CN108396165B - Three-dimensional shell ceramic skeleton-metal matrix composite material and preparation method thereof - Google Patents
Three-dimensional shell ceramic skeleton-metal matrix composite material and preparation method thereof Download PDFInfo
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- CN108396165B CN108396165B CN201810250882.5A CN201810250882A CN108396165B CN 108396165 B CN108396165 B CN 108396165B CN 201810250882 A CN201810250882 A CN 201810250882A CN 108396165 B CN108396165 B CN 108396165B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/10—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
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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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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1005—Pretreatment of the non-metallic additives
- C22C1/1015—Pretreatment of the non-metallic additives by preparing or treating a non-metallic additive preform
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Abstract
The invention discloses a three-dimensional shell ceramic skeleton-metal matrix composite material and a preparation method thereof, belonging to the field of metal matrix composite materials. The structure of the three-dimensional shell layer ceramic framework-metal matrix composite material is as follows: and metal matrixes are filled inside and outside the three-dimensional shell layer ceramic framework, wherein the three-dimensional shell layer ceramic framework is of a hollow shell structure as a whole, the interpenetration column nodes are spherical, cylindrical or square, and the wall thickness of the three-dimensional shell layer ceramic framework is 0.5-3 mm. The method effectively solves the problem that the molten metal and the ceramic reinforcement are difficult to infiltrate, and the pure matrix is wrapped inside and outside the shell layer, so that the composite material has excellent wear resistance and does not lose the plasticity and toughness of the composite material. The shapes of the joints of the framework are spherical, cylindrical and square, the joints are periodically distributed, a certain connecting strength can be provided during sintering, and the synergistic effect of the framework structure and the matrix is exerted to the maximum extent; the composite material is expected to be used in the field of friction and wear working conditions.
Description
Technical Field
The invention relates to a three-dimensional shell ceramic skeleton-metal matrix composite material and a preparation method thereof, belonging to the field of metal matrix composite materials.
Background
Ceramic particle reinforced metal matrix composites exhibit a variety of excellent properties, and composites in which the ceramic particles are uniformly distributed in the metal matrix have not been suitable for particular operating conditions. The development of ceramic preform reinforced metal matrix composite materials with specific structures is greatly needed, and the synergistic effect of ceramic and metal matrix can be exerted to the maximum extent. However, the problems of difficult infiltration of molten metal and ceramic preform, poor ductility and toughness of ceramic-metal matrix composite, design and preparation of complex ceramic structure, and the like are all the heart diseases of researchers working on metal matrix composite. Is also a difficult problem to be solved.
Chinese patent CN104874768A discloses a method for preparing a configuration composite material by 3D printing a spatial structure, which can realize the preparation of a spatial structure composite material with precise control and wide variation. However, the ceramic skeleton prepared by the method is easy to scatter during the sintering process and the casting of molten metal. The ceramic preform nodes have certain infiltration depth, the depth distribution is uneven, metal infiltration is difficult, a composite area is easy to generate defects, the plasticity and toughness of the composite material are seriously reduced, and the extrusion casting cost is high.
Chinese patent CN101912957A discloses a network interpenetrating type ceramic-metal matrix composite and a preparation method thereof, the diameter of the SiC support ceramic rib prepared by the method is 5-10 mm, the infiltration thickness of the cross-shaped node of the support and the reinforcement is inconsistent, and the metal liquid is difficult to infiltrate into the core part of the ceramic rib under normal pressure. And the repeatability of the wax mould for preparing the bracket is poor, and the efficiency is low.
Disclosure of Invention
The invention aims to provide a three-dimensional shell ceramic skeleton-metal matrix composite material, which has the following structure: and metal matrixes are filled inside and outside the three-dimensional shell layer ceramic framework, wherein the three-dimensional shell layer ceramic framework is of a hollow shell structure as a whole, the interpenetration column nodes are spherical, cylindrical or square, and the wall thickness of the three-dimensional shell layer ceramic framework is 0.5-3 mm.
The outer diameter of the spherical node is 3-8 mm; the cylindrical node is 5-10 mm in height, and the outer diameter is 3-8 mm; the side length of the square node is 3-8 mm; the length of the interpenetration column is 6-10 mm, and the outer diameter of the interpenetration column is 3-5 mm.
The invention also aims to provide a preparation method of the three-dimensional shell ceramic skeleton-metal matrix composite, which mainly solves the problems that molten metal and a ceramic preform are difficult to infiltrate, the ceramic-metal composite has poor plasticity and toughness and the ceramic preform is easy to fall apart, and specifically comprises the following steps:
(1) and designing a skeleton model by combining CAD assistance, and printing a plastic (PLA, ABS or nylon) skeleton model by adopting 3D printing and slicing software to process model slices.
(2) Carrying out multiple times of slurry coating treatment on the plastic framework obtained in the step (1) to enable the thickness of a slurry layer to reach 0.5-3 mm, drying and curing, wherein the slurry comprises the following components in the slurry coating treatment process: 20-50 wt% of ceramic powder, 30-60 wt% of metal powder, 3-8 wt% of binder and the balance of water.
(3) And (3) sintering the plastic framework with the slurry hung in the step (2).
(4) And (4) discharging the three-dimensional shell ceramic skeleton obtained in the step (3) into a casting mold with a required shape, and pouring a matrix metal liquid to obtain the three-dimensional shell ceramic skeleton-metal matrix composite.
In the step (2), the ceramic powder is Al2O3、SiO2ZrN or HfC with a particle size of 120-200 mesh.
In the step (2), the metal powder is one or more of reduced iron powder, Cr, FeMn, Co, Ni or Al, and is mixed according to any proportion, and the particle size is 150-250 meshes.
In the step (2), the binder is one or a mixture of water glass, PVA, tung oil, epoxy resin and ethylenediamine in any proportion.
The base metal liquid is one of ZGMn13, ZG65Mn and 3Cr 13.
The sintering in step (3) of the invention is divided into two stages: firstly, burning off a plastic framework, sintering at 200-850 ℃ at a heating rate of 3-5 ℃/min, and secondly, carrying out reinforced sintering molding on the three-dimensional shell ceramic framework at 850-1500 ℃ at a heating rate of 5-10 ℃/min, and keeping the temperature for 30-60 min when the temperature reaches 1500 ℃.
The invention has the beneficial effects that:
(1) the method of the invention has low production cost, and the pouring of the molten metal is completed under the conditions of normal pressure, no pressure or negative pressure, thereby reducing the equipment cost compared with extrusion casting.
(2) The shape and size of the framework can be accurately controlled by combining 3D printing, and the expanded production of products is conformed; the method has the advantages that the needed framework shape is designed through CAD software assistance, the plastic framework is guided into the 3D printer to be printed, the forming effect is good, the precision is high, the plastic framework can be generated according to a preset structure, and the repeatability and the production efficiency are high.
(3) The ceramic frameworks are regularly and orderly distributed in the matrix, so that the failure damage caused by stress concentration caused by the bonding of ceramic particles is reduced to the maximum extent; an interlocking structure is formed with the substrate, so that the initiation of cracks is hindered, and the excellent performance of the ceramic and the substrate is fully exerted; and because the shell layer framework is of a thin-wall structure, metal powder added into the framework is melted during casting, so that the porosity is increased, the metal liquid is easy to infiltrate and has the same infiltration depth, and the composite material with pure matrix metal wrapped inside and outside the shell layer is formed, so that the plastic toughness of the composite material is not lost while certain wear resistance is achieved. The ceramic skeleton node is one of a sphere, an annular cylinder or a square, and the interpenetrating columns are supported to a certain extent in the sintering process, so that the structure is not easy to collapse. The material is expected to be applied to the field of friction and wear.
Drawings
FIG. 1 is a schematic view of the structural morphology of a three-dimensional shell ceramic skeleton-metal matrix composite;
FIG. 2 is a schematic diagram of a three-dimensional shell ceramic skeleton.
In fig. 2: a-node, b-interpenetration column.
Detailed Description
The following further description is given with reference to the accompanying drawings and the detailed description, but the scope of the present invention is not limited to the contents.
Example 1
The structure of the three-dimensional shell ceramic skeleton-metal matrix composite material of the embodiment is as follows: the three-dimensional shell ceramic framework is filled with metal matrixes inside and outside, wherein the three-dimensional shell ceramic framework is in a column interpenetrating structure, the framework is a hollow structure with a certain wall thickness, interpenetrated column nodes are spherical, and the outer diameter of the spherical nodes is 5 mm; the outer diameter of each interpenetration column is 3mm, and the length of each interpenetration column is 6 mm; the wall thickness of the three-dimensional shell layer ceramic framework is 1 mm.
The preparation method of the three-dimensional shell layer ceramic skeleton-metal matrix composite material comprises the following steps:
(1) and designing a skeleton model by combining CAD assistance, and slicing the model by adopting 3D printing slicing software to obtain a plastic skeleton model made of PLA material, wherein the thickness of the printing layer is 0.1 mm.
(2) Carrying out multiple times of slurry coating treatment on the three-dimensional plastic skeleton obtained in the step (1) to enable the thickness of a slurry layer to reach 1mm, and using CO2Drying and curing by air; the sizing agent comprises the following components in the sizing treatment process: ceramic powder (120 mesh Al)2O3) 20wt% of the total weight of the composition; the metal powder (150 mesh Al powder + reduced iron powder + Cr powder) accounts for 40wt%, wherein the ratio of Al powder: reduced iron powder: cr powder =1:7: 2; the binder (water glass +1wt% epoxy resin and ethylenediamine) accounted for 5wt%, the remainder being water.
(3) And (3) moving the skeleton obtained in the step (2) into a sintering furnace, gradually heating to 200-850 ℃ to burn out the internal plastic skeleton (binder removal), wherein the heating rate is 3 ℃/min at 200-650 ℃, the temperature is kept for 20min when the temperature reaches 650 ℃, the heating rate is 5 ℃/min at 650-850 ℃, the PLA skeleton is burned out, the reinforced sintering treatment of the shell ceramic skeleton is carried out at 850-1500 ℃, the heating rate is 10 ℃/min at 850-1050 ℃, the heating rate is 6 ℃/min at 1050-1250 ℃, the heating rate is 4 ℃/min at 1250-1500 ℃, and the temperature is kept for 30min when the temperature reaches 1500 ℃, so that the skeleton has certain strength.
(4) And (4) discharging the three-dimensional shell ceramic skeleton obtained in the step (3) into a casting mold with a required shape, and pouring ZGMn13 molten steel to obtain the three-dimensional shell ceramic skeleton-metal matrix composite.
The material prepared by the method provided by the embodiment has a compact structure, has good plastic toughness of a matrix and excellent wear resistance of ceramic particles, and is suitable for being used under the working condition of impact wear.
Example 2
The structure of the three-dimensional shell ceramic skeleton-metal matrix composite material of the embodiment is as follows: the three-dimensional shell ceramic framework is filled with metal matrixes inside and outside, wherein the three-dimensional shell ceramic framework is in a column interpenetrating structure, the framework is a hollow structure with a certain wall thickness, and the interpenetrating column nodes are cylindrical, wherein the cylindrical nodes are 6mm high and the outer diameter is 6 mm; the outer diameter of each interpenetration column is 4mm, and the length of each interpenetration column is 8 mm; the wall thickness of the three-dimensional shell layer ceramic framework is 2 mm.
The preparation method of the three-dimensional shell layer ceramic skeleton-metal matrix composite material comprises the following steps:
(1) and designing a skeleton model by combining CAD assistance, and slicing the model by adopting 3D printing slicing software, wherein the thickness of the printing layer is 0.15mm, so as to prepare the plastic skeleton model made of the ABS material.
(2) Carrying out multiple times of slurry coating treatment on the plastic skeleton model obtained in the step (1) to enable the thickness of a slurry layer to reach 2mm, and using CO2The air is dried and solidified, and the slurry comprises the following components in the slurry hanging treatment process: ceramic powder (200 mesh SiO)2) 30wt%, metal powder (200 mesh FeMn) 45wt%, binder (PVA +0.8wt% epoxy resin and ethylenediamine) 6wt%, and the balance water.
(3) And (3) moving the skeleton obtained in the step (2) to a sintering furnace, gradually heating to 200-850 ℃ to burn out the internal plastic skeleton (binder removal), wherein the heating rate is 5 ℃/min, and forming the shell skeleton with low strength. And (3) performing reinforced sintering on the shell layer ceramic skeleton at 850-1500 ℃, wherein the heating rate is 8 ℃/min at 850-1250 ℃, the heating rate is 3 ℃/min at 1250-1500 ℃, and the shell layer skeleton is kept warm for 40min when the temperature reaches 1500 ℃, so that the shell layer skeleton has certain strength.
(4) And (4) discharging the three-dimensional shell ceramic skeleton obtained in the step (3) into a casting mold with a required shape, and pouring ZG65Mn molten steel to obtain the three-dimensional shell ceramic skeleton-metal matrix composite.
The material prepared by the method provided by the embodiment has a compact structure, has good plastic toughness of a matrix and excellent wear resistance of ceramic particles, and is suitable for being used under the working condition of impact wear.
Example 3
The structure of the three-dimensional shell ceramic skeleton-metal matrix composite material of the embodiment is as follows: metal matrixes are filled inside and outside the three-dimensional shell layer ceramic framework, wherein the three-dimensional shell layer ceramic framework is of a cylindrical interpenetrating structure, the framework is of a hollow structure, and nodes of the interpenetrating columns are in a square shape, wherein the side length of each square node is 6mm, the outer diameter of each interpenetrating column is 5mm, and the length of each column is 10 mm; the wall thickness of the three-dimensional shell layer ceramic framework is 3 mm.
The preparation method of the three-dimensional shell layer ceramic skeleton-metal matrix composite material comprises the following steps:
(1) and designing a framework model by combining CAD assistance, and slicing the model by adopting 3D printing slicing software to obtain a plastic framework model made of nylon, wherein the thickness of a printing layer is 0.2 mm.
(2) Carrying out multiple slurry coating treatment on the three-dimensional shell ceramic skeleton obtained in the step (1) to enable the thickness of a slurry layer to reach 3mm, drying and curing by using a blower, wherein the slurry comprises the following components in the slurry coating treatment process: 50wt% of ceramic powder (200 mesh ZrN), 30wt% of metal powder (250 mesh Co + Ni), 8wt% of binder (tung oil +0.5wt% of epoxy resin and ethylenediamine), and the balance of water.
(3) Transferring the skeleton obtained in the step (2) into a sintering furnace, gradually heating to 200-850 ℃ to burn out the internal plastic skeleton (binder removal), wherein the heating rate is 5 ℃/min, and forming a shell skeleton with low strength; and (3) performing reinforced sintering on the shell layer ceramic skeleton at 850-1500 ℃, wherein the temperature rise rate of 850-1250 ℃ is 10 ℃/min, the temperature rise rate of 1250-1500 ℃ is 5 ℃/min, and the temperature is kept for 60min when reaching 1500 ℃, so that the shell layer skeleton has certain strength.
(4) And (4) discharging the three-dimensional shell ceramic skeleton obtained in the step (3) into a casting mold with a required shape, and pouring 3Cr13 molten steel to obtain the three-dimensional shell ceramic skeleton-metal matrix composite.
The material prepared by the method provided by the embodiment has a compact structure, has good plastic toughness of a matrix and excellent wear resistance of ceramic particles, and is suitable for being used under the working condition of frictional wear.
Claims (7)
1. A preparation method of a three-dimensional shell ceramic skeleton-metal matrix composite is characterized by comprising the following steps:
(1) designing a skeleton model by combining CAD assistance, and slicing the model by adopting 3D printing slicing software to prepare a plastic skeleton model;
(2) carrying out multiple times of slurry coating treatment on the plastic skeleton model obtained in the step (1) to enable the thickness of a slurry layer to reach 0.5-3 mm, and then drying and curing, wherein the slurry comprises the following components in the slurry coating treatment process: 20-50 wt% of ceramic powder, 30-60 wt% of metal powder, 3-8 wt% of binder and the balance of water;
(3) sintering the ceramic-plastic framework with the slurry hung in the step (2);
(4) discharging the three-dimensional shell ceramic skeleton obtained in the step (3) into a casting mold with a required shape, and pouring a matrix metal liquid to obtain a three-dimensional shell ceramic skeleton-metal matrix composite material;
the three-dimensional shell ceramic skeleton-metal matrix composite is characterized in that metal matrixes are filled inside and outside the three-dimensional shell ceramic skeleton, the three-dimensional shell ceramic skeleton is of a hollow shell structure as a whole, interpenetrated column nodes are spherical, cylindrical or square, and the wall thickness of the three-dimensional shell ceramic skeleton is 0.5-3 mm.
2. The method for preparing the three-dimensional shell ceramic skeleton-metal matrix composite material according to claim 1, wherein the method comprises the following steps: the outer diameter of the spherical node is 3-8 mm; the cylindrical node is 5-10 mm in height, and the outer diameter is 3-8 mm; the side length of the square node is 3-8 mm; the length of the interpenetration column is 6-10 mm, and the outer diameter of the interpenetration column is 3-5 mm.
3. The method for preparing the three-dimensional shell ceramic skeleton-metal matrix composite material as claimed in claim 1, wherein: in the step (2), the ceramic powder is Al2O3、SiO2ZrN or HfC with a particle size of 120-200 mesh.
4. The method for preparing the three-dimensional shell ceramic skeleton-metal matrix composite material as claimed in claim 1, wherein: in the step (2), the metal powder is one or more of reduced iron powder, Cr, FeMn, Co, Ni and Al which are mixed according to any proportion, and the particle size is 150-250 meshes.
5. The method for preparing the three-dimensional shell ceramic skeleton-metal matrix composite material as claimed in claim 1, wherein: in the step (2), the binder is one or a mixture of water glass, PVA, tung oil, epoxy resin and ethylenediamine according to any proportion.
6. The method for preparing the three-dimensional shell ceramic skeleton-metal matrix composite material as claimed in claim 1, wherein: the matrix metal liquid is one of ZGMn13, ZG65Mn and 3Cr13 steel.
7. The method for preparing the three-dimensional shell ceramic skeleton-metal matrix composite material as claimed in claim 1, wherein: the sintering in the step (3) is divided into two stages: firstly, burning off a plastic framework, sintering at 200-850 ℃ at a heating rate of 3-5 ℃/min, and secondly, carrying out reinforced sintering molding on the three-dimensional shell ceramic framework at 850-1500 ℃ at a heating rate of 5-10 ℃/min, and keeping the temperature for 30-60 min when the temperature reaches 1500 ℃.
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| CN110128144A (en) * | 2019-06-11 | 2019-08-16 | 北京中煤煤炭洗选技术有限公司 | A kind of metal and ceramic composite |
| CN110744031B (en) * | 2019-08-14 | 2022-04-15 | 中材高新材料股份有限公司 | Metal ceramic wear-resistant material of three-dimensional network ceramic framework and preparation method thereof |
| CN110724847B (en) * | 2019-12-04 | 2020-10-20 | 河南科技大学 | Method for preparing bicontinuous phase composite material by pressureless infiltration |
| CN113858607A (en) * | 2020-06-30 | 2021-12-31 | 宝武装备智能科技有限公司 | Gypsum supporting method for processing deep cavity shell based on 3D printing technology |
| JP2024502902A (en) | 2020-12-10 | 2024-01-23 | マゴト・アンテルナシオナル・エス・アー | Hierarchical composite wear section with structural reinforcement |
| CN114178509A (en) * | 2021-10-21 | 2022-03-15 | 上海交通大学 | Light high-rigidity three-dimensional network structure magnesium-based composite material and preparation method thereof |
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