CN113105250B - Pomegranate-shaped black ceramic particles for additive manufacturing and preparation method and application thereof - Google Patents

Pomegranate-shaped black ceramic particles for additive manufacturing and preparation method and application thereof Download PDF

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CN113105250B
CN113105250B CN202110406699.1A CN202110406699A CN113105250B CN 113105250 B CN113105250 B CN 113105250B CN 202110406699 A CN202110406699 A CN 202110406699A CN 113105250 B CN113105250 B CN 113105250B
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刘战强
辛明泽
王兵
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Shandong University
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Abstract

The invention belongs to the technical field of DLP additive manufacturing of black powder ceramics, relates to pomegranate-shaped black ceramic particles for additive manufacturing, and a preparation method and application thereof, and particularly relates to a method for realizing high-quality and high-efficiency DLP additive manufacturing of black powder ceramics by using fusible metals. The additive manufacturing method comprises: and mixing the fusible metal and the black ceramic powder to prepare ceramic slurry, and printing, photocuring and sintering to obtain the black ceramic. Compared with the 3D printing effect of ceramic slurry prepared from single black powder, the black powder material is uniformly distributed in fusible metal, and is matched with the gas atomization method for preparing pomegranate-shaped composite particles and the two-step sintering process, so that the parameters of the curing layer thickness of the ceramic material, the density and the mechanical property of the sintered ceramic are all superior to those of the ceramic prepared from the single black powder.

Description

Pomegranate-shaped black ceramic particles for additive manufacturing and preparation method and application thereof
Technical Field
The invention belongs to the technical field of DLP additive manufacturing of black powder ceramics, relates to pomegranate-shaped black ceramic particles for additive manufacturing, and a preparation method and application thereof, and particularly relates to a method for realizing high-quality and high-efficiency DLP additive manufacturing of black powder ceramics by using fusible metals.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
With the continuous development of high-end equipment manufacturing industry and material science, a 3D additive manufacturing technology with excellent performances such as high resolution, high forming speed and the like is continuously developed and plays an important role, and a new choice is provided for the production and the manufacturing of high-performance precise parts. The ceramic parts prepared by the photocuring molding additive manufacturing technology based on the Digital Light Processing (DLP) of the mask image projection technology have high precision and excellent mechanical property, and are particularly suitable for manufacturing miniature and high-precision parts. However, DLP technology has relatively strict requirements on the absorption and scattering of ultraviolet light by materials, so that the ceramics prepared by photocuring molding are mainly limited to white oxide ceramics such as aluminum oxide materials.
Silicon carbide ceramic composite materials are receiving wide attention in various fields such as aerospace, automobiles, mechanical engineering and electronic engineering due to excellent material properties, and are beginning to become the first choice materials of high-temperature structural components. However, the inventor researches and finds that the black materials such as silicon carbide and carbon fiber have large absorption and scattering to light, so that when the DLP photocuring molding technology is applied to prepare the silicon carbide composite ceramic, the technical bottlenecks such as low thickness of a cured layer and difficulty in material molding are faced, and a serious challenge is provided for the field of photocuring molding additive manufacturing of black powder ceramic materials.
Disclosure of Invention
The invention provides pomegranate-shaped black ceramic particles for additive manufacturing and a preparation method and application thereof, aiming at solving the problems of low thickness of a cured layer and difficult material forming of the cured layer when a black material is prepared into composite ceramic by using a DLP photocuring forming technology in the prior art. According to the method, before the composite ceramic blank is manufactured by photocuring additive manufacturing, black ceramic material powder is creatively and uniformly mixed with the fusible metal in a molten state to prepare pomegranate-shaped black ceramic particles, a plurality of black ceramic powder are distributed inside the fusible metal particles, and the fusible metal and resin in the blank are effectively removed through high-temperature sintering, so that high-quality black powder ceramic is obtained. The method has simple process, can print the black ceramic powder which is difficult to print and process, does not need the support of complex equipment, has low preparation cost and is easy to popularize.
Specifically, the invention is realized by the following technical scheme:
the invention provides pomegranate-shaped black ceramic particles for additive manufacturing, which comprise black ceramic powder and fusible metal, wherein a plurality of black ceramic powder are distributed in the fusible metal particles;
the fusible metal is an alloy made of two or more of bismuth, lead, tin and cadmium.
In a second aspect of the present invention, there is provided a method for preparing pomegranate-shaped black ceramic particles for additive manufacturing, comprising: the fusible metal is heated and mixed with the black ceramic powder, and then the pomegranate-shaped black ceramic particles are prepared by an air atomization method.
In a third aspect of the present invention, there is provided a 3D printing photocuring method of black ceramic powder, comprising: preparing pomegranate-shaped black ceramic particles for additive manufacturing into ceramic slurry, and performing printing, photocuring and sintering to obtain black ceramic.
The invention provides a black ceramic prepared by the 3D printing photocuring method of black ceramic powder.
In a fifth aspect of the invention, a 3D printing photocuring method for pomegranate-shaped black ceramic particles and/or black ceramic powder for additive manufacturing is provided for application in the field of additive manufacturing.
One or more embodiments of the present invention have the following advantageous effects:
1) in the prior art, the black powder composite ceramic slurry is difficult to form, poor in forming quality, small in thickness of a cured layer and low in preparation efficiency in the photocuring additive manufacturing process, and if the ceramic product made of materials such as silicon carbide and the like is independently prepared, the prepared ceramic has poor density due to the adoption of low-solid-content slurry, high light power and long exposure time, and the prepared ceramic is easy to crack due to poor layer viscosity and sintering. Aiming at the technical limitation, the black ceramic powder is uniformly distributed in the fusible metal particles, so that the advantages of small ultraviolet absorption and scattering and good photocuring performance of the fusible metal can be fully exerted in the process of preparing the black ceramic blank by photocuring additive manufacturing, and the efficient additive manufacturing of the black ceramic is ensured. The method is simple and easy to implement, and the thickness of the single-layer cured layer of the prepared composite ceramic material can reach 120-150 mu m.
2) The method adopts two-step sintering, wherein the tin-bismuth alloy and resin in the ceramic blank are removed in the first step of sintering, the silicon carbide ceramic which is relatively compact is obtained in the second step of sintering, the binding force among particles is enhanced in the second step of sintering, the mechanical strength of the ceramic is improved, the ceramic material prepared by directly printing and sintering the silicon carbide powder has the bending strength of about 180-200MPa, the printing efficiency of the ceramic prepared by mixing the silicon carbide powder with the fusible metal is improved by 70-85%, and the bending strength is improved by 15-20%. In addition, the black ceramic material printed by the invention has small density and relatively light weight, and can be applied as a light material.
3) Compared with the common method for improving the curing performance of the black ceramic slurry in the prior art, the method for realizing black powder ceramic printing by using the fusible metal is not a conventional research idea in the field. Compared with the 3D printing effect of ceramic slurry prepared from single black powder, the black powder material is uniformly distributed in fusible metal and is matched with an air atomization method to prepare particles, so that the thickness of a cured layer in the photocuring process of the ceramic material is larger, and a light material is obtained by matching with a two-step sintering process.
4) Different from the traditional core-shell structure, the invention heats the fusible metal, mixes the fusible metal with the black ceramic powder, and prepares the pomegranate-shaped black ceramic particles by the gas atomization method, a plurality of black ceramic powders are distributed in the fusible metal particles, and a plurality of black ceramic powders are distributed in the fusible metal, thereby being beneficial to printing the light ceramic blank under the condition of smaller ultraviolet power and shorter exposure time. And because the black ceramic powder is distributed in the fusible metal particles, a blank with a thicker light curing layer can be more easily printed under the unconstrained exposure condition.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a flow chart of a method for preparing black powder ceramic with high efficiency by using fusible metal in example 1 of the present invention:
FIG. 2 is an operation schematic diagram of a method for realizing high-efficiency preparation of black powder ceramic by using fusible metal in embodiment 1 of the present invention:
FIG. 3 is a schematic view of the pomegranate-shaped black ceramic particles prepared in example 1 of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In the prior art, the black powder composite ceramic slurry is difficult to form, poor in forming quality and low in preparation efficiency in the photocuring 3D printing preparation process, and in order to solve the problems, the invention provides pomegranate-shaped black ceramic particles for additive manufacturing and a preparation method and application thereof. According to the method, before the composite ceramic blank is manufactured by photocuring additive manufacturing, black ceramic material powder is creatively and uniformly mixed with the fusible metal in a molten state to prepare pomegranate-shaped black ceramic particles, a plurality of black ceramic powder are distributed inside the fusible metal particles, and the fusible metal and resin in the blank are effectively removed through high-temperature sintering, so that the black powder ceramic with high quality, large thickness and light weight is obtained. The method has the advantages of simple process, no need of complex equipment support, low preparation cost and easy popularization.
Specifically, the invention is realized by the following technical scheme:
the invention provides pomegranate-shaped black ceramic particles for additive manufacturing, which comprise black ceramic powder and fusible metal, wherein a plurality of black ceramic powder are distributed in the fusible metal particles;
the fusible metal is an alloy made of two or more of bismuth, lead, tin and cadmium.
The black ceramic powder is uniformly dispersed in the fusible metal particles with small ultraviolet absorption and scattering, and is used for improving the photocuring performance of the silicon carbide ceramic slurry. Meanwhile, the fusible metal is easy to melt and remove under the high-temperature condition, and the pure black ceramic is finally obtained. The fusible metal material has the characteristics of low melting point, low refractive index, low absorption and scattering of ultraviolet light, good chemical compatibility with black ceramic powder and the like, and is suitable for being used as a material for improving the photocuring performance of black ceramic.
Different from the traditional core-shell structure, the invention heats the fusible metal, mixes the fusible metal with the black ceramic powder, and prepares the pomegranate-shaped black ceramic particles by the gas atomization method, a plurality of black ceramic powders are distributed in the fusible metal particles, and a plurality of black ceramic powders are distributed in the fusible metal, thereby being beneficial to printing the light ceramic blank under the condition of smaller ultraviolet power and shorter exposure time. And because the black ceramic powder is distributed in the fusible metal particles, a blank with a thicker light curing layer can be more easily printed under the unconstrained exposure condition.
In one or more embodiments of the invention, the fusible metal is selected from alloys made of two or more of bismuth, lead, tin and cadmium, preferably tin-bismuth alloys.
In one or more embodiments of the present invention, the black ceramic powder is selected from an inorganic non-metallic material and/or a carbon fiber;
preferably, the inorganic non-metallic material is selected from at least one of structural ceramics, functional ceramics and super hard ceramics;
preferably, the superhard ceramic is boron nitride and/or diamond.
In one or more embodiments of the present invention, the black ceramic powder is selected from oxide ceramic powder and/or non-oxide ceramic powder;
preferably, the non-oxide ceramic powder is selected from at least one of boron nitride, diamond, silicon carbide, aluminum nitride, tungsten carbide, titanium nitride, boron carbide.
The black ceramic powder is preferably silicon carbide, the fusible metal is preferably tin-bismuth alloy, and the bismuth alloy material has the characteristics of low melting point, low refractive index, low absorption and scattering of ultraviolet light, good chemical compatibility with a silicon carbide matrix and the like, and is suitable for being used as a material for improving the photocuring performance of the silicon carbide ceramic.
Preferably, the black ceramic powder is selected from silicon carbide fiber powder, chopped carbon fiber powder and silicon carbide powder material.
In a second aspect of the invention, there is provided a method of preparing pomegranate-shaped black ceramic particles for additive manufacturing, comprising: the fusible metal is heated and mixed with the black ceramic powder, and then the composite particle powder is prepared by an air atomization method.
By using the aerosol method, the fusible metal and the black ceramic powder can be uniformly mixed to prepare powder with smaller size so as to meet the requirement of photocuring on the particle size.
Preferably, the mass ratio of the fusible metal to the black ceramic powder is 3-10:1, preferably 5: 1;
preferably, the heating temperature is 10-20 ℃ above the melting point of the fusible metal;
preferably, the mixing method is ball milling, and the ball milling time is 12-18h, preferably 15 h.
In one or more embodiments of the present invention, the method for mixing the fusible metal and the black ceramic powder further includes a step of sieving the composite particle powder, wherein the sieve mesh number is 1000-1500 meshes, and preferably 1500 meshes.
Heating the low-melting-point fusible metal to 10-20 ℃ above the melting point to ensure the fluidity of the molten fusible metal, and ball-milling the fusible metal and the black ceramic particles for 15 hours to uniformly distribute the black ceramic particles in the molten fusible metal to prepare the molten composite material. Adding the molten composite material into an air atomization system, preparing composite particles of black ceramic and fusible metal by an air atomization method, and sieving composite particle powder with the sieve mesh number of 1000-1500 meshes to obtain the effective composite particles.
For example: the preparation method comprises the steps of taking silicon carbide powder as black ceramic powder, taking tin-bismuth alloy with the melting point of 70 ℃ as a modified material, melting the tin-bismuth alloy at the temperature of 80-90 ℃, carrying out ball milling on silicon carbide particles and the molten tin-bismuth alloy for 15 hours to uniformly disperse the silicon carbide particles and the molten tin-bismuth alloy, dispersing the mixed molten composite material into pomegranate-shaped composite particle powder again by using an air atomization system, distributing a plurality of silicon carbide particles in the tin-bismuth alloy, and sieving the silicon carbide particles by using a 1000-plus-1500-mesh sieve to obtain the composite particles capable of effectively improving the photocurability of silicon carbide.
In a third aspect of the present invention, there is provided a 3D printing photocuring method of black ceramic powder, comprising: preparing pomegranate-shaped black ceramic particles for additive manufacturing into ceramic slurry, and performing printing, photocuring and sintering to obtain black ceramic.
In one or more embodiments of the present invention, the step of preparing the ceramic slurry is mixing the composite particle powder with a photosensitive resin to prepare the ceramic slurry;
preferably, the volume fraction of the composite particle powder in the ceramic slurry is 40-50 vol%, preferably 40 vol%.
In one or more embodiments of the present invention, the photocuring parameters are: the power of the ultraviolet light is 20-40mW/cm2The exposure time is 10-20 s; the thickness of the model slice layer was 50 μm.
Preferably, the ultraviolet light wavelength is 405nm, and the optical power is 30mW/cm2The exposure time is 15 s;
multiple experiments prove that the ceramic blank with the thickness of the single-layer curing layer of 120-150 mu m can be formed by photocuring 3D additive manufacturing under the above photocuring parameters and the unconstrained exposure condition.
Preferably, the sintering adopts two-step sintering, wherein the first step of degreasing and sintering is carried out at the temperature of 900-;
preferably, the first step of sintering is vacuum degreasing sintering at 1000 ℃ for 2h, and the second step of high-temperature isostatic pressing sintering is performed at 1500 ℃, the gas pressure is 30MPa, and the sintering time is 1.5 h.
The main purpose of the first sintering step is to degrease and remove the fusible metal, and simultaneously to ensure that the blank has certain strength. And the second step of high-temperature isostatic pressing sintering is carried out, so that the ceramic blank is subjected to isotropic gas pressure, and the density of the ceramic sintered body can be improved.
The composite powder prepared by the invention can print a ceramic blank with the thickness of 120-150 mu m, solves the problem that the black ceramic material is difficult to print, and in addition, the black ceramic material printed by the invention has small density and relatively lighter weight and can be applied as a light material.
In a fourth aspect of the invention, a black ceramic prepared by the additive manufacturing method of the black ceramic powder is provided.
In a fifth aspect of the invention, there is provided a use of a method of additive manufacturing of pomegranate-shaped black ceramic particles and/or black ceramic powder for additive manufacturing in the field of additive manufacturing.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
The density testing method adopts an Archimedes drainage method.
The mechanical property measuring method comprises the steps of measuring the bending strength by a three-point bending method, measuring the hardness by a Vickers hardness tester and measuring the fracture toughness by an indentation method.
Example 1
The specification of the silicon carbide powder material is 10000 meshes, and the melting point of the tin-bismuth alloy is 70 ℃.
Weighing 500g of tin-bismuth alloy and 100g of black ceramic powder, taking the tin-bismuth alloy as a coating material, ball-milling silicon carbide powder and molten tin-bismuth alloy for 15h at 90 ℃, uniformly distributing silicon carbide in the molten tin-bismuth alloy to prepare a molten composite material, adding the molten composite material into a gas atomization system, and preparing pomegranate-shaped composite particles of the silicon carbide and the tin-bismuth alloy by a gas atomization method, namely completing the preparation of the composite particles of the silicon carbide powder and the tin-bismuth alloy material with low absorption and low scattering of ultraviolet light.
The effective composite particles obtained after sieving with a 1500-mesh sieve are mixed with photosensitive resin to prepare composite particle ceramic slurry for photocuring printing, and the solid volume fraction in the composite particle ceramic slurry is 40%.
The additive manufacturing mode is photocuring forming, and photocuring printing parameters are as follows: ultraviolet wavelength of 405nm and optical power of 30mW/cm2Exposure time 15 s; the sintering adopts two-step sintering, and the sintering process is carried out,the first step of sintering, vacuum degreasing sintering at 1000 ℃, the sintering time is 2h, the tin-bismuth alloy and resin in the material are removed, the second step of high-temperature isostatic pressing sintering, the sintering temperature is 1500 ℃, the gas pressure is 30MPa, and the sintering time is 1.5h, so that the compact ceramic is obtained.
The flow of the preparation method is shown in fig. 1, the operation of the preparation method is shown in fig. 2, and fig. 3 is a schematic diagram of the tin-bismuth alloy in which silicon carbide is distributed in a molten state in the pomegranate-shaped composite material.
Example 2
The specification of the silicon carbide powder material is 10000 meshes, and the melting point of the tin-bismuth alloy is 70 ℃.
Weighing 500g of tin-bismuth alloy and 100g of black ceramic powder, taking the tin-bismuth alloy as a coating material, ball-milling silicon carbide powder and molten tin-bismuth alloy for 15h at 90 ℃, uniformly distributing silicon carbide in the molten tin-bismuth alloy to prepare a molten composite material, adding the molten composite material into a gas atomization system, and preparing pomegranate-shaped composite particles of the silicon carbide and the tin-bismuth alloy by a gas atomization method, namely completing the preparation of the composite particles of the silicon carbide powder and the tin-bismuth alloy material with low absorption and low scattering of ultraviolet light.
The effective composite particles obtained after sieving with a 1500-mesh sieve are mixed with photosensitive resin to prepare composite particle ceramic slurry for photocuring printing, and the solid volume fraction in the composite particle ceramic slurry is 40%.
The additive manufacturing mode is photocuring forming, and photocuring printing parameters are as follows: ultraviolet wavelength of 405nm and optical power of 30mW/cm2Exposure time 15 s; the sintering adopts two-step sintering, the first step of sintering is carried out, the vacuum sintering is carried out at 1100 ℃, the sintering time is 2 hours, the tin-bismuth alloy and the resin in the material are removed, the second step of high-temperature isostatic pressing sintering is carried out, the sintering temperature is 1400 ℃, the gas pressure is 30MPa, and the sintering time is 1.5 hours.
Example 3
The specification of the silicon carbide powder material is 10000 meshes, and the melting point of the tin-bismuth alloy is 70 ℃.
Weighing 500g of tin-bismuth alloy and 100g of black ceramic powder, taking the tin-bismuth alloy as a coating material, ball-milling silicon carbide powder and molten tin-bismuth alloy for 15h at 90 ℃, uniformly distributing silicon carbide in the molten tin-bismuth alloy to prepare a molten composite material, adding the molten composite material into a gas atomization system, and preparing pomegranate-shaped composite particles of the silicon carbide and the tin-bismuth alloy by a gas atomization method, namely completing the preparation of the composite particles of the silicon carbide powder and the tin-bismuth alloy material with low absorption and low scattering of ultraviolet light.
The effective composite particles obtained after sieving with a 1500-mesh sieve are mixed with photosensitive resin to prepare composite particle ceramic slurry for photocuring printing, and the solid volume fraction in the composite particle ceramic slurry is 40%.
The additive manufacturing mode is photocuring forming, and photocuring printing parameters are as follows: ultraviolet wavelength of 405nm and optical power of 30mW/cm2Exposure time 20 s; the sintering adopts two-step sintering, the first step of sintering is carried out, the vacuum sintering is carried out at 1000 ℃, the sintering time is 2h, the tin-bismuth alloy and the resin in the material are removed, the second step of high-temperature isostatic pressing sintering is carried out, the sintering temperature is 1500 ℃, the gas pressure is 30MPa, and the sintering time is 1.5h, so that the compact ceramic is obtained.
Comparative example 1
Ball milling the silicon carbide powder for 15h at the temperature of 90 ℃, and drying.
The composite particle ceramic slurry is prepared by mixing effective particles obtained after sieving with a 1500-mesh sieve and photosensitive resin and is subjected to photocuring printing, and the solid volume fraction in the composite particle ceramic slurry is 30%.
The additive manufacturing mode is photocuring forming, and photocuring printing parameters are as follows: ultraviolet wavelength of 405nm and optical power of 30mW/cm2Exposure time 60 s; the sintering adopts two-step sintering, the first step of sintering is carried out at 1000 ℃ for 2h, the second step of high-temperature isostatic pressing sintering is carried out at 1500 ℃, the gas pressure is 30MPa, and the sintering time is 1.5 h.
Compared with the embodiment 1, the difference is that: the silicon carbide powder is directly used for preparing the slurry, so that the solid content of the slurry is reduced, and the exposure time is prolonged. The thickness of the solidified layer is low, the printing efficiency is low, and simultaneously, the compactness of the material is slightly poor and the mechanical strength of the material is poor due to low solid content.
Comparative example 2
The difference from example 1 is that only one sintering step is used: vacuum sintering at 1000 ℃ for 2 h. The remaining parameters were the same as in example 1.
Compared with the embodiment 1, only the first step of degreasing sintering is carried out, the main purpose of the sintering is to degrease and remove the fusible metal, and simultaneously, the blank has certain strength, but the sintering temperature of 1000 ℃ has lower promotion effect on the grain growth, so the mechanical property of the material is poor.
Comparative example 3
The difference from example 1 is that only one sintering step is used: and (3) high-temperature isostatic pressing sintering, wherein the sintering temperature is 1500 ℃, the gas pressure is 30MPa, and the sintering time is 1.5 h. The remaining parameters were the same as in example 1.
Compared with the embodiment 1, the process steps of degreasing and removing the fusible metal are not carried out before the material densification sintering, the material degreasing and the densification sintering are carried out synchronously, the material densification is relatively poor, and the mechanical property is low.
Comparative example 4
The difference from the embodiment 1 is that the sintering adopts two-step sintering, and the vacuum degreasing sintering at 1000 ℃ is adopted, and the sintering time is 2 h. The remaining parameters were the same as in example 1.
Compared with the embodiment 1, the densification sintering adopts vacuum sintering, the sintering temperature is low, the growth promotion to crystal grains is small, the bonding strength between the crystal grains is poor, and the mechanical property of the material is poor. Meanwhile, compared with isostatic pressing sintering, the promotion effect on the densification process of the material is poor.
Comparative example 5
The difference from the example 1 is that the sintering adopts two-step sintering, and high-temperature isostatic pressing sintering is adopted, the sintering temperature is 1500 ℃, the gas pressure is 30MPa, and the sintering time is 1.5 h. The remaining parameters were the same as in example 1.
Compared with the embodiment 1, the mechanical property of the material is improved slightly, but the sintering temperature and the sintering time are longer, and the resource loss is larger.
The thickness parameters of the single-layer cured layers under the unconstrained exposure conditions for the examples and comparative examples are shown in table 1. The thickness of the single-layer solidified layer refers to the maximum solidified layer thickness of the slurry which can be achieved by carrying out unconstrained exposure on the slurry. Compared with the comparative example 1, the thickness of the cured layer is obviously increased, the preparation efficiency is improved, and the density and the mechanical property of the sintered material are improved. Although comparative examples 2-5 are close to example 1 in curing thickness due to the same photocuring parameters, the change of sintering parameters in comparative examples 2-5 has a significant effect on the densification and mechanical properties of the ceramic.
TABLE 1 comparison of the curing Properties of the ceramic particles of the examples and comparative examples
Figure BDA0003022564620000091
Figure BDA0003022564620000101
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (25)

1. The pomegranate-shaped black ceramic particles for additive manufacturing comprise black ceramic powder and fusible metal, wherein a plurality of black ceramic powder are distributed inside the fusible metal particles;
the fusible metal is an alloy made of two or more of bismuth, lead, tin and cadmium.
2. The pomegranate-shaped black ceramic particles for additive manufacturing of claim 1, wherein the black ceramic powder is selected from inorganic non-metallic materials.
3. The pomegranate-shaped black ceramic particles for additive manufacturing of claim 2, wherein the inorganic non-metallic material is selected from at least one of a structural ceramic, a functional ceramic, and an ultra-hard ceramic.
4. The pomegranate-shaped black ceramic particles for additive manufacturing of claim 3, wherein the superhard ceramic is boron nitride and/or diamond.
5. The pomegranate-shaped black ceramic particles for additive manufacturing of claim 1, wherein the black ceramic powder is selected from oxide ceramic powder and/or non-oxide ceramic powder.
6. The pomegranate-shaped black ceramic particles for additive manufacturing of claim 5, wherein the non-oxide ceramic powder is selected from at least one of silicon nitride, boron nitride, diamond, silicon carbide, aluminum nitride, tungsten carbide, titanium nitride, titanium carbonitride, boron carbide and titanium diboride.
7. The pomegranate-shaped black ceramic particles for additive manufacturing of claim 5, wherein the black ceramic powder is selected from the group consisting of silicon carbide fiber powder, chopped carbon fiber powder, silicon carbide powder material.
8. The pomegranate-shaped black ceramic particles for additive manufacturing of any one of claims 1 to 7, wherein the method of mixing the fusible metal with the black ceramic powder comprises: the fusible metal is heated and mixed with the black ceramic powder, and then the composite particle powder is prepared by an air atomization method.
9. The pomegranate-shaped black ceramic particles for additive manufacturing of claim 8, wherein a mass ratio of the fusible metal to the black ceramic powder is 3-10: 1.
10. The pomegranate-shaped black ceramic particles for additive manufacturing of claim 8, wherein a mass ratio of the fusible metal to the black ceramic powder is 5: 1.
11. The pomegranate-shaped black ceramic particle for additive manufacturing of claim 8, wherein the heating temperature is 10-20 ℃ above the melting point of the fusible metal.
12. The pomegranate-shaped black ceramic particles for additive manufacturing of claim 8, wherein the mixing method is ball milling for 12-18 h.
13. The pomegranate-shaped black ceramic particles for additive manufacturing of claim 8, wherein the mixing method is ball milling for 15 h.
14. The pomegranate-shaped black ceramic particles for additive manufacturing of claim 8, further comprising a step of sieving the composite particle powder, wherein the sieve mesh number is 1000-1500.
15. The pomegranate-shaped black ceramic particles for additive manufacturing of claim 8, further comprising the step of sieving the composite particle powder, wherein the sieve mesh number is 1500.
16. A3D printing photocuring method of black ceramic powder is characterized by comprising the following steps: preparing the pomegranate-shaped black ceramic particles for additive manufacturing of any one of claims 1 to 15 into a ceramic slurry, and performing printing, photocuring and sintering to obtain a black ceramic.
17. The method for 3D printing photocuring of black ceramic powder according to claim 16, wherein the step of preparing ceramic slurry is to mix composite particle powder with photosensitive resin to prepare ceramic slurry.
18. The method for 3D printing photocuring of black ceramic powder of claim 16 wherein the volume fraction of composite particle powder in the ceramic slurry is 40-50%.
19. The method for 3D printing photocuring of black ceramic powder of claim 16 wherein the volume fraction of composite particle powder in the ceramic slurry is 40%.
20. The method for 3D printing photocuring of black ceramic powder of claim 16 wherein the photocuring parameters are: the power of the ultraviolet light is 20-40mW/cm2The exposure time is 10-20 s.
21. The method for 3D printing photocuring of black ceramic powder of claim 20 wherein the uv light wavelength is 405nm and the optical power is 30mW/cm2The exposure time was 15 s.
22. The 3D printing photocuring method of black ceramic powder as defined in claim 20, wherein the sintering is performed in two steps, the first step sintering is performed at 900-1200 ℃ for 1-2h, the second step sintering is performed at 1400-1600 ℃ under 30-50MPa and 1-3 h.
23. The 3D printing photocuring method of black ceramic powder as claimed in claim 22, characterized in that the first sintering step is a 1000 ℃ vacuum sintering with a sintering time of 2h, and the second sintering step is a high temperature isostatic pressing sintering with a sintering temperature of 1500 ℃, a gas pressure of 30MPa and a sintering time of 1.5 h.
24. A black ceramic produced by the 3D printing photocuring method of a black ceramic powder according to any one of claims 16 to 23.
25. Use of the pomegranate-shaped black ceramic particles for additive manufacturing of any one of claims 1 to 15 and/or the black ceramic powder of any one of claims 16 to 23 for a 3D printing photocuring method in the field of additive manufacturing.
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