CN112916867B - Photocuring 3D printing nanoparticle reinforced metal piece and preparation method thereof - Google Patents
Photocuring 3D printing nanoparticle reinforced metal piece and preparation method thereof Download PDFInfo
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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
- 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
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
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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
- B22F1/17—Metallic particles coated with metal
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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
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1017—Multiple heating or additional steps
- B22F3/1021—Removal of binder or filler
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- 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
- B33Y10/00—Processes of additive manufacturing
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- 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
- B33Y80/00—Products made by additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/02—Amorphous alloys with iron as the major constituent
Abstract
The invention relates to a photocuring 3D printing nanoparticle reinforced metal piece and a preparation method thereof, wherein the preparation method comprises the following steps: mixing amorphous powder and a coating agent, adding a coupling agent and metal powder at a set temperature, and stirring to carry out a coating step; carrying out post-treatment on the product obtained in the coating step to obtain an amorphous layer coated metal powder material; coating the amorphous layer with a metal powder material, a photosensitive resin, an ultraviolet initiator and a dispersing agent to prepare photocuring 3D printing slurry; carrying out photocuring forming treatment on the photocuring 3D printing paste by using a photocuring 3D printer to obtain a photocuring 3D printing biscuit; and (4) degreasing and sintering the photocuring 3D printing biscuit to obtain the photocuring 3D printing nanoparticle reinforced metal piece. According to the invention, the metal powder is prepared into the amorphous layer with the powdery core-shell structure and is coated with the metal powder material, so that the dispersibility of the metal powder in the photosensitive resin slurry is improved, and the photocuring 3D printing nanoparticle reinforced metal piece is prepared.
Description
Technical Field
The invention relates to the technical field of 3D printing additive manufacturing, in particular to a photocuring 3D printing nanoparticle reinforced metal piece and a preparation method thereof.
Background
At present, the mechanical industry in China is changed in a mode of accelerating development, the production mode is changed to energy conservation, emission reduction and green manufacturing, the traditional material reduction manufacturing is developed to the direction of material increase manufacturing, and the near net shape manufacturing technology of the material increase manufacturing is generally concerned by people. The metal additive manufacturing technology mainly focuses on the Selective Laser Melting (SLM), Electron Beam Melting (EBM), and other technologies, but the above processes result in material defects of thermal cracks or thermal stress due to the large energy input to the material during the manufacturing process. In order to reduce defects of the prepared material and improve mechanical properties, it is important to explore a new metal additive manufacturing technology.
The photocuring 3D printing technology is an additive manufacturing technology based on the photocuring principle of ultraviolet light on photosensitive resin, and the whole printing layer is cured and molded in a short time, so that the photocuring 3D printing technology has the remarkable characteristics of high efficiency and high precision net and near molding. Compared with a metal additive manufacturing technology adopting a high-energy beam as a heat source, the photocuring 3D printing has the advantages of high forming speed and no residual thermal stress, and is expected to solve the problems existing in the existing metal additive manufacturing.
The most critical link of the photocuring 3D printing technology is to prepare the slurry for the preparation material, and the printing material in the slurry is required to be uniformly and stably distributed and have certain penetrability to ultraviolet light. However, in the existing stage, when the metal material is prepared by photocuring 3D printing, because the surface energy of the metal powder is higher, the agglomeration among particles is easily caused, and the dispersibility of the metal powder in the photosensitive resin is poor; in addition, ultraviolet light cannot penetrate due to agglomeration of the powder, photosensitive resin in the slurry cannot be cured, and finally, a complete photocuring structure cannot be obtained. The problem becomes to limit the wide use of the photocuring 3D printing technology in the field of metal additive manufacturing, so it is very critical to modify the metal powder to improve the dispersion property in the slurry to obtain stable slurry.
Disclosure of Invention
In view of the above, the invention provides a photocuring 3D printing nanoparticle reinforced metal piece and a preparation method thereof, and mainly aims to improve the dispersibility of metal powder in photosensitive resin slurry by preparing metal powder into an amorphous layer with a powdery core-shell structure and coating the amorphous layer with a metal powder material, so as to realize the preparation of the photocuring 3D printing nanoparticle reinforced metal piece by using a photocuring 3D printing technology.
In order to achieve the purpose, the invention mainly provides the following technical scheme:
in one aspect, an embodiment of the present invention provides a method for preparing a photocuring 3D-printed nanoparticle-reinforced metal part, including the following steps:
preparing an amorphous layer coated metal powder material: mixing amorphous powder and a coating agent, adding a coupling agent and metal powder at a first set temperature, and stirring to carry out a coating step; carrying out post-treatment on the product obtained in the coating step to obtain an amorphous layer coated metal powder material; wherein the metal powder is pure metal powder and/or alloy powder;
preparing photocuring 3D printing slurry: coating the amorphous layer with a metal powder material, a photosensitive resin, an ultraviolet initiator and a dispersing agent to prepare a photocuring 3D printing slurry;
preparing a photo-curing 3D printing biscuit: carrying out photocuring forming treatment on the photocuring 3D printing paste by using a photocuring 3D printer to obtain a photocuring 3D printing biscuit;
degreasing and sintering: and carrying out degreasing and sintering treatment on the photocuring 3D printing biscuit to obtain the photocuring 3D printing nanoparticle reinforced metal piece.
Preferably, in the step of preparing the amorphous layer coated metal powder material, the used raw materials are as follows in parts by weight:
55-70 parts of metal powder;
15-25 parts of amorphous powder;
10-15 parts of a coating agent;
5-10 parts of coupling agent.
Preferably, in the step of preparing the amorphous layer coated metal powder material:
the particle size of the metal powder is 10-30 μm; and/or
The metal powder is one or more of FeCrTiAlWMoTaCBZr, FeTiAlNbCB, FeCrAlSiMoBMn, NiCrAlBMo, CoAlNiMnFe and TiZrNiCuBe;
the metal powder is spherical powder or quasi-spherical powder; and/or
The amorphous powder is one or more of FeCrMoCB, FeAlNbB, FeCrSiBMn, NiCrBMo, AlNiMnFe and TiZrNiCuBe powder with the grain diameter of 80-120 nm; preferably, the amorphous powder is spherical powder or spheroidal powder; and/or
The coating agent is one or more of polyacrylic acid, crotonic acid, chloroacrylic acid and titanate; and/or
The coupling agent is one or more of benzoyl peroxide and tert-butyl peroxybenzoate.
Preferably, in the step of preparing the amorphous layer coated metal powder material:
mixing the amorphous powder and the coating agent, stirring the mixture at a second set temperature for a first set time, raising the temperature to the first set temperature, adding the coupling agent and the metal powder while stirring, and continuously stirring the mixture for the second set time to obtain a coated product;
and cleaning and drying the coating product to obtain the amorphous layer coated metal powder material.
Preferably, the second set temperature is 50-60 ℃, and the first set time is 60-120 minutes; and/or the first set temperature is 70-100 ℃, and the second set time is 10-12 hours; and/or the step of cleaning treatment comprises cleaning the coated product with alcohol and deionized water; the drying treatment step comprises: the drying temperature is 80-100 ℃, and the drying time is 5-8 hours.
Preferably, the amorphous layer-coated metal powder material is in a spherical or spheroidal powder shape, and/or the grain diameter of the amorphous layer-coated metal powder material is 10.1-32 microns; and/or the amorphous layer coated metal powder material is a core-shell structure powdery material taking metal powder as a core and an amorphous layer as a shell; the amorphous layer comprises an organic matter formed by the reaction of a coating agent and a coupling agent and amorphous powder dispersed in the organic matter; preferably, the amorphous layer has a thickness of 0.1 to 2 microns.
Preferably, in the step of preparing the photo-curing 3D printing paste, the raw materials used are in parts by weight:
coating 55-70 parts by weight of metal powder material on the amorphous layer;
20-30 parts of photosensitive resin;
1-5 parts of ultraviolet initiator;
5-10 parts of dispersing agent.
Preferably, in the step of formulating a photocurable 3D printing paste:
the photosensitive resin is acrylic resin; and/or
The ultraviolet light initiator is BASF 819; and/or
The dispersant is sodium polyacrylate.
Preferably, the step of degreasing and sintering comprises: in a protective atmosphere with the negative pressure of 0.05-0.08MPa, the photocuring 3D printing biscuit is heated from room temperature to 200-280 ℃ at the heating rate of 1-2 ℃/min, is kept at the temperature of 200-280 ℃ for 240min, is heated to 300-500 ℃ at the heating rate of 2-3 ℃/min, is kept at the temperature of 300-500 ℃ for 360min, and is cooled to room temperature at the cooling rate of 5-8 ℃/min.
On the other hand, the embodiment of the invention provides a photocuring 3D printing nanoparticle reinforced metal piece, wherein the crack density of the photocuring 3D printing nanoparticle reinforced metal piece is not more than 2.8%; preferably, the content of the nanoparticles in the photocuring 3D printing nanoparticle-reinforced metal part is as follows: 15.7-35.7 wt%; preferably, the average grain size of the photocuring 3D printing nanoparticle reinforced metal piece is 9-11 μm;
preferably, the specific strength of the photocuring 3D printing nanoparticle reinforced metal piece is 0.19-0.21 MPa-Kg- 1m3(ii) a Preferably, the photocuring 3D printing nanoparticle reinforced metal part is prepared by the preparation method of the photocuring 3D printing nanoparticle reinforced metal part.
Compared with the prior art, the photocuring 3D printing nanoparticle reinforced metal piece and the preparation method thereof have at least the following beneficial effects:
according to the preparation method of the photocuring 3D printing nanoparticle reinforced metal piece, the organic matter formed by the coating agent and the coupling agent is used for coating the amorphous powder outside the metal powder, and the obtained amorphous layer coating metal powder material with the powdery core-shell structure is good in dispersibility in photosensitive resin slurry; the dispersion characteristic of metal powder in the printing slurry in the photocuring process is improved by utilizing the good interface wettability of the amorphous material to organic matters and metal materials, accordingly, the transmittance of the 3D printing slurry to ultraviolet light is increased, the requirements of photocuring 3D printing are met, and a high-precision printing entity is obtained; and further removing organic matters and resin through degreasing and sintering steps, thereby obtaining the photocuring 3D printing nanoparticle reinforced metal piece. Here, it should be noted that: the amorphous material has the characteristic of easy crystallization and heat release, and reduces the degreasing and sintering temperature of the printed entity. The invention correspondingly reduces the sintering and degreasing temperatures, can reserve the fine grain size of the metal powder to the maximum extent, and can enhance the mechanical property of the prepared metal piece due to the nano alloy particles introduced in situ by amorphous crystallization in the processes of low-temperature degreasing and sintering. Furthermore, the composition of the nano crystal grains formed by amorphous crystallization is consistent with that of the metal powder elements, and the nano crystal grains can also play a role in fine crystal strengthening, so that the mechanical property of the photocuring 3D printing metal part is further enhanced.
In conclusion, the photocuring 3D printing nanoparticle reinforced metal piece and the preparation method thereof can obtain stable photocuring 3D printing slurry, reduce the sintering degreasing temperature and introduce the nano alloy particles in situ, so that the prepared nanoparticle reinforced metal piece has higher mechanical properties.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
Fig. 1 is a process flow diagram of a method for manufacturing a photocuring 3D-printed nanoparticle-reinforced metal part according to an embodiment of the present invention;
fig. 2 is a schematic cross-sectional structure diagram of spherical powder particles of an amorphous layer coated with a metal powder material according to an embodiment of the present invention.
Detailed Description
To further explain the technical means and effects of the present invention adopted to achieve the predetermined object, the following detailed description of the embodiments, structures, features and effects according to the present invention will be made with reference to the accompanying drawings and preferred embodiments. In the following description, different "one embodiment" or "an embodiment" refers to not necessarily the same embodiment. Furthermore, the particular features, structures, or characteristics may be combined in any suitable manner in one or more embodiments.
In the prior art, when a metal part is prepared by photocuring 3D printing, because the surface energy of metal powder is high, the agglomeration among particles is easily caused, and the dispersibility of the metal powder in photosensitive resin is poor; in addition, ultraviolet light cannot penetrate due to agglomeration of the powder, photosensitive resin in the slurry cannot be cured, and finally, a complete photocuring structure cannot be obtained.
Based on the problems, the invention provides a photocuring 3D printing nanoparticle reinforced metal piece prepared by a photocuring 3D printing technology, wherein an amorphous layer is coated on the surface of metal powder to improve the dispersibility of the metal powder in photosensitive resin slurry. The specific scheme is as follows:
in one aspect, embodiments of the present invention provide a method for photocuring a 3D-printed nanoparticle-reinforced metal part, where "nanoparticles" are referred to as "nano-alloy particles". As shown in fig. 1, it includes the following steps:
preparing an amorphous layer coated metal powder material: mixing amorphous powder and a coating agent, adding a coupling agent and metal powder at a first set temperature, and stirring to carry out a coating step; carrying out post-treatment on the product obtained in the coating step to obtain an amorphous layer coated metal powder material; wherein the metal powder is pure metal powder and/or alloy powder.
The method comprises the following steps: mixing the amorphous powder and the coating agent in a beaker, heating to 50-60 ℃, mechanically stirring for 60-120 minutes, then heating to 70-100 ℃, slowly adding the coupling agent and the metal powder while mechanically stirring, and continuously stirring for 10-12 hours. And taking out the product powder, washing the product powder with alcohol and deionized water, and then drying the product powder in an oven at the temperature of 80-100 ℃ for 5-8 hours to obtain the amorphous layer coated metal powder material.
In the step, the used raw materials are as follows by weight: 55-70 parts of metal powder, 15-25 parts of amorphous powder, 10-15 parts of coating agent and 5-10 parts of coupling agent.
In the step, the metal powder is one or more of FeCrTiAlWMoTaCBZr, FeTiAlNbCB, FeCrAlSiMoBMn, NiCrAlBMo, CoAlNiMnFe and TiZrNiCuBe spherical powder with the grain diameter of 10-30 mu m. The amorphous powder is one or more of FeCrMoCB, FeAlNbB, FeCrSiBMn, NiCrBMo, AlNiMnFe and TiZrNiCuBe spherical powder with the grain diameter of 80-120 nm. The coating agent is one or more of polyacrylic acid, crotonic acid, chloroacrylic acid and titanate. The coupling agent is one or more of benzoyl peroxide and tert-butyl peroxybenzoate.
Preparing photocuring 3D printing slurry: and coating the amorphous layer with a metal powder material, photosensitive resin, an ultraviolet initiator and a dispersing agent to prepare the photocuring 3D printing slurry.
The method comprises the following steps: and mixing 55-70 parts by weight of an amorphous layer coating metal powder material, 20-30 parts by weight of photosensitive resin, 1-5 parts by weight of initiator and 5-10 parts by weight of dispersant, and ball-milling to obtain the photocuring 3D printing slurry.
Preferably, the photosensitive resin is acrylic resin, the ultraviolet light initiator is BASF 819, and the dispersant is sodium polyacrylate.
Preparing a photo-curing 3D printing biscuit: and carrying out photocuring forming treatment on the photocuring 3D printing paste by using a photocuring 3D printer to obtain a photocuring 3D printing biscuit.
Degreasing and sintering: and carrying out degreasing and sintering treatment on the photocuring 3D printing biscuit to obtain the photocuring 3D printing nanoparticle reinforced metal piece.
The method comprises the following steps: in the Ar protective atmosphere with the negative pressure of 0.05-0.08MPa, the biscuit is heated up to 200-minus-plus-280 ℃ from the room temperature at the heating rate of 1-2 ℃/min, and is kept at the temperature of 200-minus-plus-280 ℃ for 240min, and is heated up to 300-minus-plus-500 ℃ at the heating rate of 2-3 ℃/min, and is kept at the temperature of 300-minus-plus-500 ℃ for 180-minus-plus-360 min, and is cooled down to the room temperature at the cooling rate of 5-8 ℃/min.
According to the preparation method of the photocuring 3D printing nanoparticle reinforced metal piece, provided by the embodiment of the invention, the metal powder is prepared into the amorphous coated metal powder material with a powdery core-shell structure (the amorphous powder is coated outside the metal powder by using an organic matter formed by a coating agent and a coupling agent, and the obtained amorphous coated metal powder material is coated), so that the dispersibility of the metal powder in photosensitive resin slurry is improved; the better interface wettability of the amorphous material to organic matters and metal materials is utilized to improve the dispersion characteristic of metal powder in the printing slurry in the photocuring process, accordingly, the transmittance of the 3D printing slurry to ultraviolet light is increased, the requirements of photocuring 3D printing are met, and therefore a high-precision printing entity is obtained. In addition, the amorphous material has the characteristic of easy crystallization and heat release, the invention correspondingly reduces the sintering and degreasing temperature, can reserve the fine grain size of the metal powder to the maximum extent, and can enhance the mechanical property of the prepared metal parts due to the nano alloy particles introduced in situ by amorphous crystallization in the process of low-temperature degreasing and sintering. Furthermore, the composition of the nano crystal grains formed by amorphous crystallization is consistent with that of the metal powder elements, and the nano crystal grains can also play a role in fine crystal strengthening, so that the mechanical property of the photocuring 3D printing metal part is further enhanced.
Here, it should be noted that: the content of the nano particles in the nano particle reinforced metal piece prepared by the method is consistent with the proportion of the amorphous powder in the preparation formula (the amorphous powder and the metal powder); when 55-70 parts by weight of metal powder and 15-25 parts by weight of amorphous powder, the content of the nanoparticles in the photocuring 3D printing nanoparticle reinforced metal piece is as follows: 15.7-35.7 wt%.
In conclusion, the technical scheme of the invention can obtain stable photocuring 3D printing slurry, reduce sintering degreasing temperature and introduce nano alloy particles in situ, so that the prepared nano particle reinforced metal piece has higher mechanical property.
The present invention will be described in further detail with reference to specific examples.
Example 1
The preparation of the photocuring 3D printing nanoparticle reinforced metal piece in this embodiment specifically includes the following steps:
preparing an amorphous layer coated metal powder material: firstly, 250g of FeCrMoCB amorphous powder with the grain diameter of 80nm (wherein the mass fraction of Fe is 57%, the mass fraction of Cr is 23%, the mass fraction of Mo is 18%, the mass fraction of C is 1.5%, and the mass fraction of B is 0.5%) and 100g of polyacrylic acid are placed in a beaker to be mixed, the temperature is raised to 50 ℃, mechanical stirring is carried out for 60 minutes, then the temperature is raised to 100 ℃, to this, 50g of benzoyl peroxide and 700g of FeCrTiAlWMoTaCBZr metal powder having a particle diameter of 10 μm (wherein the mass fraction of Fe is 58.25, the mass fraction of Cr is 21%, the mass fraction of Ti is 8%, the mass fraction of Al is 4.5%, the mass fraction of W is 4%, the mass fraction of Mo is 2%, the mass fraction of Ta is 2%, the mass fraction of C is 0.05%, the mass fraction of B is 0.05%, and the mass fraction of Zr is 0.15%) were slowly added while mechanically stirring (alloy powder), and the coating step was carried out for 12 hours with continuous stirring. And taking out the product powder in the coating step, washing the product powder with alcohol and deionized water, and drying the product powder in an oven at 80 ℃ for 5 hours to obtain the amorphous layer coated metal powder material.
Preparing photocuring 3D printing slurry: 700g of amorphous layer coated metal powder material, 240g of acrylic resin, 10g of BASF 819 and 50g of sodium polyacrylate are mixed and subjected to ball milling, and the photocuring 3D printing slurry is obtained.
Preparing a photo-curing 3D printing biscuit: carrying out photocuring forming on the photocuring 3D printing paste by using photocuring 3D printing equipment to obtain a photocuring 3D printing biscuit;
degreasing and sintering: degreasing and sintering the photo-cured biscuit to obtain a photo-cured 3D printing nano particle reinforced metal piece; wherein the degreasing and sintering treatment steps comprise:
in the Ar protective atmosphere with the negative pressure of 0.05MPa, the biscuit is heated to 280 ℃ from the room temperature at the heating rate of 1 ℃/min, and is kept at the temperature of 280 ℃ for 120min, then is heated to 300 ℃ at the heating rate of 2 ℃/min, is kept at the temperature of 300 ℃ for 360min, and then is cooled to the room temperature at the cooling rate of 8 ℃/min.
FIG. 2 is a schematic cross-sectional view of the metal powder material coated with an amorphous layer; referring to fig. 1, amorphous powder 2 is coated outside metal powder 1 by using an organic substance 3 obtained by a reaction of a coating agent and a coupling agent. The grain diameter of the spherical powder of the metal powder material covered by the amorphous layer is about 10.1 microns, the surface of the metal powder 1 is covered by the amorphous layer (comprising organic matters and amorphous powder dispersed in the organic matters) of about 150 nanometers, and the amorphous layer improves the penetration depth and the characteristics of easy agglomeration and poor dispersibility of the metal powder in the light curing process.
In addition, the test data of the average grain size, crack density and specific strength of the photo-cured 3D printed nanoparticle reinforced metal article prepared in this example are shown in table 1.
Example 2
The preparation of the photocuring 3D printing nanoparticle reinforced metal piece in this embodiment specifically includes the following steps:
preparing an amorphous layer coated metal powder material: firstly, 150g of FeAlNbB amorphous powder (wherein the mass fraction of Fe is 71.5%, the mass fraction of Al is 24%, the mass fraction of Nb is 4%, and the mass fraction of B is 0.5%) with the particle size of 120nm and 150g of chloropropenoic acid are placed in a beaker to be mixed, the temperature is raised to 60 ℃, after mechanical stirring is carried out for 90 minutes, the temperature is raised to 90 ℃, 100g of tert-butyl peroxybenzoate and 600g of FeTiAlNbCB metal powder (alloy powder, wherein the mass fraction of Fe is 60%, the mass fraction of Ti is 18%, the mass fraction of Al is 17%, the mass fraction of Nb is 4%, the mass fraction of C is 0.5%, and the mass fraction of B is 0.5%) with the particle size of 30 microns are slowly added while mechanical stirring, and the coating step is carried out by continuously stirring for 11 hours. And taking out the product powder in the coating step, washing the product powder with alcohol and deionized water, and drying the product powder in an oven at 100 ℃ for 6 hours to obtain the amorphous layer coated metal powder material.
Preparing photocuring 3D printing slurry: 600g of the amorphous layer coated with the metal powder material, 300g of the acrylic resin, 50g of the BASF 819 and 50g of the sodium polyacrylate are mixed and subjected to ball milling, and the photocuring 3D printing paste is obtained.
Preparing a photo-curing 3D printing biscuit: and carrying out photocuring forming on the photocuring 3D printing paste by using photocuring 3D printing equipment to obtain a photocuring 3D printing biscuit.
Degreasing and sintering: degreasing and sintering the photo-cured biscuit to obtain a photo-cured 3D printing nano particle reinforced metal piece; wherein the degreasing and sintering treatment steps comprise:
in the Ar protective atmosphere with the negative pressure of 0.08MPa, the biscuit is heated to 200 ℃ from the room temperature at the heating rate of 2 ℃/min, and is kept at the temperature of 200 ℃ for 240min, then heated to 500 ℃ at the heating rate of 3 ℃/min, is kept at the temperature of 500 ℃ for 300min, and then is cooled to the room temperature at the cooling rate of 5 ℃/min.
In this embodiment, the amorphous metal powder is coated outside the metal powder by using an organic substance obtained by the reaction of the coating agent and the coupling agent, so as to obtain an amorphous layer coated metal powder material. The amorphous layer coated metal powder material prepared in this example is in the form of spherical powder, the particle size is about 32 microns, and the shell thickness is about 2 microns.
The test data for average grain size, crack density, and specific strength of the photo-cured 3D printed nanoparticle reinforced metal articles prepared in this example are shown in table 1.
Example 3
The preparation of the photocuring 3D printing nanoparticle reinforced metal piece in this embodiment specifically includes the following steps:
preparing an amorphous layer coated metal powder material: 200g of FeCrSiBMn amorphous powder (the mass fraction of Fe is 69.5%, the mass fraction of Cr is 24%, the mass fraction of Si is 4%, the mass fraction of B is 0.5%, the mass fraction of Mn is 2%) with 100nm particle size and 120g of polyacrylic acid are placed in a beaker to be mixed, the temperature is raised to 55 ℃, after mechanical stirring is carried out for 100 minutes, the temperature is raised to 80 ℃, 80g of benzoyl peroxide and 600g of FeCrAlSiMoBMn metal powder (alloy powder, wherein the mass fraction of Fe is 58%, the mass fraction of Cr is 21%, the mass fraction of Al is 17%, the mass fraction of Si is 2%, the mass fraction of Mo is 1%, the mass fraction of B is 0.5%, and the mass fraction of Mn is 0.5%) with 20 microns particle size are slowly added while mechanical stirring, and the stirring is continued for 10 hours to carry out the coating step. And taking out the product powder in the coating step, washing the product powder with alcohol and deionized water, and drying the product powder in an oven at 80 ℃ for 8 hours to obtain the amorphous layer coated metal powder material.
Preparing photocuring 3D printing slurry: 600g of amorphous layer coated metal powder material, 250g of acrylic resin, 50g of BASF 819 and 100g of sodium polyacrylate are mixed and subjected to ball milling to obtain the photocuring 3D printing metal slurry.
Preparing a photo-curing 3D printing biscuit: and carrying out photocuring forming on the photocuring 3D printing paste by using photocuring 3D printing equipment to obtain a photocuring 3D printing biscuit.
Degreasing and sintering: degreasing and sintering the photo-cured biscuit to obtain a photo-cured 3D printing nano particle reinforced metal piece; wherein the degreasing and sintering treatment steps comprise:
in the Ar protective atmosphere with the negative pressure of 0.07MPa, the biscuit is heated to 250 ℃ from the room temperature at the heating rate of 1 ℃/min, the temperature is preserved for 200min at the temperature of 250 ℃, then is heated to 300 ℃ at the heating rate of 2 ℃/min, the temperature is preserved for 360min at the temperature of 300 ℃, and then is cooled to the room temperature at the cooling rate of 5 ℃/min.
In this embodiment, the amorphous metal powder is coated outside the metal powder by using an organic substance obtained by the reaction of the coating agent and the coupling agent, so as to obtain an amorphous layer coated metal powder material. The amorphous layer coated metal powder material prepared in this example was in the form of spherical powder with a particle size of about 21 microns and a shell thickness of about 1 micron.
The test data for average grain size, crack density, and specific strength of the photo-cured 3D printed nanoparticle reinforced metal articles prepared in this example are shown in table 1.
Comparative example 1
Comparative example 1 a fecrtial wmotacarbor alloy part (mass fraction of Fe 58.25%, mass fraction of Cr 21%, mass fraction of Ti 8%, mass fraction of Al 4.5%, mass fraction of W4%, mass fraction of Mo 2%, mass fraction of Ta 2%, mass fraction of C0.05%, mass fraction of B0.05%, mass fraction of Zr 0.15%) was prepared; comparative example 1 mainly uses a Selective Laser Melting (SLM) process to prepare fecrtialmwmotacbzr metal powder into fecrtialmwmotacbzr alloy parts.
The average grain size, crack density and specific strength test data of the FeCrTiAlWMoTaCBZr alloy parts prepared in comparative example 1 are shown in Table 1.
Table 1 shows the average grain size, crack density and specific strength test data for the metal parts obtained in examples 1 to 3 and comparative example 1.
TABLE 1
Note: "average grain size" refers to the average grain size of a plurality of samples prepared by the same process.
The average grain size and the crack density were obtained by SEM examination and analysis using the image processing software ImagePro. The specific strength is obtained by testing with a mechanical testing machine, the sample mass is obtained by testing with a balance, the volume of the sample is obtained by testing with a drainage and gas collection method, and the formula is used: specific intensity is (intensity x volume)/mass.
As can be seen from table 1: the average grain size of the photocuring 3D printing nanoparticle reinforced metal piece prepared by the embodiment of the invention is smaller, and the main reasons are as follows: firstly, amorphous material is crystallized to obtain a large amount of nanocrystalline with smaller grain size which is dispersed and distributed in the material, and secondly, the sintering temperature is reduced due to the coating of the amorphous material, so that the smaller grain size in alloy and metal powder is retained to the maximum extent in the preparation process. Compared with the material prepared by the selective laser melting process, the metal parts prepared by the method provided by the embodiment of the invention have fewer defects such as cracks and the like, mainly because the preparation process inherent in the photocuring preparation process has no large temperature change and high-temperature treatment. The metal piece prepared by the method provided by the embodiment of the invention has obviously improved specific strength, and the main reason is that the defects such as fine crystal strengthening effect and microcracks in the material are less.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (14)
1. A preparation method of a photocuring 3D printing nanoparticle reinforced metal piece is characterized by comprising the following steps:
preparing an amorphous layer coated metal powder material: mixing amorphous powder and a coating agent, adding a coupling agent and metal powder at a first set temperature, and stirring to carry out a coating step; carrying out post-treatment on the product obtained in the coating step to obtain an amorphous layer coated metal powder material; wherein the metal powder is pure metal powder and/or alloy powder; the amorphous layer coated metal powder material is a core-shell structure powder material taking metal powder as a core and an amorphous layer as a shell; the amorphous layer comprises an organic matter formed by the reaction of a coating agent and a coupling agent and amorphous powder dispersed in the organic matter;
preparing photocuring 3D printing slurry: coating the amorphous layer with a metal powder material, a photosensitive resin, an ultraviolet initiator and a dispersing agent to prepare a photocuring 3D printing slurry;
preparing a photo-curing 3D printing biscuit: carrying out photocuring forming treatment on the photocuring 3D printing paste by using a photocuring 3D printer to obtain a photocuring 3D printing biscuit;
degreasing and sintering: degreasing and sintering the photocuring 3D printing biscuit to obtain a photocuring 3D printing nanoparticle reinforced metal piece;
wherein the metal powder is one or more of FeCrTiAlWMoTaCBZr, FeTiAlNbCB, FeCrAlSiMoBMn, NiCrAlBMo, CoAlNiMnFe and TiZrNiCuBe;
the amorphous powder is one or more of FeCrMoCB, FeAlNbB, FeCrSiBMn, NiCrBMo, AlNiMnFe and TiZrNiCuBe powder with the grain diameter of 80-120 nm;
the coating agent is one or more of polyacrylic acid, crotonic acid, chloroacrylic acid and titanate;
the coupling agent is one or more of benzoyl peroxide and tert-butyl peroxybenzoate.
2. The method for preparing the photocuring 3D printing nanoparticle-reinforced metal piece according to claim 1, wherein in the step of preparing the amorphous layer-coated metal powder material, the raw materials are used in parts by weight:
55-70 parts of metal powder;
15-25 parts of amorphous powder;
10-15 parts of a coating agent;
5-10 parts of coupling agent.
3. The method for preparing the photocuring 3D printing nanoparticle-reinforced metal piece as claimed in claim 1, wherein in the step of preparing the amorphous layer coated with the metal powder material:
the particle size of the metal powder is 10-30 μm; and/or
The metal powder is spherical powder or quasi-spherical powder.
4. The method of claim 1, wherein the amorphous powder is a spherical powder or a spheroidal powder.
5. The method for preparing a photocured 3D printed nanoparticle-reinforced metal part according to any one of claims 1 to 4, wherein in the step of preparing the amorphous layer coated metal powder material:
mixing the amorphous powder and the coating agent, stirring the mixture at a second set temperature for a first set time, raising the temperature to the first set temperature, adding the coupling agent and the metal powder while stirring, and continuously stirring the mixture for the second set time to obtain a coated product;
and cleaning and drying the coating product to obtain the amorphous layer coated metal powder material.
6. The method of manufacturing a photocuring 3D printing nanoparticle-reinforced metal part of claim 5,
the second set temperature is 50-60 ℃, and the first set time is 60-120 minutes; and/or
The first set temperature is 70-100 ℃, and the second set time is 10-12 hours; and/or
The step of cleaning treatment comprises the step of cleaning the coated product by using alcohol and deionized water;
the drying treatment step comprises: the drying temperature is 80-100 ℃, and the drying time is 5-8 hours.
7. The method of manufacturing a photo-cured 3D printed nanoparticle reinforced metal part according to any one of claims 1 to 4,
the amorphous layer is coated with metal powder material and is spherical or quasi-spherical powder; and/or
The grain diameter of the amorphous layer coated metal powder material is 10.1-32 microns; and/or
The thickness of the amorphous layer is 0.1-2 microns.
8. The method for preparing the photocured 3D printed nanoparticle-reinforced metal part according to any one of claims 1 to 4, wherein in the step of preparing the photocured 3D printing paste, the raw materials are prepared from the following raw materials in parts by weight:
55-70 parts by weight of amorphous layer coated metal powder material;
20-30 parts of photosensitive resin;
1-5 parts of ultraviolet initiator;
5-10 parts of a dispersing agent.
9. The method for preparing a photocured 3D printed nanoparticle-reinforced metal part according to any one of claims 1 to 4, wherein in the step of formulating a photocured 3D printing paste:
the photosensitive resin is acrylic resin; and/or
The ultraviolet light initiator is BASF 819; and/or
The dispersant is sodium polyacrylate.
10. The method of manufacturing a photocured 3D printed nanoparticle-reinforced metal part of claim 1, wherein the step of degreasing and sintering comprises:
in a protective atmosphere with the negative pressure of 0.05-0.08MPa, the photocuring 3D printing biscuit is heated from room temperature to 200-280 ℃ at the heating rate of 1-2 ℃/min, is kept at the temperature of 200-280 ℃ for 240min, is heated to 300-500 ℃ at the heating rate of 2-3 ℃/min, is kept at the temperature of 300-500 ℃ for 360min, and is cooled to room temperature at the cooling rate of 5-8 ℃/min.
11. The photocuring 3D printing nanoparticle reinforced metal piece is characterized in that the crack density of the photocuring 3D printing nanoparticle reinforced metal piece is not more than 2.8%; the photocuring 3D printing nanoparticle reinforced metal piece is prepared by the preparation method of the photocuring 3D printing nanoparticle reinforced metal piece according to any one of claims 1 to 10.
12. The photocured 3D printed nanoparticle-reinforced metal part of claim 11, wherein the content of nanoparticles in the photocured 3D printed nanoparticle-reinforced metal part is: 15.7-35.7 wt%.
13. The photocurable 3D printed nanoparticle-reinforced metal piece of claim 11, wherein the average grain size of the photocurable 3D printed nanoparticle-reinforced metal piece is 9-11 μ ι η.
14. The photocured 3D printed nanoparticle-reinforced metal part of claim 11, wherein the photocured 3D printed nanoparticle-reinforced metal part has a specific strength of 0.19-0.21 MPa-Kg-1m3。
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