CN116041065B - Preparation method of 3D printing B4C-based composite ceramic - Google Patents
Preparation method of 3D printing B4C-based composite ceramic Download PDFInfo
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- CN116041065B CN116041065B CN202211502333.5A CN202211502333A CN116041065B CN 116041065 B CN116041065 B CN 116041065B CN 202211502333 A CN202211502333 A CN 202211502333A CN 116041065 B CN116041065 B CN 116041065B
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- 239000002131 composite material Substances 0.000 title claims abstract description 66
- 239000000919 ceramic Substances 0.000 title claims abstract description 64
- 238000010146 3D printing Methods 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052580 B4C Inorganic materials 0.000 claims abstract description 39
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 15
- 229920005989 resin Polymers 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 12
- 239000010439 graphite Substances 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 238000009837 dry grinding Methods 0.000 claims description 14
- 238000005238 degreasing Methods 0.000 claims description 13
- 239000011863 silicon-based powder Substances 0.000 claims description 13
- 238000005475 siliconizing Methods 0.000 claims description 12
- 238000007639 printing Methods 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 9
- 238000000110 selective laser sintering Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 6
- 239000003822 epoxy resin Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920000647 polyepoxide Polymers 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 235000015895 biscuits Nutrition 0.000 claims description 4
- 238000003754 machining Methods 0.000 claims description 4
- 239000000758 substrate Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 description 8
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 238000007088 Archimedes method Methods 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000003698 anagen phase Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000003814 drug Substances 0.000 description 1
- 239000005007 epoxy-phenolic resin Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 238000001272 pressureless sintering Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/563—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on boron carbide
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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
- 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
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
- C04B2235/425—Graphite
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/428—Silicon
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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Abstract
The invention discloses a 3D printing B 4 Preparation method of C-based composite ceramic, B 4 The C-based composite ceramic powder consists of the following components in percentage by mass 4 C: 50-80 percent of organic resin: 20-50% of spheroidal graphite: 0-5% of a weight percentage of the components, wherein the sum of the weight percentages of the components is 100%; wherein the average grain diameter of the boron carbide is 1-10 mu m, the average grain diameter of the organic resin is 5-50 mu m, and the average grain diameter of the spherical graphite is 3-30 mu m. The boron carbide-based formed piece prepared by the 3D printing forming process has better density and basically meets the requirement of the current B 4 The quality requirement of the C-based composite ceramic is high, a die is not needed, and the preparation temperature is greatly reduced.
Description
Technical Field
The invention belongs to the technical field of ceramic additive manufacturing, and particularly relates to a 3D printing B 4 A preparation method of C-based composite ceramic.
Background
Boron carbide has excellent comprehensive properties and is the lightest known ceramic material (2.52 g/cm 3 ) The composite material has the advantages of high corrosion resistance, high temperature resistance, high wear resistance and high neutron absorption capacity, and thus has wide application in the fields of aerospace, national defense, military industry, nuclear industry and the like.
The 3D printing technology can be used for forming a workpiece with a complex internal structure, can be used for customizing production and rapid forming, reduces cost, can customize components and properties, can remarkably reduce material loss, and is a near net forming technology. 3D printing is popular in the fields of aerospace, medical treatment, energy sources, automobiles and the like, and is mainly used for designing and producing high-performance components. But the progress of the nuclear industry in using 3D printing technology is slightly slower than other industries.
Ceramic 3D printing technology has a huge market, and has begun to enter a high-speed growth phase. However, ceramics have high hardness and shrink during sintering, so that the maximum size of 3D printed ceramic parts that can be manufactured is limited, which is a serious challenge for 3D printed ceramic applications. At present, 3D printing technology research is mainly focused on metals and alloys thereof, such as Al alloys, cu alloys, ni alloys, etc., and related researches on carbides, borides are few.
In recent years, in Swedish, a structure studied prepares boron carbide composite filaments from boron carbide and copolyamide, and the boron carbide composite filaments are successfully applied to radiation shielding, so that the process of 3D printing of boron carbide is started. Experts in JJ X-Ray developed the first image of boron carbide powder (10B 4 C) The prepared binder sprays the 3D printing boron carbide collimator, which is important to the innovation of developing high-performance computers, armors, effective medicaments and the like. The 3D printing technology of boron carbide is late to start, is slow to develop at present, and has huge development space. However, the shape and irregularity of the boron carbide powder and poor flowability, pure boron carbide powder is not suitable for 3D printing.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or problems occurring in the prior art.
The invention aims to provide a 3D printing B 4 Preparation method of C-based composite ceramic, 3D printing B is prepared by designing proportions among raw materials 4 C-base composite ceramic.
In order to solve the technical problems, the invention provides the following technical scheme: 3D prints B 4 The preparation method of the C-based composite ceramic comprises the following steps of,
the powder raw material is prepared from the following components in percentage by mass 4 C: 50-80 percent of organic resin: 20-50% of spheroidal graphite: 0-5% of a weight percentage of the components, wherein the sum of the weight percentages of the components is 100%;
dry grinding the prepared powder raw materials to obtain composite ceramic powder;
the composite ceramic powder is used for selective laser sintering to form a boron carbide/organic resin preform;
placing the boron carbide/organic resin preform in a vacuum atmosphere for degreasing treatment to obtain a degreased blank;
carrying out siliconizing reaction sintering treatment on the degreased blank body in vacuum to obtain 3D printed B 4 C-base composite ceramic.
3D printing B as the present invention 4 A preferable scheme of the preparation method of the C-based composite ceramic comprises the following steps: the average grain size of the boron carbide is 1-10 mu m, the average grain size of the organic resin is 5-50 mu m, and the average grain size of the spherical graphite is 3-30 mu m.
3D printing B as the present invention 4 A preferable scheme of the preparation method of the C-based composite ceramic comprises the following steps: the organic resin comprises one of phenolic resin and epoxy resin.
3D printing B as the present invention 4 A preferable scheme of the preparation method of the C-based composite ceramic comprises the following steps: and the dry grinding treatment is carried out, the dry grinding rotating speed is 200-600 rpm, and the dry grinding time is 18-24 h.
3D printing B as the present invention 4 A preferable scheme of the preparation method of the C-based composite ceramic comprises the following steps: the selective laser sintering is carried out, and the laser is CO 2 The laser power of the laser is 15-120W.
3D printing B as the present invention 4 A preferable scheme of the preparation method of the C-based composite ceramic comprises the following steps: and (3) degreasing, namely heating the boron carbide/organic resin preform to a degreasing temperature of 400-600 ℃ in vacuum, and preserving heat for 60-180 min.
3D printing B as the present invention 4 A preferable scheme of the preparation method of the C-based composite ceramic comprises the following steps: and (3) carrying out siliconizing reaction sintering treatment, placing the degreased blank body on silicon powder, and carrying out reaction sintering in a vacuum atmosphere.
3D printing B as the present invention 4 A preferable scheme of the preparation method of the C-based composite ceramic comprises the following steps ofIn (a): the average grain diameter of the silicon powder is 0.1-3 mm, and the mass ratio of the silicon powder to the degreasing blank is 1-3:1.
3D printing B as the present invention 4 A preferable scheme of the preparation method of the C-based composite ceramic comprises the following steps: the siliconizing reaction sintering treatment is carried out at 1500-1700 ℃ for 30-90 min.
3D printing B as the present invention 4 A preferable scheme of the preparation method of the C-based composite ceramic comprises the following steps: the siliconizing reaction sintering treatment is carried out, the temperature of the degreased blank body is raised to 700-900 ℃ at a heating rate of 0.5-1 ℃/min, the temperature is kept for 30-60 min, and then the temperature is continuously raised to 1500-1700 ℃ at a heating rate of 5-10 ℃/min for siliconizing.
Compared with the prior art, the invention has the following beneficial effects:
the invention prepares the 3D printing B by reasonably designing the proportion of the components and combining SLS and reaction sintering technology 4 C-base composite ceramic. Ensuring that B with higher density is prepared 4 On the premise of C-based composite ceramic, the cost is reduced to the greatest extent.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
(1) The boron carbide composite powder is prepared, wherein the specific chemical composition is 70% of boron carbide, 28% of epoxy resin (with the trade name of E42 and purchased from microphone), 2% of spheroidal graphite and 100% of the sum of the mass percentages of the components. The average grain diameter of the micron-sized boron carbide powder is about 1.88 mu m; the average particle diameter of the organic resin is 10 μm; the average particle diameter of the spheroidal graphite was 10. Mu.m. All the raw material powder is put into a ball mill for dry grinding, the rotation speed of the dry grinding is 400rpm, and the dry grinding time is 20 hours.
(2) For the prepared 3D printing B 4 The C-based composite ceramic powder is subjected to selective laser sintering, and the printing parameters are as follows: the input laser power is 30W, and the layer thickness is about 100 mu m; printing and forming B according to three-dimensional model 4 And separating the formed part from the substrate by adopting a wire-cut electric discharge machining process.
(3) Degreasing the preform in a vacuum sintering furnace, wherein the degreasing process is to heat the preform to 450 ℃ in vacuum at a heating rate of 0.5 ℃/min and keep the temperature for 60min.
(4) The degreased block is placed on silicon powder, and reaction sintering is carried out in a vacuum atmosphere. The average grain diameter of the silicon powder is 1mm, and the mass ratio of the silicon powder to the preform is 2:1. heating the biscuit to 700 ℃ at a heating rate of 0.6 ℃/min and preserving heat for 45min during reactive sintering, then continuously heating to 1600 ℃ at a heating rate of 5 ℃/min for siliconizing, and obtaining the 3D printing B after the reaction time is 60min 4 C-base composite ceramic sintered body.
For the obtained 3D printing B 4 The C-based composite ceramic is subjected to physical property test, water is used as a medium, and the density of the C-based composite ceramic is measured by using an Archimedes method, so that the result shows that the relative density of the C-based composite ceramic is 80%.
Example 2
(1) Preparing boron carbide composite powder, wherein the concrete chemical composition of the boron carbide composite powder is 75% by weight, the epoxy resin (brand E42, purchased from microphone) is 20%, the spherical graphite is 5%, and the sum of the mass percentages of the components is 100%; the average grain diameter of the micron-sized boron carbide powder is about 1.88 mu m; the average particle diameter of the organic resin is 10 μm; the average particle diameter of the spheroidal graphite was 10. Mu.m. All the raw material powder is put into a ball mill for dry grinding, the rotation speed of the dry grinding is 400rpm, and the dry grinding time is 20 hours.
(2) Carrying out selective laser sintering on the prepared 3D printing B4C-based composite ceramic powder, wherein the printing parameters are as follows: the input laser power is 30W, and the layer thickness is about 100 mu m; and printing and molding the B4C-based composite ceramic preform according to the three-dimensional model, and separating the molded part from the substrate by adopting a wire-cut electric discharge machining process.
(3) Degreasing the preform in a vacuum sintering furnace, wherein the degreasing process is to heat the preform to 450 ℃ in vacuum at a heating rate of 0.5 ℃/min and keep the temperature for 50min.
(4) The degreased block is placed on silicon powder, and reaction sintering is carried out in a vacuum atmosphere. The average grain diameter of the silicon powder is 10m, and the mass ratio of the silicon powder to the preform is 2:1. during reaction sintering, firstly heating the biscuit to 800 ℃ at a heating rate of 0.6 ℃/min, preserving heat for 45min, then continuously heating to 1600 ℃ at a heating rate of 5 ℃/min for siliconizing, and obtaining the 3D printing B4C/base composite ceramic sintered body after the reaction time is 60min.
For the obtained 3D printing B 4 The C-based composite ceramic was tested and showed a relative density of 78%.
Example 3
This example 3 preparation of 3D print B using the same method as in example 1 4 The C-based composite ceramic powder is characterized in that the powder raw materials are different in types and proportions, the concrete chemical composition comprises 65% of boron carbide, 30% of phenolic resin (brand BR, purchased from microphone), 5% of spherical graphite and 100% of the sum of the components in percentage by weight. The rest of the procedure was carried out in the same manner as in example 1 to give B 4 C-base composite ceramic powder sintered body.
For the obtained 3D printing B 4 The C-based composite ceramic is subjected to performance test, and the result shows that the relative density of the C-based composite ceramic is 74%.
Example 4
This example 4 preparation of 3D print B using the same method as in example 1 4 C-based composite ceramic powder is distinguished in thatThe printing parameters used are different, and the printing parameters are as follows: the input laser power is 50W, and the layer thickness is about 100 mu m; printing and forming B according to three-dimensional model 4 And separating the formed part from the substrate by adopting a wire-cut electric discharge machining process. The rest of the procedure was carried out in the same manner as in example 1 to give B 4 C-base composite ceramic powder sintered body.
For the obtained 3D printing B 4 The C-based composite ceramic is subjected to performance test, and the result shows that the relative density is 69%.
Example 5
This example 5 preparation of 3D print B using the same method as in example 1 4 The C-based composite sintered ceramic is characterized in that the mass ratio of silicon powder to a preform during reactive sintering is 1:1. the rest of the procedure was carried out in the same manner as in example 1 to give B 4 C-base composite ceramic powder sintered body.
For the obtained 3D printing B 4 The C-based composite ceramic is subjected to performance test, and the result shows that the relative density of the C-based composite ceramic is 65%. When the silicon content is low, the reaction sintering is not completely carried out, and the siliconizing effect is poor.
Example 6
This example 6 preparation of 3D print B using the same method as in example 1 4 The C-based composite sintered ceramic is different in heating conditions of reaction sintering, firstly, the heating rate of 0.6 ℃/min is used for heating the biscuit to 700 ℃ and preserving heat for 45min, then the heating rate of 10 ℃/min is used for continuously heating to 1600 ℃ for siliconizing, and the reaction time is 30min. The remaining steps were carried out in the same manner as in example 1 to obtain 3D print B 4 C-base composite ceramic sintered body.
For the obtained 3D printing B 4 The C-based composite ceramic is subjected to performance test, and the result shows that the relative density is 63%. Because of the rapid temperature rise and the short reaction time, the siliconizing reaction proceeds quite rapidly and incompletely, which affects the yield of silicon carbide.
Comparative example 1
Comparative example 1 3D print B was prepared in the same manner as in example 1 4 C-based composite ceramic powder and printing, the difference is the powderThe raw materials have different components, the specific chemical composition is 75% of boron carbide, 25% of polyamide, no extra spheroidal graphite is added as other carbon sources, and the sum of the mass percentages of the components is 100%. During degreasing, the boron carbide-based preform is deformed.
Comparative example 2
Comparative example 2 3D print B was prepared in the same manner as in example 1 4 The C-based composite ceramic powder is printed and degreased, and the difference is that the reactive sintering is not performed, and the finally obtained boron carbide composite material has extremely low density and no practical significance.
The invention provides a 3D printing B 4 The preparation method of the C-based composite ceramic prepares the 3D printing B by combining selective laser sintering and reaction sintering technology through designing the proportion among the raw materials 4 C-base composite ceramic.
The boron carbide/silicon carbide forming piece prepared by the 3D printing forming process has better density and basically meets the requirement of the current B 4 The quality requirement of the C-based composite ceramic is high, the mold is not needed, and meanwhile, the preparation temperature is greatly reduced.
The boron carbide powder has irregular shape and poor fluidity. According to the invention, the boron carbide and the organic resin are subjected to dry grinding, so that the organic resin can be coated on the surface of the boron carbide powder, the sharpening phenomenon of the boron carbide is weakened, and the subsequent selective laser sintering of the composite powder is facilitated.
The organic resin selected by the invention is resin with higher carbon residue rate, and comprises epoxy resin, phenolic resin and the like. After degreasing, the preform can also have a certain content of carbon remained in the matrix, which is beneficial to the post-reaction sintering of the preform.
After the 3D printing ceramic preform is subjected to selective laser sintering and degreasing, the strength and mechanical properties of the 3D printing ceramic preform cannot meet the requirements, so that the 3D printing ceramic preform is further reinforced by reaction sintering. The reaction sintering is siliconizing reaction, and the temperature of the reaction sintering is about 1600 ℃ generally, which is far lower than the temperature of preparing boron carbide by pressureless sintering. Capillary phenomenon existing in the carbon-silicon reaction is utilized in the reaction sintering, and capillary action of liquid silicon can drive densification of the degreased preform. The activity and amount of other carbon sources can have an effect on the reaction and capillary channels.
3D printing B prepared by the method 4 The C-based composite ceramic nickel-based superalloy forming part has better density and basically meets the requirement of the current B 4 The quality requirement of the C-based composite ceramic is high, a die is not needed, and the preparation temperature is greatly reduced.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (1)
1. 3D prints B 4 The preparation method of the C-based composite ceramic is characterized by comprising the following steps: comprising the steps of (a) a step of,
(1) Preparing boron carbide composite powder, wherein the specific chemical composition of the boron carbide composite powder is 70% by weight, the epoxy resin E42 is 28% by weight, the spherical graphite is 2% by weight, and the sum of the mass percentages of the components is 100%; the average grain diameter of the micron-sized boron carbide powder is 1.88 mu m; the average particle diameter of the organic resin is 10 μm; the average particle diameter of the spherical graphite is 10 mu m; all the raw material powder is put into a ball mill for dry grinding, the rotation speed of the dry grinding is 400rpm, and the dry grinding time is 20 hours;
(2) For the prepared 3D printing B 4 The C-based composite ceramic powder is subjected to selective laser sintering, and the printing parameters are as follows: the input laser power is 30W, and the layer thickness is 100 mu m; printing and forming B according to three-dimensional model 4 Separating the formed part from the substrate by adopting a wire-cut electric discharge machining process;
(3) Degreasing the preform in a vacuum sintering furnace, wherein the degreasing process is to heat the preform to 450 ℃ in vacuum at a heating rate of 0.5 ℃/min and keep the temperature for 60 min;
(4) Placing the degreased block on silicon powder, and performing reaction sintering in a vacuum atmosphere; the average grain diameter of the silicon powder is 1mm, and the mass ratio of the silicon powder to the preform is 2:1, a step of; heating the biscuit to 700 ℃ at a heating rate of 0.6 ℃/min and preserving heat for 45min during reactive sintering, then continuously heating to 1600 ℃ at a heating rate of 5 ℃/min for siliconizing, and obtaining the 3D printing B after the reaction time is 60min 4 C-base composite ceramic sintered body.
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