcement in the composite material is low; 3) the carbon nanotube/metal composite powder prepared by combining the binder and the ball milling process has large internal porosity, so that the metal matrix composite prepared by 3D printing has many internal pore defects. The above problems all cause the performance of the metal-based composite material to be reduced, and the development requirements of additive manufacturing and additive remanufacturing on high-performance metal composite powder and metal-based composite forming layer materials cannot be met.
Disclosure of Invention
In view of the above, the present invention provides a composite powder for additive manufacturing and remanufacturing, a method for preparing the same, and a metal matrix composite forming layer and a method for preparing the same. The composite powder provided by the invention can be used for additive manufacturing and additive remanufacturing of mechanical parts, and can effectively improve the hardness, wear resistance and mechanical properties of materials.
The invention provides a preparation method of composite powder for additive manufacturing and remanufacturing, which comprises the following steps:
a) carrying out acid treatment on the metal powder by using a nitrate solution to obtain acid-treated powder;
b) carrying out chemical vapor deposition treatment on the acid-treated powder in a mixed gas environment of hydrocarbon gas, hydrogen and inert gas to obtain carbon nanotube-metal composite powder;
the nitrate in the nitrate solution is selected from one or more of ferric nitrate, nickel nitrate and magnesium nitrate.
Preferably, the nitrate solution is a mixed solution of nitrate and dilute nitric acid;
the concentration of the dilute nitric acid is 0.2-0.6 mol/L;
the concentration of nitrate ions in the nitrate solution is 0.5-1.0 mol/L.
Preferably, the acid treatment is ultrasonic acid washing treatment;
the ultrasonic pickling treatment conditions are as follows: the heating temperature is 50-60 ℃, and the power density is 0.8-1.2W/cm2The ultrasonic frequency is 32-40 KHz, and the processing time is 5-10 min.
Preferably, the metal powder is one or more selected from titanium powder, titanium alloy powder, copper alloy powder, aluminum powder and aluminum alloy powder.
Preferably, the chemical vapor deposition treatment is a plasma enhanced chemical vapor deposition treatment;
the process of the plasma enhanced chemical vapor deposition treatment comprises the following steps:
placing the acid treatment powder in plasma enhanced chemical vapor deposition equipment, vacuumizing a reaction cavity, heating to a target temperature, introducing hydrocarbon gas, hydrogen and inert gas into the reaction cavity, and simultaneously switching on a power supply to perform a plasma enhanced chemical vapor deposition reaction to form carbon nanotube-metal composite powder;
the vacuum pumping is carried out until the vacuum degree is 10-4～10-5Pa；
The target temperature is 400-450 ℃;
the flow rate of the hydrocarbon gas is 8-10 sccm;
the flow rate of the inert gas is 40-60 sccm;
the flow rate of the hydrogen is 20-30 sccm;
the reaction power is 40-60W, and the reaction time is 20-30 min.
Preferably, after the step a) and before the step b), the method further comprises: drying the acid-treated powder;
the drying temperature is 120-180 ℃, and the drying time is 2-4 hours.
The invention also provides the composite powder for additive manufacturing and remanufacturing, which is prepared by the preparation method in the technical scheme.
The invention also provides a preparation method of the metal matrix composite forming layer, which comprises the following steps:
preparing a forming layer on a metal matrix by taking the composite powder as a raw material to obtain a metal matrix composite forming layer;
the composite powder is the composite powder for additive manufacturing described in the above technical scheme.
Preferably, the method of preparing the shaping layer is selected from the group consisting of: laser cladding, thermal spraying, plasma cladding, TIG cladding, hot pressing sintering or hot isostatic pressing;
the laser cladding conditions are as follows: the laser power is 0.8-1.5 KW, the diameter of a light spot is 1-3 mm, the scanning speed is 400-600 mm/min, and the multi-channel cladding overlapping rate is 10-20%;
the metal matrix is selected from: a titanium substrate, a titanium alloy substrate, a copper alloy substrate, an aluminum substrate, or an aluminum alloy substrate.
The invention also provides a metal matrix composite forming layer prepared by the preparation method in the technical scheme.
The invention provides a preparation method of composite powder for additive manufacturing and remanufacturing, which comprises the following steps: a) carrying out acid treatment on the metal powder by using a nitrate solution to obtain acid-treated powder; b) carrying out chemical vapor deposition treatment on the acid-treated powder in a mixed gas environment of hydrocarbon gas, hydrogen and inert gas to obtain carbon nanotube-metal composite powder; the nitrate in the nitrate solution is selected from one or more of ferric nitrate, nickel nitrate and magnesium nitrate. The method comprises the steps of firstly carrying out acid treatment on metal-based powder by using nitrate solution, and then carrying out chemical vapor deposition treatment in a hydrocarbon-containing gas environment, so that the metal powder forms a carbon nano tube layer in situ, and the metal powder coated by the carbon nano tube is obtained. The composite powder can be used for preparing a forming layer on the surface of a metal matrix, improves the hardness and mechanical property of the material, and is applied to the field of additive manufacturing and remanufacturing.
The experimental result shows that the microhardness of the composite forming layer prepared by the invention is 675HV0.2The above; sigmabReaches more than 935MPa, sigma0.2Reaches above 843MPa, and delta reaches above 14.8 percent, and shows excellent mechanical property.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an SEM image of a titanium alloy raw material powder Ti6Al4V (TC 4);
FIG. 2 is an SEM image of CNTs/TC4 composite powder prepared in section 1.1 of example 1;
FIG. 3 is an SEM image of CNTs/TC4 composite powder prepared in section 1.1 of example 2;
FIG. 4 is an SEM image of CNTs/TC4 composite powder prepared in section 1.1 of example 3;
FIG. 5 is an SEM image of CNTs/TC4 composite powder prepared in section 1.1 of comparative example 1;
FIG. 6 is a macro topography of a TC4 board composite shape layer material prepared in example 1;
FIG. 7 is an XRD pattern of the composite shaped layer prepared in example 1;
FIG. 8 is a microstructure view of a composite shaped layer prepared in example 1;
FIG. 9 is a microstructure view of a composite shaped layer prepared in comparative example 1;
FIG. 10 is a microstructure view of the composite shaped layer prepared in comparative example 2;
FIG. 11 is a histogram of the microhardness of the composite molded layers obtained in examples 1 to 3 and comparative examples 1 to 2.
Detailed Description
The invention provides a preparation method of composite powder for additive manufacturing and remanufacturing, which comprises the following steps:
a) carrying out acid treatment on the metal powder by using a nitrate solution to obtain acid-treated powder;
b) carrying out chemical vapor deposition treatment on the acid-treated powder in a mixed gas environment of hydrocarbon gas, hydrogen and inert gas to obtain carbon nanotube-metal composite powder;
the nitrate in the nitrate solution is selected from one or more of ferric nitrate, nickel nitrate and magnesium nitrate.
The method comprises the steps of firstly carrying out acid treatment on metal powder by using a nitrate solution, and then carrying out heat treatment in a hydrocarbon-containing gas environment, so that the metal powder forms a carbon nano tube layer in situ, and the metal-based powder coated by the carbon nano tubes is obtained. The composite powder can be used for preparing a composite forming layer on the surface of a metal matrix, improves the hardness and mechanical property of the material, and is applied to the field of additive manufacturing and remanufacturing.
With respect to step a): and carrying out acid treatment on the metal powder by using a nitrate solution to obtain acid-treated powder.
In the invention, the nitrate solution is a mixed solution of nitrate and dilute nitric acid. Wherein the nitrate is selected from one or more of ferric nitrate, nickel nitrate and magnesium nitrate. The concentration of the dilute nitric acid is preferably 0.2-0.6 mol/L. The concentration of nitrate ions in the nitrate solution is preferably 0.5-1.0 mol/L.
In the invention, the metal powder is preferably one or more of titanium powder, titanium alloy powder, copper alloy powder, aluminum powder and aluminum alloy powder; more preferably titanium powder and/or titanium alloy powder. The titanium alloy powder is preferably Ti6Al4V powder.
In the invention, the acid treatment is preferably ultrasonic acid washing treatment; the specific operation process can be as follows: the metal powder was placed in a container containing a nitrate solution and transferred to an ultrasonic cleaning apparatus for ultrasonic treatment. In the present invention, the amount of the metal-containing powder and the nitrate solution is not particularly limited, and the nitrate solution may completely immerse the metal-containing powder. In the present invention, the conditions of the ultrasonic pickling treatment are preferably: the heating temperature is 50-60 ℃, and the power density is 0.8-1.2W/cm2The ultrasonic frequency is 32-40 KHz, and the processing time is 5-10 min.
According to the invention, the nitrate solution is utilized to carry out acid washing treatment on the metal powder, on one hand, the dilute nitric acid and the surface of the metal or alloy powder are subjected to chemical reaction at a certain temperature to carry out corrosion treatment on the metal surface, so that a rough powder surface is obtained, the specific surface area of the powder is increased, and the subsequent in-situ self-generated carbon nanotube growth is facilitated; on the other hand, nitrate ions in the dilute nitric acid and the nitrate salt have strong oxidizability, and oxides generated on the surface of the corroded metal powder can be reduced in plasma enhanced chemical vapor deposition equipment and then used as a catalyst for in-situ growth of carbon nanotubes to promote growth of the metal-based powder on the surfaceCarbon nanotubes. If the concentration of the nitric acid solution is too low or dilute nitric acid is not added, the surface of the metal powder is too smooth, the growth of the carbon nano tube is not facilitated, and the carbon nano tube is easy to cause low adhesion on the surface of the metal powder, uneven coverage and sparse distribution; if the concentration of nitric acid is too high, the active metal reacts violently, melting the powder, or rendering the inactive metal (e.g., Al, Ti) non-corrodible. The nitrate solution functions mainly to provide nitrate ions (NO) having strong oxidizing property together with nitric acid3 -)，NO3 -The concentration of the ions determines the amount of carbon nanotube coating on the surface of the metal powder. The coverage rate, the form and the content of the carbon nano tube on the surface of the composite powder can be adjusted by adjusting the concentration of the dilute nitric acid and the nitrate.
In the present invention, after the acid treatment, it is preferable to further perform: solid-liquid separation and drying. Separating the metal-based powder from the nitrate solution by solid-liquid separation; the solid-liquid separation method is not particularly limited in the present invention, and may be a conventional separation method known to those skilled in the art, such as filtration. In the invention, the drying temperature is preferably 120-180 ℃, and the drying time is preferably 2-4 h. After the above treatment, acid-treated powder was obtained.
With respect to step b): and carrying out chemical vapor deposition treatment on the acid-treated powder in a mixed gas environment of hydrocarbon gas, hydrogen and inert gas to obtain the carbon nano tube-metal composite powder.
In the invention, the hydrocarbon gas is preferably one or more of acetylene, ethane and methane. In the present invention, the kind of the inert gas is not particularly limited, and may be a conventional inert gas known to those skilled in the art, such as nitrogen or argon. In the invention, in the mixed gas of the hydrocarbon gas, the hydrogen gas and the inert gas, the flow rate of the hydrocarbon gas is preferably 8-10 sccm, and more preferably 10 sccm; the flow rate of the hydrogen is preferably 20-30 sccm, and more preferably 25 sccm; the flow rate of the inert gas is preferably 40 to 60sccm, and more preferably 50 sccm.
In the present invention, the chemical vapor deposition treatment is preferably a plasma enhanced chemical vapor deposition treatment. In the invention, the plasma enhanced chemical vapor deposition treatment process comprises the following steps: and placing the acid treatment powder in plasma enhanced chemical vapor deposition equipment, vacuumizing a reaction cavity, heating to a target temperature, introducing hydrocarbon gas, hydrogen and inert gas into the reaction cavity, and simultaneously switching on a power supply to perform a plasma enhanced chemical vapor deposition reaction to form the carbon nano tube-metal composite powder.
The acid treatment powder is placed in plasma enhanced chemical vapor deposition equipment, and specifically, the acid treatment powder is coated by using an aluminum foil and then placed on a cathode plate in the deposition equipment, and a filtering electrode device is arranged above the acid treatment powder. In the present invention, the evacuation is preferably performed so that the degree of vacuum reaches 10-4～10-5Pa. In the invention, the target heating temperature is preferably 400-450 ℃, and more preferably 450 ℃; after the cathode plate reaches the target temperature, gas is introduced; the type and flow rate of the gas are the same as those in the above technical solution, and are not described herein again. And (3) switching on a power supply while introducing gas, setting power and reaction time, and carrying out the plasma enhanced chemical vapor deposition reaction. In the invention, the power is preferably 40-60W, and more preferably 50W; the time is preferably 20-30 min, and more preferably 25 min. Through the plasma enhanced chemical vapor deposition reaction, a carbon nanotube coating layer is formed on the surface of the metal-containing powder, wherein the carbon nanotubes vertically grow on the surface of the metal-containing powder and are tightly combined with the powder.
In the present invention, after the completion of the plasma enhanced chemical vapor deposition reaction, it is preferable to further perform: and turning off a power supply, stopping heating, stopping introducing hydrocarbon gas, continuously introducing inert gas and hydrogen, cooling to room temperature along with the furnace, and taking the material to obtain the carbon nano tube-metal composite powder.
The invention also provides the composite powder for additive manufacturing and remanufacturing, which is prepared by the preparation method in the technical scheme.
The invention also provides a preparation method of the metal matrix composite forming layer, which comprises the following steps:
preparing a forming layer on a metal matrix by taking the composite powder as a raw material to obtain a metal-based composite forming layer material; the composite powder is used for additive manufacturing and remanufacturing in the technical scheme.
In the present invention, the metal matrix is preferably: a titanium substrate, a titanium alloy substrate, a copper alloy substrate, an aluminum substrate, or an aluminum alloy substrate; more preferably a titanium substrate or a titanium alloy substrate.
In the present invention, the method of preparing the shaping layer is preferably: laser cladding, thermal spraying, plasma cladding, TIG cladding, hot pressing sintering or hot isostatic pressing; more preferably laser cladding.
In the invention, the laser cladding conditions are as follows: the laser power is preferably 0.8-1.5 KW, and more preferably 1.2 KW; the diameter of the light spot is preferably 1-3 mm, and more preferably 2 mm; the scanning speed is preferably 400-600 mm/min, and more preferably 500 mm/min; the overlapping rate of the multi-pass cladding is preferably 10-20%, and more preferably 15%. By the above-described treatment, a formed layer is formed on the surface of the metal base, and a composite material having a metal matrix composite formed layer is obtained. In the invention, the thickness of the forming layer is not particularly limited, and can be selected according to the requirements of additive manufacturing and remanufacturing.
The invention also provides a metal-based composite forming layer material prepared by the preparation method in the technical scheme.
Compared with the prior art, the composite powder and metal matrix composite forming layer material prepared by the invention has the following beneficial effects:
the in-situ carbon nanotube/metal-based composite powder prepared by the invention has the advantages that the carbon nanotube on the surface is completely coated and tightly combined with the surface of the metal powder, and the carbon nanotube content on the surface of the composite powder is high; the composite forming layer material prepared by the composite powder has compact structure and no defect inside, the particle size of the in-situ authigenic carbide ceramic reinforcing phase inside the forming layer is nano-scale, the in-situ authigenic carbide ceramic reinforcing phase inside the forming layer is uniformly dispersed inside a metal matrix phase, the in-situ authigenic carbide ceramic reinforcing phase is tightly combined with the metal matrix, and the interface is clean, so that the material has higher microhardness and mechanical property.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
In the following examples, the metal powder used was a spherical powder of Ti6Al4V (TC4) for laser cladding, and the particle size was 30 to 50 μm.
The metal matrix adopts TC4 titanium alloy hot rolled plate, and the preparation process, components, organization structure and performance meet the relevant requirements of aviation titanium and titanium alloy plate and strip specification (GJB2505-95) and TC4 titanium alloy thick plate (GB/T31298-2014). The thickness of the plate is 5.0mm, and the annealing heat treatment conditions are as follows: keeping the temperature at 800 ℃ for 2h, and cooling in air;
when the TC4 powder is subjected to acid cleaning treatment in ultrasonic cleaning equipment, the heating temperature of the solution is 55 ℃, and the power density of the ultrasonic cleaning equipment is 1.0W/cm2Ultrasonic frequency 35kHz, and treatment time 8 min.
Example 1
1.1 preparation of CNTs/TC4 composite powder
S1, carrying out ultrasonic pickling treatment on the TC4 powder by using a mixed solution of dilute nitric acid and magnesium nitrate, wherein the concentration of the dilute nitric acid is 0.2mol/L, and the concentration of the magnesium nitrate in the mixed solution is 0.25mol/L (the concentration of nitrate ions is 0.5 mol/L). And after the ultrasonic pickling is finished, filtering and drying to obtain acid-treated powder.
S2, coating the acid-treated powder with aluminum foil, placing the coated powder on a cathode plate of a plasma enhanced chemical vapor deposition device, and meanwhile, installing a filtering electrode device above the coated powder; the reaction cavity is vacuumized to 10-4Heating is started after Pa, and when the temperature of the cathode plate reaches 450 ℃, acetylene, argon and hydrogen are introduced into the cavity, wherein the flow rates of the acetylene, the argon and the hydrogen are respectively 10sccm, 50sccm and 25 sccm; switching on a power supply, setting the power to be 50W and setting the reaction time to be 25 min; and after the reaction is finished, turning off the power supply, stopping heating, continuously introducing argon and hydrogen, turning off the carbon source, cooling to room temperature along with the furnace, and taking out the sample to obtain the TC4 powder coated by the carbon nano tube.
1.2 preparation of Metal-based composite Forming layer Material
The composite powder obtained in section 1.1 is used as a raw material, an in-situ autogenous TiC reinforced titanium-based composite forming layer with the thickness of 5.0mm is prepared on a TC4 plate substrate by a laser cladding process, and the process parameters are as follows: the laser power is 1.2KW, the diameter of a light spot is 2mm, the scanning speed is 500mm/min, and the multi-channel cladding overlapping rate is 15%.
Example 2
1.1 preparation of CNTs/TC4 composite powder
The procedure is as in example 1, except that the dilute nitric acid concentration is 0.4mol/L and the magnesium nitrate concentration is 0.375mol/L (corresponding to a nitrate ion concentration of 0.75 mol/L).
1.2 preparing metal matrix composite forming layer material: the same as in example 1.
Example 3
1.1 preparation of CNTs/TC4 composite powder
The procedure is as in example 1, except that the dilute nitric acid concentration is 0.6mol/L and the magnesium nitrate concentration is 0.5mol/L (corresponding to a nitrate ion concentration of 1.0 mol/L).
1.2 preparing metal matrix composite forming layer material: the same as in example 1.
Comparative example 1
1.1 preparation of CNTs/TC4 composite powder
The procedure is as in example 1, except that the dilute nitric acid is replaced by deionized water.
1.2, preparing a metal matrix composite forming layer material: the same as in example 1.
Comparative example 2
1.1 preparation of CNTs/TC4 composite powder
And (2) directly mixing TC4 powder and the carbon nano tubes (the mass percentage of the carbon nano tubes in the mixture is 10%) by adopting a wet mechanical ball milling process, wherein the ball milling speed is 120r/min, the ball milling time is 30min, and the ball milling medium is absolute ethyl alcohol. After the ball milling is finished, filtering and drying are carried out, thus obtaining CNTs/TC4 composite powder.
1.2, preparing a metal matrix composite forming layer material: the same as in example 1.
Example 4 characterization and Performance testing
(1) SEM characterization of composite powders
The morphology of the titanium alloy raw material powder Ti6Al4V (TC4) and the CNTs/TC4 composite powder prepared in section 1.1 of each example was analyzed by a Scanning Electron Microscope (SEM). FIG. 1 is an SEM image of Ti6Al4V (TC4) as a raw material powder of a titanium alloy, FIGS. 2 to 4 are SEM images of CNTs/TC4 composite powder prepared in section 1.1 of examples 1 to 3, respectively, and FIG. 5 is an SEM image of CNTs/TC4 composite powder prepared in section 1.1 of comparative example 1; wherein, the right side is an overall appearance graph, and the left side is a partial enlarged view.
It can be seen that the titanium alloy raw material powder Ti6Al4V is approximately spherical, and the surface of the powder is smooth and flat. The surface of the CNTs/TC4 composite powder is uniformly covered with a carbon nano tube coating layer, wherein the carbon nano tube grows along the direction vertical to the surface of the titanium alloy powder. Along with the increase of the concentration of the nitric acid solution and the concentration of the nitrate radical during the acid washing treatment in the preparation process of the composite powder, the density of the carbon nano tube coated on the surface of the powder is increased, the length of the carbon nano tube is increased, and the length is increased from 400-600 nm in the embodiment 1 to 800-1000 nm in the embodiment 3. The CNTs/TC4 composite powder prepared in comparative example 1 has sparse carbon nanotube coating surface and has an area which is not completely covered.
(2) Macro topography of the shaping layer
FIG. 6 is a macro topography of the TC4 board composite shape layer material prepared in example 1. It can be seen that the formed layer is about 5mm thick, the surface is flat and crack-free. Meanwhile, the titanium alloy matrix is not deformed.
(3) XRD analysis of the shaping layer
FIG. 7 is an XRD pattern of the composite shaped layer prepared in example 1. It can be seen that the shaping layer is composed of a Ti matrix phase (consisting of a large amount of a-Ti and a small amount of β -Ti) and a TiC reinforcement phase.
(4) Microstructure of the shaping layer
FIG. 8 is a microstructure of the composite formed layer prepared in example 1, which shows that TiC reinforcement is uniformly distributed in the formed layer, and the particle diameter ranges from 100 nm to 300nm, thus proving that uniformly distributed nano-scale TiC reinforcement is formed in the formed layer.
FIG. 9 is a microstructure diagram of the composite formed layer prepared in comparative example 1, and it can be seen that the content of the reinforcement in the formed layer is significantly lower than that of example 1, mainly due to the fact that the content of the carbon nanotubes formed on the surface of the composite powder is small.
FIG. 10 is a microstructure of the composite formed layer prepared in comparative example 2, which shows that the TiC reinforcement in the formed layer is unevenly distributed, the TiC content in the local region is high, the TiC is not distributed in the local region, and meanwhile, the particle size of TiC particles is 0.5-3 μm, and the particle size is significantly increased.
(5) Micro-hardness of formed layer
The results of the microhardness tests of the composite molded layers obtained in examples 1 to 3 and comparative examples 1 to 2 are shown in table 1 and fig. 11, and fig. 11 is a bar graph of the microhardness of the composite molded layers obtained in examples 1 to 3 and comparative examples 1 to 2.
TABLE 1 microhardness of composite formed layers obtained in examples 1 to 3 and comparative examples 1 to 2
Sample (I) microhardness/HV0.2
Example 1 675
Example 2 756
Example 3 874
Comparative example 1 598
Comparative example 2 532
As can be seen from the test results, the microhardness of the composite formed layer obtained in examples 1 to 3 of the present invention is significantly improved as compared with comparative examples 1 to 2. In examples 1 to 3, the microhardness of the formed layer increased with the increase of the carbon nanotube content on the surface of the composite powder from 675HV0.2Gradually increases to 874HV0.2The hardness of the alloy is more than 2 times of that of TC4 titanium alloy (the hardness of the TC4 titanium alloy substrate is about 310-330 HV)0.2) This is mainly caused by the gradual increase of the content of the in-situ synthesized TiC reinforcing phase in the forming layer. The microhardness of the formed layer of comparative example 1 is significantly reduced, related to the low amount of TiC reinforcement phase in it. The microhardness of the formed layer of comparative example 2 was significantly reduced and the data scatter increased, mainly due to non-uniform distribution of TiC reinforcement within the formed layer, large particle size, and non-uniform particle size distribution.
(6) Tensile strength of the shaping layer
The composite formed layers obtained in examples 1 to 3 and comparative examples 1 to 2 were subjected to a cutting treatment with a titanium alloy substrate by wire cutting, and the surface of the formed layer and the interface adjacent to the substrate were ground by grinding machine processing, and only the formed layer having a thickness of 3mm was left, and the tensile properties at room temperature were measured, and the results are shown in table 2.
TABLE 2 tensile Properties of titanium-based composites obtained in examples 1 to 3 and comparative examples 1 to 2
Sample (I) σb/MPa(MPa) σ0.2/MPa δ/％
Example 1 935 871 14.8
Example 2 957 896 16.5
Example 3 942 843 15.2
Comparative example 1 930 840 14.3
Comparative example 2 855 782 11.6
Note: in Table 2,. sigma.bRepresenting the maximum stress, σ, that the standard tensile specimen of the formed layer can withstand before breaking0.2The yield strength at 0.2% deformation of the formed layer specimen is represented, and δ represents the elongation after tensile failure of the formed layer specimen.
As can be seen from the test results, the tensile mechanical properties of the composite formed layers obtained in examples 1 to 3 of the present invention are improved as compared with those of comparative examples 1 to 2.
Examples 5 to 6
1.1 preparation of CNTs/TC4 composite powder
The procedure is as in example 2, except that magnesium nitrate is replaced with iron nitrate and nickel nitrate, respectively.
1.2 preparing metal matrix composite forming layer material: the same as in example 1.
The microhardness of the composite formed layers obtained in examples 5 to 6 was measured as in example 4 and the results are shown in Table 3:
TABLE 3 microhardness of composite molded layers obtained in examples 5 to 6
Sample (I) microhardness/HV0.2
Example 5 684
Example 6 692
The tensile properties of the TC4 board composite forming layer materials obtained in examples 5 to 6 were tested as in example 4 and the results are shown in table 4:
TABLE 4 tensile Properties of the titanium-based composites obtained in examples 5 to 6
Sample(s) σb/MPa(MPa) σ0.2/MPa δ/％
Examples5 941 862 14.9
Example 6 947 886 15.1
As can be seen from the test results in tables 3-4, when ferric nitrate and nickel nitrate are used, the material has excellent microhardness and mechanical properties.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (6)

1. A method for preparing composite powder for additive manufacturing and remanufacturing, comprising the steps of:
a) carrying out acid treatment on the metal powder by using a nitrate solution to obtain acid-treated powder;
b) carrying out chemical vapor deposition treatment on the acid-treated powder in a mixed gas environment of hydrocarbon gas, hydrogen and inert gas to obtain carbon nanotube-metal composite powder;
the nitrate in the nitrate solution is selected from one or more of ferric nitrate, nickel nitrate and magnesium nitrate;
the nitrate solution is a mixed solution of nitrate and dilute nitric acid;
the concentration of the dilute nitric acid is 0.2-0.6 mol/L;
the concentration of nitrate ions in the nitrate solution is 0.5-1.0 mol/L;
the chemical vapor deposition treatment is plasma enhanced chemical vapor deposition treatment;
the process of the plasma enhanced chemical vapor deposition treatment comprises the following steps:
placing the acid treatment powder in plasma enhanced chemical vapor deposition equipment, vacuumizing a reaction cavity, heating to a target temperature, introducing hydrocarbon gas, hydrogen and inert gas into the reaction cavity, and simultaneously switching on a power supply to perform a plasma enhanced chemical vapor deposition reaction to form carbon nanotube-metal composite powder;
the vacuum pumping is carried out until the vacuum degree is 10-4～10-5Pa；
The target temperature is 400-450 ℃;
the flow rate of the hydrocarbon gas is 8-10 sccm;
the flow rate of the inert gas is 40-60 sccm;
the flow rate of the hydrogen is 20-30 sccm;
the reaction power is 40-60W, and the reaction time is 20-30 min.
2. The production method according to claim 1, wherein the acid treatment is an ultrasonic pickling treatment;
the conditions of the ultrasonic pickling treatment are as follows: the heating temperature is 50-60 ℃, and the power density is 0.8-1.2W/cm2The ultrasonic frequency is 32-40 KHz, and the processing time is 5-10 min.
3. The method according to claim 1, wherein the metal powder is one or more selected from the group consisting of titanium powder, titanium alloy powder, copper alloy powder, aluminum powder, and aluminum alloy powder.
4. The method of claim 1, further comprising, after step a) and before step b): drying the acid-treated powder;
the drying temperature is 120-180 ℃, and the drying time is 2-4 hours.
5. A method for preparing a metal matrix composite forming layer is characterized by comprising the following steps:
preparing a forming layer on a metal matrix by taking the composite powder as a raw material to obtain a metal matrix composite forming layer;
the composite powder is prepared by the preparation method of any one of claims 1-4 and used for additive manufacturing.
6. The method for producing as claimed in claim 5, wherein the method for producing the shaping layer is selected from the group consisting of: laser cladding, thermal spraying, plasma cladding, TIG cladding, hot pressing sintering or hot isostatic pressing;
the laser cladding conditions are as follows: the laser power is 0.8-1.5 KW, the diameter of a light spot is 1-3 mm, the scanning speed is 400-600 mm/min, and the multi-channel cladding overlapping rate is 10% -20%;
the metal matrix is selected from: a titanium substrate, a titanium alloy substrate, a copper alloy substrate, an aluminum substrate, or an aluminum alloy substrate.
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