CN113878113B - Ceramic-stainless steel composite material and preparation method thereof - Google Patents

Ceramic-stainless steel composite material and preparation method thereof Download PDF

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CN113878113B
CN113878113B CN202111005153.1A CN202111005153A CN113878113B CN 113878113 B CN113878113 B CN 113878113B CN 202111005153 A CN202111005153 A CN 202111005153A CN 113878113 B CN113878113 B CN 113878113B
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stainless steel
ceramic
steel composite
composite material
powder
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CN113878113A (en
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路建宁
王娟
冯晓伟
郑开宏
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Institute of New Materials of Guangdong Academy of Sciences
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/10—Formation of a green body
    • B22F10/16—Formation of a green body by embedding the binder within the powder bed
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/60—Treatment of workpieces or articles after build-up
    • B22F10/62—Treatment of workpieces or articles after build-up by chemical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/60—Treatment of workpieces or articles after build-up
    • B22F10/64—Treatment of workpieces or articles after build-up by thermal means
    • 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
    • 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
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Abstract

The invention discloses a ceramic-stainless steel composite material and a preparation method thereof, wherein the ceramic-stainless steel composite material takes composite powder obtained by uniformly mixing ceramic powder and stainless steel powder as aggregate, organic additives are added to uniformly wrap the composite powder to prepare thermoplastic particles with high solid content and stability, a ceramic-stainless steel composite material biscuit is formed by a 3D printing technology, and the formed green body is degreased and sintered to prepare the ceramic-stainless steel composite material. According to the invention, the ethylene-vinyl acetate copolymer (EVA) and the high-density polyethylene (HDPE) are synergistically enhanced, and are embedded into the surface of the composite powder in different modes, so that the transmission mode of compound potential is increased, the segregation of organic additives in slurry is prevented, the uniformity of the slurry at low temperature is improved, the flowability and the forming performance of the slurry are improved, and the strength of a composite biscuit and the shape of the biscuit are ensured not to change in the degreasing process.

Description

Ceramic-stainless steel composite material and preparation method thereof
Technical Field
The invention relates to the technical field of composite materials and additive manufacturing, in particular to a ceramic-stainless steel composite material and a preparation method thereof.
Background
The ceramic-stainless steel composite material is a new material formed by combining ceramic and stainless steel materials with different properties through a physical or chemical method, and various materials complement each other in performance, generate a synergistic effect, have a plurality of excellent performances such as high hardness, high wear resistance, high thermal conductivity, low linear expansion coefficient, good dimensional stability and the like, and are widely applied to the fields of electronic packaging, precise instruments, aerospace and the like.
At present, the common preparation methods of the ceramic-stainless steel composite material mainly comprise a powder metallurgy method, a stirring casting method and the like. These conventional manufacturing techniques are highly dependent on molds, and the types of product shapes produced are limited, and even if more complex products can be manufactured, the manufacturing costs (labor costs, raw material costs, etc.) thereof are drastically increased as the complexity of the product shapes increases. In contrast, the 3D printing technology gets rid of the serious dependence of the traditional preparation method on the die, breaks through the limitation of geometric configuration, can form products of any shape, simplifies the manufacturing process of the products, shortens the development period of the products, improves the efficiency and reduces the cost.
Disclosure of Invention
The invention aims to provide a ceramic-stainless steel composite material and a preparation method thereof, wherein composite powder obtained by uniformly mixing ceramic powder and stainless steel powder is taken as aggregate, organic additives comprising paraffin, ethylene-vinyl acetate copolymer, high-density polyethylene and stearic acid are added, a banburying method is adopted to prepare thermoplastic ceramic-stainless steel composite particles with high solid content and stability and uniformity, a ceramic-stainless steel composite material biscuit is formed through a 3D printing technology, and finally the formed blank is degreased and sintered to prepare the ceramic-stainless steel composite material.
In order to achieve the above purpose, the technical scheme provided by the invention is as follows:
the ceramic-stainless steel composite material comprises the following components in percentage by mass as 100 percent: 40-50% of ceramic powder and 50-60% of stainless steel powder.
The ceramic-stainless steel composite material comprises, by mass, 100% of the total weight, 55-60% of ceramic-stainless steel composite powder and 40-45% of organic additives; the ceramic-stainless steel composite powder comprises the following components in percentage by mass as 100 percent: 40-50% of ceramic powder and 50-60% of stainless steel powder; the organic additive comprises the following components in percentage by mass as 100 percent: 35-45% of paraffin, 30-35% of ethylene-vinyl acetate copolymer, 15-20% of high-density polyethylene and 5-10% of stearic acid.
The ceramic-stainless steel composite material is prepared by taking ceramic powder and stainless steel powder which are uniformly mixed as aggregate, uniformly coating the composite powder by adding an organic additive to prepare thermoplastic particles with high solid content, stability, uniformity and good low-temperature fluidity, forming a ceramic-stainless steel composite material biscuit by a 3D printing technology, and degreasing and sintering the formed green body.
As a further improvement of the scheme, the raw materials of the ceramic-stainless steel composite material comprise 60% of ceramic-stainless steel composite powder and 40% of organic additive in terms of 100% of total mass percent; the organic additive comprises the following components in percentage by mass as 100 percent: 45% paraffin wax, 30% ethylene-vinyl acetate copolymer, 20% high density polyethylene and 5% stearic acid.
As a further improvement of the scheme, the raw materials of the ceramic-stainless steel composite material comprise 60% of ceramic-stainless steel composite powder and 40% of organic additive in terms of 100% of total mass percent; the organic additive comprises the following components in percentage by mass as 100 percent: 45% paraffin wax, 35% ethylene-vinyl acetate copolymer, 15% high density polyethylene and 5% stearic acid.
As a further improvement of the scheme, the ceramic powder is one of alumina ceramic powder, zirconia ceramic powder and ZTA ceramic powder; the average grain diameter of the ceramic powder is 1-5 mu m, and the average grain diameter of the stainless steel powder is 5-50 mu m.
The invention also provides a preparation method of the ceramic-stainless steel composite material, which comprises the following steps:
(1) Preparing granules of the thermoplastic ceramic-stainless steel composite material with high solid content and stability and uniformity by adopting an internal mixing method;
(2) Preparing a ceramic-stainless steel composite material biscuit from the particle material of the ceramic-stainless steel composite material by adopting a 3D printing technology;
(3) And (3) sequentially adopting degreasing and sintering processes to prepare the ceramic-stainless steel composite material biscuit into the ceramic-stainless steel composite material.
The specific steps in the step (1) are as follows: filling micron-sized ceramic powder and metal powder into a mixing tank, and placing the mixture on a three-dimensional motion mixer for mixing for 6-12 hours to obtain a uniformly mixed ceramic-stainless steel composite powder raw material; adding paraffin into an internal mixer at a low temperature of 135-175 ℃ for melting, then adding ethylene-vinyl acetate copolymer (EVA), high-density polyethylene (HDPE) and Stearic Acid (SA), and starting a rotor to uniformly mix the organic additives; after the temperature is raised to the initial temperature of 135-175 ℃, adding the uniformly mixed ceramic-stainless steel composite powder into an organic additive in an internal mixer cavity, and banburying for 60-120 min to obtain composite slurry in a fluid state; and opening an internal mixer, cooling the slurry to room temperature, and granulating for later use.
The specific steps in the step (2) are as follows: filling the thermoplastic ceramic-stainless steel composite particles prepared in the step (1) into a 3D printer charging barrel, and carrying out extrusion molding on the ceramic-stainless steel composite biscuit according to a pre-designed model, wherein the technological parameters are as follows: the temperature of the nozzle of the printer is 130-180 ℃, the temperature of the hot bed is 40-60 ℃, the thickness of the printing layer is 0.05-0.15 mm, and the moving speed of the nozzle is 15-25 mm/s.
The step (3) adopts a solvent degreasing and thermal degreasing two-step degreasing method to remove the organic additive, wherein the solvent degreasing process is to put a ceramic-stainless steel composite biscuit into n-heptane (C) 7 H 16 ) Preserving the temperature of 50-80 ℃ in the solution for 10-20 min, taking out the biscuit, and drying for 1h at 80 ℃; the thermal degreasing process adopts gradient heating, and comprises the following specific processes: in the first stage, heating from room temperature to 150 ℃ at a heating rate of 1-2 ℃/min, and preserving heat for 120-240 min; the second stage, heating from 150 ℃ to 250 ℃ at a heating rate of 0.5-1 ℃/min, and preserving heat for 90-180 min; third, heating from 250 ℃ to 300 ℃ at a heating rate of 1-2 ℃/min, and preserving heat for 90-180 min; a fourth stage, heating from 300 ℃ to 380 ℃ at a heating rate of 1.5-3 ℃/min, and preserving heat for 90-180 min; a fifth step of heating the mixture at a heating rate of 1.5-3 ℃/min from 38Heating to 450 ℃ at 0 ℃ and preserving heat for 120-240 min.
Sintering is vacuum sintering, gradient heating is adopted, and the specific process is as follows: in the first stage, heating from room temperature to 450 ℃ at a heating rate of 2-3 ℃/min, and preserving heat for 60-90 min; a second stage, heating from 450 ℃ to 750 ℃ at a heating rate of 3-4 ℃/min, and preserving heat for 60-90 min; in the third stage, heating from 750 ℃ to 1200 ℃ at a heating rate of 4-5 ℃/min, and preserving heat for 60-90 min; and in the fourth stage, heating from 1200 ℃ to 1375 ℃ at a heating rate of 1-2 ℃/min, and preserving heat for 120-240 min.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, the ratio of EVA to HDPE in the multi-element organic additive is controlled, so that the rheological property and the forming property of the composite material granule at low temperature can be obviously improved, the ethylene-vinyl acetate copolymer (EVA) and the high-density polyethylene (HDPE) in the organic additive have a synergistic effect, the strength of a composite material biscuit and the shape of a green body in the degreasing process can be ensured not to be changed, the EVA and the HDPE are embedded into the surface of composite powder in different ways, the transmission mode of compound potential is increased, thereby preventing the segregation of the organic additive in the slurry, and improving the uniformity, the fluidity and the forming property of the slurry at low temperature; the prepared granules of the thermoplastic ceramic-stainless steel composite material have the advantages of high solid phase content, stability, uniformity, good low-temperature fluidity and the like; the ceramic reinforcing phase in the prepared ceramic-stainless steel composite material is uniformly distributed, the ceramic-stainless steel bonding interface is excellent, and the composite material has the advantages of the toughness of stainless steel, the high hardness and wear resistance of ceramic and the like, and has excellent comprehensive performance.
2. The organic additive is a multi-component organic polymer mixture, wherein paraffin provides low-temperature fluidity in the organic additive system, so that composite particles can be smoothly extruded from a spray head of a 3D printer without blocking the spray head; stearic Acid (SA) is used as a surfactant to connect the organic part and the composite powder, so that layering between the organic part and the composite powder is prevented.
3. The invention adopts micron-sized ceramic powder and stainless steel metal powder, and the cost of raw materials is low.
4. The preparation method provided by the invention can integrally form materials with different components, so that the three-dimensional free design of the material components is realized; the method can also rapidly prepare components/products with any complex shape, and effectively shortens the development flow of new products; in addition, the utilization rate of materials can be effectively improved by adopting the 3D printing near-net forming technology.
Drawings
FIGS. 1 (a) to (c) are graphs showing thermal weight loss (TG-DTG) curves from room temperature to 700℃of the ceramic-stainless steel composite particles prepared in comparative examples 1, 2 and 1, respectively;
FIGS. 2 (a) to (c) are microstructure diagrams of the ceramic-stainless steel composite materials prepared in examples 1, 4 and 5, respectively, under a scanning microscope;
FIGS. 3 (a) to (c) are SEM images of the microscopic morphologies of the ceramic-stainless steel composite material prepared in example 1 of the present invention before degreasing, after degreasing, and after sintering, respectively.
Detailed Description
For a better description of the objects, technical solutions and advantages of the present invention, the present invention will be further described with reference to the following specific examples.
Example 1:
the preparation method of the ZTA ceramic-stainless steel composite material comprises the following steps:
s1, preparing ZTA ceramic-stainless steel composite particles:
the grain material is prepared by taking 60 weight percent of ZTA ceramic-stainless steel composite powder as aggregate and adding 40 weight percent of organic additive according to the total mass percent of 100 percent;
the method specifically comprises the following steps:
s1.1, preparing ZTA ceramic-stainless steel composite powder: the ZTA ceramic powder with the weight percentage of 45 percent and the stainless steel powder with the weight percentage of 55 percent are filled into a mixing tank, and are placed on a three-dimensional motion mixer to be mixed for 6 hours, so as to obtain uniformly mixed ZTA ceramic-stainless steel composite powder;
s1.2 preparation of organic additives: adding 45 weight percent of paraffin into an internal mixer at 150 ℃ to melt, then adding 25 weight percent of ethylene-vinyl acetate copolymer (EVA), 25 weight percent of high-density polyethylene (HDPE) and 5 weight percent of Stearic Acid (SA), and starting a rotor to uniformly mix organic matters;
s1.3, preparing ZTA ceramic-stainless steel composite slurry: after the temperature of the internal mixer is raised to 150 ℃, adding the uniformly mixed ZTA ceramic-stainless steel composite powder into a multi-component organic additive in a cavity of the internal mixer, and carrying out internal mixing for 60min to obtain ZTA ceramic-stainless steel composite material slurry in a fluid state;
S1.4, opening an internal mixer, and granulating after the ZTA ceramic-stainless steel composite material slurry is cooled to room temperature to prepare ZTA ceramic-stainless steel composite material particles for later use;
s2 3D printing and forming ZTA ceramic-stainless steel composite biscuit: filling the ZTA ceramic-stainless steel composite particles prepared in the step S1 into a 3D printer charging barrel, and extruding and molding a composite material biscuit according to a pre-designed model, wherein 3D printing parameters are as follows: the temperature of the nozzle of the printer is 150 ℃, the temperature of the hot bed is 50 ℃, the thickness of the printing layer is 0.10mm, and the moving speed of the nozzle is 20mm/s;
s3 degreasing and sintering to prepare the ZTA ceramic-stainless steel composite material: removing the multi-element organic additive by adopting a solvent degreasing and thermal degreasing two-step degreasing method, and sintering by adopting vacuum sintering, wherein the method specifically comprises the following steps of:
s3.1, dissolving and degreasing: putting the ZTA ceramic-stainless steel composite biscuit prepared in the step S2 into a beaker, and adding n-heptane (C 7 H 16 ) Placing the solution into a constant temperature water bath, preserving heat at 80 ℃ for 20min, finally taking out the biscuit, and drying in a drying oven at 80 ℃ for 1h;
s3.2, thermal degreasing: transferring the solvent-degreased ZTA ceramic-stainless steel composite material biscuit into a degreasing furnace for thermal degreasing, wherein the technological parameters are as follows: a. the temperature is kept for 120min at Room Temperature (RT) to 150 ℃ at a heating rate of 2 ℃/min; b, maintaining the temperature at 150-250 ℃ at a heating rate of 1 ℃/min for 90min; c.250-300 ℃, heating up at a rate of 1 ℃/min, and preserving heat for 90min; d, maintaining the temperature for 90min at the temperature of 300-380 ℃ and the heating rate of 3 ℃/min; e, maintaining the temperature for 120min at 380-450 ℃ and a heating rate of 3 ℃/min;
S3.3 sintering: vacuum sintering is adopted for sintering, and ZTA ceramic-stainless steel composite material is obtained after cooling along with a furnace, wherein specific sintering parameters are as follows: a. the temperature is kept at Room Temperature (RT) to 450 ℃, the heating rate is 3 ℃/min, and the temperature is kept for 60min; b, maintaining the temperature for 60min at the temperature of 450-750 ℃ and the heating rate of 4 ℃/min; c, 750-1200 ℃, heating up at a speed of 5 ℃/min, and preserving heat for 60min; d, keeping the temperature for 120min at 1200-1375 ℃ and a heating rate of 2 ℃/min.
Example 2:
the preparation method of the ZTA ceramic-stainless steel composite material comprises the following steps:
s1, preparing ZTA ceramic-stainless steel composite particles:
the grain material is prepared by taking 60 weight percent of ZTA ceramic-stainless steel composite powder as aggregate and adding 40 weight percent of organic additive according to the total mass percent of 100 percent;
the method specifically comprises the following steps:
s1.1, preparing ZTA ceramic-stainless steel composite powder: the ZTA ceramic powder with the weight percentage of 45 percent and the stainless steel powder with the weight percentage of 55 percent are filled into a mixing tank, and are placed on a three-dimensional motion mixer to be mixed for 6 hours, so as to obtain uniformly mixed ZTA ceramic-stainless steel composite powder;
s1.2 preparation of organic additives: adding 45 weight percent of paraffin into an internal mixer at 150 ℃ to melt, adding 30 weight percent of ethylene-vinyl acetate copolymer (EVA), 20 weight percent of high-density polyethylene (HDPE) and 5 weight percent of Stearic Acid (SA), and starting a rotor to uniformly mix organic matters;
S1.3, preparing ZTA ceramic-stainless steel composite slurry: after the temperature of the internal mixer is raised to 150 ℃, adding the uniformly mixed ZTA ceramic-stainless steel composite powder into a multi-component organic additive in a cavity of the internal mixer, and carrying out internal mixing for 60min to obtain ZTA ceramic-stainless steel composite material slurry in a fluid state;
s1.4, opening an internal mixer, and granulating after the ZTA ceramic-stainless steel composite material slurry is cooled to room temperature to prepare ZTA ceramic-stainless steel composite material particles for later use;
s2 3D printing and forming ZTA ceramic-stainless steel composite biscuit: filling the ZTA ceramic-stainless steel composite particles prepared in the step S1 into a 3D printer charging barrel, and extruding and molding a composite material biscuit according to a pre-designed model, wherein 3D printing parameters are as follows: the temperature of the nozzle of the printer is 150 ℃, the temperature of the hot bed is 50 ℃, the thickness of the printing layer is 0.10mm, and the moving speed of the nozzle is 20mm/s;
s3 degreasing and sintering to prepare the ZTA ceramic-stainless steel composite material: removing the multi-element organic additive by adopting a solvent degreasing and thermal degreasing two-step degreasing method, and sintering by adopting vacuum sintering, wherein the method specifically comprises the following steps of:
s3.1, dissolving and degreasing: putting the ZTA ceramic-stainless steel composite biscuit prepared in the step S2 into a beaker, and adding n-heptane (C 7 H 16 ) Placing the solution into a constant temperature water bath, preserving heat at 80 ℃ for 20min, finally taking out the biscuit, and drying in a drying oven at 80 ℃ for 1h;
s3.2, thermal degreasing: transferring the solvent-degreased ZTA ceramic-stainless steel composite material biscuit into a degreasing furnace for thermal degreasing, wherein the technological parameters are as follows: a. the temperature is kept for 120min at Room Temperature (RT) to 150 ℃ at a heating rate of 2 ℃/min; b, maintaining the temperature at 150-250 ℃ at a heating rate of 1 ℃/min for 90min; c.250-300 ℃, heating up at a rate of 1 ℃/min, and preserving heat for 90min; d, maintaining the temperature for 90min at the temperature of 300-380 ℃ and the heating rate of 3 ℃/min; e, maintaining the temperature for 120min at 380-450 ℃ and a heating rate of 3 ℃/min;
s3.3 sintering: vacuum sintering is adopted for sintering, and ZTA ceramic-stainless steel composite material is obtained after cooling along with a furnace, wherein specific sintering parameters are as follows: a. the temperature is kept at Room Temperature (RT) to 450 ℃, the heating rate is 3 ℃/min, and the temperature is kept for 60min; b, maintaining the temperature for 60min at the temperature of 450-750 ℃ and the heating rate of 4 ℃/min; c, 750-1200 ℃, heating up at a speed of 5 ℃/min, and preserving heat for 60min; d, keeping the temperature for 120min at 1200-1375 ℃ and a heating rate of 2 ℃/min.
Example 3:
the preparation method of the ZTA ceramic-stainless steel composite material comprises the following steps:
s1, preparing ZTA ceramic-stainless steel composite particles:
The grain material is prepared by taking 60 weight percent of ZTA ceramic-stainless steel composite powder as aggregate and adding 40 weight percent of organic additive according to the total mass percent of 100 percent;
the method specifically comprises the following steps:
s1.1, preparing ZTA ceramic-stainless steel composite powder: the ZTA ceramic powder with the weight percentage of 45 percent and the stainless steel powder with the weight percentage of 55 percent are filled into a mixing tank, and are placed on a three-dimensional motion mixer to be mixed for 6 hours, so as to obtain uniformly mixed ZTA ceramic-stainless steel composite powder;
s1.2 preparation of organic additives: adding 45 weight percent of paraffin into an internal mixer at 150 ℃ to melt, then adding 35 weight percent of ethylene-vinyl acetate copolymer (EVA), 15 weight percent of high-density polyethylene (HDPE) and 5 weight percent of Stearic Acid (SA), and starting a rotor to uniformly mix organic matters;
s1.3, preparing ZTA ceramic-stainless steel composite slurry: after the temperature of the internal mixer is raised to 150 ℃, adding the uniformly mixed ZTA ceramic-stainless steel composite powder into a multi-component organic additive in a cavity of the internal mixer, and carrying out internal mixing for 60min to obtain ZTA ceramic-stainless steel composite material slurry in a fluid state;
s1.4, opening an internal mixer, and granulating after the ZTA ceramic-stainless steel composite material slurry is cooled to room temperature to prepare ZTA ceramic-stainless steel composite material particles for later use;
S2 3D printing and forming ZTA ceramic-stainless steel composite biscuit: filling the ZTA ceramic-stainless steel composite particles prepared in the step S1 into a 3D printer charging barrel, and extruding and molding a composite material biscuit according to a pre-designed model, wherein 3D printing parameters are as follows: the temperature of the nozzle of the printer is 150 ℃, the temperature of the hot bed is 50 ℃, the thickness of the printing layer is 0.10mm, and the moving speed of the nozzle is 20mm/s;
s3 degreasing and sintering to prepare the ZTA ceramic-stainless steel composite material: removing the multi-element organic additive by adopting a solvent degreasing and thermal degreasing two-step degreasing method, and sintering by adopting vacuum sintering, wherein the method specifically comprises the following steps of:
s3.1, dissolving and degreasing: putting the ZTA ceramic-stainless steel composite biscuit prepared in the step S2 into a beaker, and adding n-heptane (C 7 H 16 ) The solution is put into a constant temperature water bath kettle, the temperature is kept for 20min at 80 ℃, and finally the biscuit is taken out, and the temperature is kept at 80 DEG CDrying in a drying oven at the temperature of 1h;
s3.2, thermal degreasing: transferring the solvent-degreased ZTA ceramic-stainless steel composite material biscuit into a degreasing furnace for thermal degreasing, wherein the technological parameters are as follows: a. the temperature is kept for 120min at Room Temperature (RT) to 150 ℃ at a heating rate of 2 ℃/min; b, maintaining the temperature at 150-250 ℃ at a heating rate of 1 ℃/min for 90min; c.250-300 ℃, heating up at a rate of 1 ℃/min, and preserving heat for 90min; d, maintaining the temperature for 90min at the temperature of 300-380 ℃ and the heating rate of 3 ℃/min; e, maintaining the temperature for 120min at 380-450 ℃ and a heating rate of 3 ℃/min;
S3.3 sintering: vacuum sintering is adopted for sintering, and ZTA ceramic-stainless steel composite material is obtained after cooling along with a furnace, wherein specific sintering parameters are as follows: a. the temperature is kept at Room Temperature (RT) to 450 ℃, the heating rate is 3 ℃/min, and the temperature is kept for 60min; b, maintaining the temperature for 60min at the temperature of 450-750 ℃ and the heating rate of 4 ℃/min; c, 750-1200 ℃, heating up at a speed of 5 ℃/min, and preserving heat for 60min; d, keeping the temperature for 120min at 1200-1375 ℃ and a heating rate of 2 ℃/min.
Example 4:
the preparation method of the ZTA ceramic-stainless steel composite material comprises the following steps:
s1, preparing ZTA ceramic-stainless steel composite particles:
the grain material is prepared by taking 58 weight percent of ZTA ceramic-stainless steel composite powder as aggregate and adding 42 weight percent of organic additive according to the total mass percent of 100 percent;
the method specifically comprises the following steps:
s1.1, preparing ZTA ceramic-stainless steel composite powder: the ZTA ceramic powder with the weight percentage of 45 percent and the stainless steel powder with the weight percentage of 55 percent are filled into a mixing tank, and are placed on a three-dimensional motion mixer to be mixed for 6 hours, so as to obtain uniformly mixed ZTA ceramic-stainless steel composite powder;
s1.2 preparation of organic additives: adding 45 weight percent of paraffin into an internal mixer at 150 ℃ to melt, then adding 25 weight percent of ethylene-vinyl acetate copolymer (EVA), 25 weight percent of high-density polyethylene (HDPE) and 5 weight percent of Stearic Acid (SA), and starting a rotor to uniformly mix organic matters;
S1.3, preparing ZTA ceramic-stainless steel composite slurry: after the temperature of the internal mixer is raised to 150 ℃, adding the uniformly mixed ZTA ceramic-stainless steel composite powder into a multi-component organic additive in a cavity of the internal mixer, and carrying out internal mixing for 60min to obtain ZTA ceramic-stainless steel composite material slurry in a fluid state;
s1.4, opening an internal mixer, and granulating after the ZTA ceramic-stainless steel composite material slurry is cooled to room temperature to prepare ZTA ceramic-stainless steel composite material particles for later use;
s2 3D printing and forming ZTA ceramic-stainless steel composite biscuit: filling the ZTA ceramic-stainless steel composite particles prepared in the step S1 into a 3D printer charging barrel, and extruding and molding a composite material biscuit according to a pre-designed model, wherein 3D printing parameters are as follows: the temperature of the nozzle of the printer is 150 ℃, the temperature of the hot bed is 50 ℃, the thickness of the printing layer is 0.10mm, and the moving speed of the nozzle is 20mm/s;
s3 degreasing and sintering to prepare the ZTA ceramic-stainless steel composite material: removing the multi-element organic additive by adopting a solvent degreasing and thermal degreasing two-step degreasing method, and sintering by adopting vacuum sintering, wherein the method specifically comprises the following steps of:
s3.1, dissolving and degreasing: putting the ZTA ceramic-stainless steel composite biscuit prepared in the step S2 into a beaker, and adding n-heptane (C 7 H 16 ) Placing the solution into a constant temperature water bath, preserving heat at 80 ℃ for 20min, finally taking out the biscuit, and drying in a drying oven at 80 ℃ for 1h;
s3.2, thermal degreasing: transferring the solvent-degreased ZTA ceramic-stainless steel composite material biscuit into a degreasing furnace for thermal degreasing, wherein the technological parameters are as follows: a. the temperature is kept for 120min at Room Temperature (RT) to 150 ℃ at a heating rate of 2 ℃/min; b, maintaining the temperature at 150-250 ℃ at a heating rate of 1 ℃/min for 90min; c.250-300 ℃, heating up at a rate of 1 ℃/min, and preserving heat for 90min; d, maintaining the temperature for 90min at the temperature of 300-380 ℃ and the heating rate of 3 ℃/min; e, maintaining the temperature for 120min at 380-450 ℃ and a heating rate of 3 ℃/min;
s3.3 sintering: vacuum sintering is adopted for sintering, and ZTA ceramic-stainless steel composite material is obtained after cooling along with a furnace, wherein specific sintering parameters are as follows: a. the temperature is kept at Room Temperature (RT) to 450 ℃, the heating rate is 3 ℃/min, and the temperature is kept for 60min; b, maintaining the temperature for 60min at the temperature of 450-750 ℃ and the heating rate of 4 ℃/min; c, 750-1200 ℃, heating up at a speed of 5 ℃/min, and preserving heat for 60min; d, keeping the temperature for 120min at 1200-1375 ℃ and a heating rate of 2 ℃/min.
Example 5:
the preparation method of the ZTA ceramic-stainless steel composite material comprises the following steps:
s1, preparing ZTA ceramic-stainless steel composite particles:
The grain material is prepared by taking 55wt% of ZTA ceramic-stainless steel composite powder as aggregate and adding 45wt% of organic additive according to the total mass percentage of 100%;
the method specifically comprises the following steps:
s1.1, preparing ZTA ceramic-stainless steel composite powder: the ZTA ceramic powder with the weight percentage of 45 percent and the stainless steel powder with the weight percentage of 55 percent are filled into a mixing tank, and are placed on a three-dimensional motion mixer to be mixed for 6 hours, so as to obtain uniformly mixed ZTA ceramic-stainless steel composite powder;
s1.2 preparation of organic additives: adding 45 weight percent of paraffin into an internal mixer at 150 ℃ to melt, then adding 25 weight percent of ethylene-vinyl acetate copolymer (EVA), 25 weight percent of high-density polyethylene (HDPE) and 5 weight percent of Stearic Acid (SA), and starting a rotor to uniformly mix organic matters;
s1.3, preparing ZTA ceramic-stainless steel composite slurry: after the temperature of the internal mixer is raised to 150 ℃, adding the uniformly mixed ZTA ceramic-stainless steel composite powder into a multi-component organic additive in a cavity of the internal mixer, and carrying out internal mixing for 60min to obtain ZTA ceramic-stainless steel composite material slurry in a fluid state;
s1.4, opening an internal mixer, and granulating after the ZTA ceramic-stainless steel composite material slurry is cooled to room temperature to prepare ZTA ceramic-stainless steel composite material particles for later use;
S2 3D printing and forming ZTA ceramic-stainless steel composite biscuit: filling the ZTA ceramic-stainless steel composite particles prepared in the step S1 into a 3D printer charging barrel, and extruding and molding a composite material biscuit according to a pre-designed model, wherein 3D printing parameters are as follows: the temperature of the nozzle of the printer is 150 ℃, the temperature of the hot bed is 50 ℃, the thickness of the printing layer is 0.10mm, and the moving speed of the nozzle is 20mm/s;
s3 degreasing and sintering to prepare the ZTA ceramic-stainless steel composite material: removing the multi-element organic additive by adopting a solvent degreasing and thermal degreasing two-step degreasing method, and sintering by adopting vacuum sintering, wherein the method specifically comprises the following steps of:
s3.1, dissolving and degreasing: putting the ZTA ceramic-stainless steel composite biscuit prepared in the step S2 into a beaker, and adding n-heptane (C 7 H 16 ) Placing the solution into a constant temperature water bath, preserving heat at 80 ℃ for 20min, finally taking out the biscuit, and drying in a drying oven at 80 ℃ for 1h;
s3.2, thermal degreasing: transferring the solvent-degreased ZTA ceramic-stainless steel composite material biscuit into a degreasing furnace for thermal degreasing, wherein the technological parameters are as follows: a. the temperature is kept for 120min at Room Temperature (RT) to 150 ℃ at a heating rate of 2 ℃/min; b, maintaining the temperature at 150-250 ℃ at a heating rate of 1 ℃/min for 90min; c.250-300 ℃, heating up at a rate of 1 ℃/min, and preserving heat for 90min; d, maintaining the temperature for 90min at the temperature of 300-380 ℃ and the heating rate of 3 ℃/min; e, maintaining the temperature for 120min at 380-450 ℃ and a heating rate of 3 ℃/min;
S3.3 sintering: vacuum sintering is adopted for sintering, and ZTA ceramic-stainless steel composite material is obtained after cooling along with a furnace, wherein specific sintering parameters are as follows: a. the temperature is kept at Room Temperature (RT) to 450 ℃, the heating rate is 3 ℃/min, and the temperature is kept for 60min; b, maintaining the temperature for 60min at the temperature of 450-750 ℃ and the heating rate of 4 ℃/min; c, 750-1200 ℃, heating up at a speed of 5 ℃/min, and preserving heat for 60min; d, keeping the temperature for 120min at 1200-1375 ℃ and a heating rate of 2 ℃/min.
Example 6:
the preparation method of the ZTA ceramic-stainless steel composite material comprises the following steps:
s1, preparing ZTA ceramic-stainless steel composite particles:
the grain material is prepared by taking 60 weight percent of ZTA ceramic-stainless steel composite powder as aggregate and adding 40 weight percent of organic additive according to the total mass percent of 100 percent;
the method specifically comprises the following steps:
s1.1, preparing ZTA ceramic-stainless steel composite powder: filling 50 weight percent of ZTA ceramic powder and 50 weight percent of stainless steel powder into a mixing tank, and placing the materials on a three-dimensional motion mixer for mixing for 8 hours to obtain uniformly mixed ZTA ceramic-stainless steel composite powder;
s1.2 preparation of organic additives: adding 45 weight percent of paraffin into an internal mixer at 135 ℃ to melt, then adding 25 weight percent of ethylene-vinyl acetate copolymer (EVA), 25 weight percent of high-density polyethylene (HDPE) and 5 weight percent of Stearic Acid (SA), and starting a rotor to uniformly mix organic matters;
S1.3, preparing ZTA ceramic-stainless steel composite slurry: after the temperature of the internal mixer is raised to 135 ℃, adding the uniformly mixed ZTA ceramic-stainless steel composite powder into a multi-component organic additive in a cavity of the internal mixer, and carrying out internal mixing for 90min to obtain ZTA ceramic-stainless steel composite material slurry in a fluid state;
s1.4, opening an internal mixer, and granulating after the ZTA ceramic-stainless steel composite material slurry is cooled to room temperature to prepare ZTA ceramic-stainless steel composite material particles for later use;
s2 3D printing and forming ZTA ceramic-stainless steel composite biscuit: filling the ZTA ceramic-stainless steel composite particles prepared in the step S1 into a 3D printer charging barrel, and extruding and molding a composite material biscuit according to a pre-designed model, wherein 3D printing parameters are as follows: the temperature of the nozzle of the printer is 180 ℃, the temperature of the hot bed is 60 ℃, the thickness of the printing layer is 0.15mm, and the moving speed of the nozzle is 25mm/s;
s3 degreasing and sintering to prepare the ZTA ceramic-stainless steel composite material: removing the multi-element organic additive by adopting a solvent degreasing and thermal degreasing two-step degreasing method, and sintering by adopting vacuum sintering, wherein the method specifically comprises the following steps of:
s3.1, dissolving and degreasing: putting the ZTA ceramic-stainless steel composite biscuit prepared in the step S2 into a beaker, and adding n-heptane (C 7 H 16 ) Placing the solution into a constant temperature water bath, preserving heat at 80 ℃ for 20min, finally taking out the biscuit, and drying in a drying oven at 80 ℃ for 1h;
s3.2, thermal degreasing: transferring the solvent-degreased ZTA ceramic-stainless steel composite material biscuit into a degreasing furnace for thermal degreasing, wherein the technological parameters are as follows: a. the temperature is kept for 180min at Room Temperature (RT) to 150 ℃ at a heating rate of 1.5 ℃/min; b, maintaining the temperature at 150-250 ℃ at a heating rate of 1 ℃/min for 120min; c.250-300 ℃, the temperature rising rate is 1.5 ℃/min, and the temperature is kept for 120min; d, maintaining the temperature for 120min at 300-380 ℃ at a heating rate of 2 ℃/min; e, maintaining the temperature for 180min at 380-450 ℃ and a heating rate of 2 ℃/min;
s3.3 sintering: vacuum sintering is adopted for sintering, and ZTA ceramic-stainless steel composite material is obtained after cooling along with a furnace, wherein specific sintering parameters are as follows: a. the temperature is kept at Room Temperature (RT) to 450 ℃, the heating rate is 2 ℃/min, and the temperature is kept for 60min; b, maintaining the temperature for 60min at the temperature of 450-750 ℃ and the heating rate of 4 ℃/min; c, 750-1200 ℃, heating up at a speed of 5 ℃/min, and preserving heat for 60min; d, keeping the temperature for 120min at 1200-1375 ℃ and a heating rate of 2 ℃/min.
Example 7:
the preparation method of the ZTA ceramic-stainless steel composite material comprises the following steps:
s1, preparing ZTA ceramic-stainless steel composite particles:
The grain material is prepared by taking 60 weight percent of ZTA ceramic-stainless steel composite powder as aggregate and adding 40 weight percent of organic additive according to the total mass percent of 100 percent;
the method specifically comprises the following steps:
s1.1, preparing ZTA ceramic-stainless steel composite powder: the ZTA ceramic powder with the weight percentage of 55wt% and the stainless steel powder with the weight percentage of 45wt% are filled into a mixing tank, and are placed on a three-dimensional motion mixer to be mixed for 12 hours, so as to obtain uniformly mixed ZTA ceramic-stainless steel composite powder;
s1.2 preparation of organic additives: adding 45 weight percent of paraffin into an internal mixer at 175 ℃ to melt, then adding 25 weight percent of ethylene-vinyl acetate copolymer (EVA), 25 weight percent of high-density polyethylene (HDPE) and 5 weight percent of Stearic Acid (SA), and starting a rotor to uniformly mix organic matters;
s1.3, preparing ZTA ceramic-stainless steel composite slurry: after the temperature of the internal mixer is raised to 175 ℃, adding the uniformly mixed ZTA ceramic-stainless steel composite powder into a multi-component organic additive in a cavity of the internal mixer, and carrying out internal mixing for 120min to obtain ZTA ceramic-stainless steel composite material slurry in a fluid state;
s1.4, opening an internal mixer, and granulating after the ZTA ceramic-stainless steel composite material slurry is cooled to room temperature to prepare ZTA ceramic-stainless steel composite material particles for later use;
S2 3D printing and forming ZTA ceramic-stainless steel composite biscuit: filling the ZTA ceramic-stainless steel composite particles prepared in the step S1 into a 3D printer charging barrel, and extruding and molding a composite material biscuit according to a pre-designed model, wherein 3D printing parameters are as follows: the temperature of the nozzle of the printer is 160 ℃, the temperature of the hot bed is 50 ℃, the thickness of the printing layer is 0.05mm, and the moving speed of the nozzle is 15mm/s;
s3 degreasing and sintering to prepare the ZTA ceramic-stainless steel composite material: removing the multi-element organic additive by adopting a solvent degreasing and thermal degreasing two-step degreasing method, and sintering by adopting vacuum sintering, wherein the method specifically comprises the following steps of:
s3.1, dissolving and degreasing: putting the ZTA ceramic-stainless steel composite biscuit prepared in the step S2 into a beaker, and adding n-heptane (C 7 H 16 ) Placing the solution into a constant temperature water bath, preserving heat at 80 ℃ for 20min, finally taking out the biscuit, and drying in a drying oven at 80 ℃ for 1h;
s3.2, thermal degreasing: transferring the solvent-degreased ZTA ceramic-stainless steel composite material biscuit into a degreasing furnace for thermal degreasing, wherein the technological parameters are as follows: a. the temperature is kept at Room Temperature (RT) to 150 ℃ at a heating rate of 1 ℃/min and at a temperature of 240min; b, maintaining the temperature at 150-250 ℃ at a heating rate of 0.5 ℃/min for 180min; c.250-300 ℃, heating up at a rate of 1 ℃/min, and preserving heat for 180min; d, maintaining the temperature for 180min at 300-380 ℃ at a heating rate of 1.5 ℃/min; e, maintaining the temperature at 380-450 ℃ at a heating rate of 1.5 ℃/min for 240min;
S3.3 sintering: vacuum sintering is adopted for sintering, and ZTA ceramic-stainless steel composite material is obtained after cooling along with a furnace, wherein specific sintering parameters are as follows: a. the temperature is kept for 90min at the Room Temperature (RT) to 450 ℃ at the heating rate of 2 ℃/min; 450-750 ℃, heating up at a rate of 3 ℃/min, and preserving heat for 90min; c, 750-1200 ℃, heating up at a speed of 4 ℃/min, and preserving heat for 90min; d.1200-1375 ℃, heating up at a speed of 1 ℃/min, and preserving heat for 240min.
Example 8:
the preparation method of the alumina ceramic-stainless steel composite material comprises the following steps:
s1, preparing an alumina ceramic-stainless steel composite granule:
the granule is prepared by taking 60 weight percent of alumina ceramic-stainless steel composite powder as aggregate and adding 40 weight percent of organic additive according to the total mass percent of 100 percent;
the method specifically comprises the following steps:
s1.1, preparing aluminum oxide ceramic-stainless steel composite powder: alumina powder with the weight percentage of 45 percent and stainless steel powder with the weight percentage of 55 percent are filled into a mixing tank, and are placed on a three-dimensional motion mixer to be mixed for 6 hours, thus obtaining evenly mixed alumina ceramic-stainless steel composite powder;
s1.2 preparation of organic additives: adding 45 weight percent of paraffin into an internal mixer at 150 ℃ to melt, then adding 25 weight percent of ethylene-vinyl acetate copolymer (EVA), 25 weight percent of high-density polyethylene (HDPE) and 5 weight percent of Stearic Acid (SA), and starting a rotor to uniformly mix organic matters;
S1.3, preparing alumina ceramic-stainless steel composite slurry: after the temperature of the internal mixer is raised to 150 ℃, adding the uniformly mixed alumina ceramic-stainless steel composite powder into a multi-component organic additive in a cavity of the internal mixer, and carrying out internal mixing for 60 minutes to obtain alumina ceramic-stainless steel composite material slurry in a fluid state;
s1.4, opening an internal mixer, and granulating after the alumina ceramic-stainless steel composite slurry is cooled to room temperature to prepare alumina ceramic-stainless steel composite particles for later use;
s2 3D printing and forming an alumina ceramic-stainless steel composite biscuit: putting the alumina ceramic-stainless steel composite particles prepared in the step S1 into a 3D printer charging barrel, extruding and forming a composite material biscuit according to a pre-designed model, wherein 3D printing parameters are as follows: the temperature of the nozzle of the printer is 150 ℃, the temperature of the hot bed is 50 ℃, the thickness of the printing layer is 0.10mm, and the moving speed of the nozzle is 20mm/s;
s3 degreasing and sintering to prepare the aluminum oxide ceramic-stainless steel composite material: removing the multi-element organic additive by adopting a solvent degreasing and thermal degreasing two-step degreasing method, and sintering by adopting vacuum sintering, wherein the method specifically comprises the following steps of:
s3.1, dissolving and degreasing: placing the alumina ceramic-stainless steel composite biscuit prepared in the step S2 into a beaker, and adding n-heptane (C 7 H 16 ) Placing the solution into a constant temperature water bath, preserving heat at 80 ℃ for 20min, finally taking out the biscuit, and drying in a drying oven at 80 ℃ for 1h;
s3.2, thermal degreasing: transferring the aluminum oxide ceramic-stainless steel composite material biscuit degreased by the solvent into a degreasing furnace for thermal degreasing, wherein the technological parameters are as follows: a. the temperature is kept for 120min at Room Temperature (RT) to 150 ℃ at a heating rate of 2 ℃/min; b, maintaining the temperature at 150-250 ℃ at a heating rate of 1 ℃/min for 90min; c.250-300 ℃, heating up at a rate of 1 ℃/min, and preserving heat for 90min; d, maintaining the temperature for 90min at the temperature of 300-380 ℃ and the heating rate of 3 ℃/min; e, maintaining the temperature for 120min at 380-450 ℃ and a heating rate of 3 ℃/min;
s3.3 sintering: the sintering adopts vacuum sintering, and alumina ceramic-stainless steel composite material is obtained after furnace cooling, and specific sintering parameters are as follows: a. the temperature is kept at Room Temperature (RT) to 450 ℃, the heating rate is 3 ℃/min, and the temperature is kept for 60min; b, maintaining the temperature for 60min at the temperature of 450-750 ℃ and the heating rate of 4 ℃/min; c, 750-1200 ℃, heating up at a speed of 5 ℃/min, and preserving heat for 60min; d, keeping the temperature for 120min at 1200-1375 ℃ and a heating rate of 2 ℃/min.
Example 9:
the preparation method of the zirconia ceramic-stainless steel composite material comprises the following steps:
s1, preparing zirconia ceramic-stainless steel composite particles:
The granular material is prepared by taking 60 weight percent of zirconia ceramic-stainless steel composite powder as aggregate and adding 40 weight percent of organic additive according to the total mass percent of 100 percent;
the method specifically comprises the following steps:
s1.1, preparing zirconia ceramic-stainless steel composite powder: putting 45 weight percent of zirconia powder and 55 weight percent of stainless steel powder into a mixing tank, and placing the zirconia powder and the stainless steel powder on a three-dimensional motion mixer for mixing for 6 hours to obtain uniformly mixed zirconia ceramic-stainless steel composite powder;
s1.2 preparation of organic additives: adding 45 weight percent of paraffin into an internal mixer at 150 ℃ to melt, then adding 25 weight percent of ethylene-vinyl acetate copolymer (EVA), 25 weight percent of high-density polyethylene (HDPE) and 5 weight percent of Stearic Acid (SA), and starting a rotor to uniformly mix organic matters;
s1.3, preparing zirconia ceramic-stainless steel composite slurry: after the temperature of the internal mixer is raised to 150 ℃, adding the uniformly mixed zirconia ceramic-stainless steel composite powder into a multi-component organic additive in a cavity of the internal mixer, and carrying out internal mixing for 60 minutes to obtain zirconia ceramic-stainless steel composite material slurry in a fluid state;
s1.4, opening an internal mixer, and granulating after the zirconia ceramic-stainless steel composite slurry is cooled to room temperature to prepare zirconia ceramic-stainless steel composite particles for later use;
S2 3D printing and forming a zirconia ceramic-stainless steel composite biscuit: putting the zirconia ceramic-stainless steel composite particles prepared in the step S1 into a 3D printer charging barrel, extruding and forming a composite material biscuit according to a pre-designed model, wherein 3D printing parameters are as follows: the temperature of the nozzle of the printer is 150 ℃, the temperature of the hot bed is 50 ℃, the thickness of the printing layer is 0.10mm, and the moving speed of the nozzle is 20mm/s;
s3 degreasing and sintering to prepare the zirconia ceramic-stainless steel composite material: removing the multi-element organic additive by adopting a solvent degreasing and thermal degreasing two-step degreasing method, and sintering by adopting vacuum sintering, wherein the method specifically comprises the following steps of:
s3.1, dissolving and degreasing: placing the zirconia ceramic-stainless steel composite biscuit prepared in the step S2 into a beaker, and adding n-heptane (C 7 H 16 ) Placing the solution into a constant temperature water bath, preserving heat at 80 ℃ for 20min, finally taking out the biscuit, and drying in a drying oven at 80 ℃ for 1h;
s3.2, thermal degreasing: transferring the zirconium oxide ceramic-stainless steel composite material biscuit subjected to solvent degreasing into a degreasing furnace for thermal degreasing, wherein the technological parameters are as follows: a. the temperature is kept for 120min at Room Temperature (RT) to 150 ℃ at a heating rate of 2 ℃/min; b, maintaining the temperature at 150-250 ℃ at a heating rate of 1 ℃/min for 90min; c.250-300 ℃, heating up at a rate of 1 ℃/min, and preserving heat for 90min; d, maintaining the temperature for 90min at the temperature of 300-380 ℃ and the heating rate of 3 ℃/min; e, maintaining the temperature for 120min at 380-450 ℃ and a heating rate of 3 ℃/min;
S3.3 sintering: the sintering adopts vacuum sintering, and zirconia ceramic-stainless steel composite material is obtained after furnace cooling, and specific sintering parameters are as follows: a. the temperature is kept at Room Temperature (RT) to 450 ℃, the heating rate is 3 ℃/min, and the temperature is kept for 60min; b, maintaining the temperature for 60min at the temperature of 450-750 ℃ and the heating rate of 4 ℃/min; c, 750-1200 ℃, heating up at a speed of 5 ℃/min, and preserving heat for 60min; d, keeping the temperature for 120min at 1200-1375 ℃ and a heating rate of 2 ℃/min.
Comparative example 1:
comparative example 1 is the same as example 1 except that: the organic additive added in the preparation of the ZTA ceramic-stainless steel composite material does not contain ethylene-vinyl acetate copolymer (EVA), and the organic additive comprises the following components: 45wt% Paraffin Wax (PW), 50wt% High Density Polyethylene (HDPE), 5wt% Stearic Acid (SA).
Comparative example 2:
comparative example 2 is the same as example 1 except that: the organic additive added in the preparation of the ZTA ceramic-stainless steel composite material does not contain High Density Polyethylene (HDPE), and the components in the organic additive are as follows: 45wt% Paraffin Wax (PW), 50wt% ethylene-vinyl acetate copolymer (EVA), 5wt% Stearic Acid (SA).
Effect example 1:
the properties of the ceramic-stainless steel composite materials prepared in examples 1 to 9 and comparative examples 1 to 2 were examined. The low-temperature fluidity, uniformity and weight loss of the composite members during degreasing of the ceramic-stainless steel composite particles prepared in examples 1 to 3 and comparative examples 1 to 2 were examined according to national standards, and the examination results are shown in tables 1, 2 and fig. 1 (a) to (c). The shrinkage properties of the composite green bodies of examples 1 and 4-5 during sintering preparation were characterized according to national standards and the results are shown in Table 3 and FIGS. 2 (a) - (c). The structure of the ceramic-stainless steel composite green body prepared in example 1 before and after degreasing and after sintering was characterized according to national standards, and the results are shown in fig. 3 (a) to (c).
TABLE 1 Effect of organic additives on Low temperature flowability of ceramic-stainless Steel granules
Figure BDA0003236936750000191
TABLE 2 Effect of organic additives on composite slurry density standard deviation
Figure BDA0003236936750000192
Figure BDA0003236936750000201
As can be seen from the above detection results by combining table 1, table 2 and fig. 1 (a) to (c), there is a good synergistic effect between the ethylene-vinyl acetate copolymer (EVA) and the High Density Polyethylene (HDPE), so that not only the rheological property and uniformity of the composite slurry itself become more excellent, but also the structural integrity of the 3D printing forming member is ensured as a skeleton structure. Specifically:
(1) Effect on rheological properties of composite slurries: table 1 reflects the viscosities of ceramic-stainless steel composite particles at different temperatures at a shear rate of 1/s, as can be seen from Table 1, the viscosities of composite slurries (examples 1-3) with both the EVA and HDPE two complex-phase macromolecular organic additives are much higher than those of composite slurries with only one macromolecular organic additive (comparative examples 1-2); the ceramic-stainless steel composite slurry in comparative examples 1-2 has low viscosity and good fluidity, is easy to cause poor forming capability, has the phenomenon of extrusion wire deformation in the subsequent 3D printing process, and cannot be formed into a required shape; by comparing examples 2 and 3 with comparative examples 1 and 2, it is proved that the EVA and HDPE can exert synergistic effect when being mixed for use, the viscosity of the slurry is obviously improved, and the forming property is further improved; however, the mixing effect of EVA and HDPE in the embodiment 1 is far less than that of the embodiments 2-3, the viscosity of the ceramic-stainless steel composite material slurry in the embodiment 1 is changed severely along with the temperature rise, the slurry is cooled to a certain extent when being extruded from a cylinder with fixed temperature to contact air in the printing process, and the slurry suspended in the half space is separated from the slurry to be extruded due to the overlarge viscosity change in a small temperature interval, so that a phenomenon of wire breakage occurs; therefore, it can be seen from examples 1 to 3 that the rheological property and the molding property of the composite material particles at low temperature can be remarkably improved by further controlling the weight ratio of the EVA to the HDPE in the organic additive (EVA: HDPE=3-3.5:1.5-2) on the basis of adding the EVA to the HDPE, so that the EVA and the HDPE show a synergistic effect.
(2) Effect on composite slurry uniformity: table 2 shows that the density deviation value of the slurry added with EVA is obviously lower than that of the slurry without EVA, which indicates that the addition of EVA is more beneficial to improving the uniformity of the slurry. The density deviation values of the slurry added with the complex-phase macromolecules are lower than those of the slurry added with only one macromolecule, because as can be seen from the microstructure of the slurry formed into a biscuit in fig. 3 (a), different macromolecules are embedded into the surface of the powder in different ways, and the transmission mode of compound potential is increased, so that the segregation of organic additives in the slurry is prevented.
(3) Effect on degreasing of composite 3D printing member material: as can be seen from fig. 1 (a) to (c), the composite slurries corresponding to comparative examples 1 to 2 and example 1 all show two stages of mass loss with increasing temperature, and the mass loss in the first stage is larger than that in the second stage. The thermal decomposition temperatures of PW and EVA are not different, both are about 230 ℃, and the corresponding comparative example 2 composite material in fig. 1 (b) lacks the presence of a framework-type macromolecule in the first stage, so that it is difficult to maintain the shape of the green body in the thermal degreasing process; whereas the second stage in FIGS. 1 (a) and (c) is the decomposition of HDPE, which is relatively delayed due to its better high temperature resistance (300 ℃); because of the large difference of the decomposition temperatures of PW, EVA and HDPE, the existence of skeleton macromolecules (shown as microstructure after degreasing in the figure 3 (b)) of the ceramic-stainless steel composite material in the heating stage of thermal degreasing is ensured, and the phenomena of collapse and the like of a blank are effectively avoided.
In conclusion, the synergistic effect of the composite slurry and the HDPE can be fully exerted by reasonably controlling the ratio of the EVA to the HDPE in terms of the characteristics of the composite slurry and the forming performance of the composite slurry.
TABLE 3 shrinkage Properties of ceramic-stainless Steel composite blanks
Figure BDA0003236936750000211
As shown in table 3, with the increase of the solid content of the composite powder, the sintering shrinkage of the green body gradually decreases, which is beneficial to maintaining the original shape of the composite member, uniformly shrinking in all directions, and eliminating the defects of holes, cracks and the like; by observing the changes in microstructure of the ceramic-stainless steel composite in fig. 2 (a) to (c), it can be found that: with the improvement of the solid content of the composite powder and the reduction of the corresponding shrinkage rate, the particles in the composite material prepared by sintering are distributed more uniformly in the matrix, and the defects such as holes gradually disappear, thereby being beneficial to improving the overall performance of the ceramic-stainless steel composite material.
By observing the fracture morphology of the ceramic-stainless steel composite biscuit in fig. 3 (a), the powder particles are uniformly distributed in the organic binder, and the binder segregation phenomenon does not occur. Fig. 3 (b) shows that the ceramic and stainless steel in the degreased composite simply pile up like powder, but the green body is able to retain its printed structure and shape. Fig. 3 (c) shows that the sintering process adopted by the invention is reasonable, the densification effect of the ceramic-stainless steel composite material in the sintering process is good, the stainless steel is continuously distributed to form a matrix, and the dark ceramic particles are uniformly dispersed in the stainless steel matrix.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and substitutions can be made by those skilled in the art without departing from the technical principles of the present invention, and these modifications and substitutions should also be considered as being within the scope of the present invention.

Claims (9)

1. The ceramic-stainless steel composite material is characterized in that the raw materials of the ceramic-stainless steel composite material comprise 55-60% of ceramic-stainless steel composite powder and 40-45% of organic additives according to the total mass percentage of 100%; the ceramic-stainless steel composite powder comprises the following components in percentage by mass as 100 percent: 40-50% of ceramic powder and 50-60% of stainless steel powder; the organic additive comprises the following components in percentage by mass as 100 percent: 35-45% of paraffin, 30-35% of ethylene-vinyl acetate copolymer, 15-20% of high-density polyethylene and 5-10% of stearic acid; controlling the weight ratio of the ethylene-vinyl acetate copolymer to the high-density polyethylene in the organic additive to be 3-3.5:1.5-2; the ceramic powder is one of alumina ceramic powder, zirconia ceramic powder and ZTA ceramic powder, the ceramic-stainless steel composite material is prepared by taking ceramic powder and stainless steel powder which are uniformly mixed as aggregate, uniformly wrapping the composite powder by adding an organic additive to prepare thermoplastic particles with high solid phase content, stability, uniformity and good low-temperature fluidity, forming a ceramic-stainless steel composite material biscuit by a 3D printing technology, and degreasing and sintering the formed green body.
2. The ceramic-stainless steel composite material according to claim 1, wherein the raw materials of the ceramic-stainless steel composite material comprise 60% of ceramic-stainless steel composite powder and 40% of organic additives in terms of 100% of total mass percent; the organic additive comprises the following components in percentage by mass as 100 percent: 45% paraffin wax, 30% ethylene-vinyl acetate copolymer, 20% high density polyethylene and 5% stearic acid.
3. The ceramic-stainless steel composite material according to claim 1 or 2, wherein the raw materials of the ceramic-stainless steel composite material comprise 60% of ceramic-stainless steel composite powder and 40% of organic additive in terms of 100% of total mass percent; the organic additive comprises the following components in percentage by mass as 100 percent: 45% paraffin wax, 35% ethylene-vinyl acetate copolymer, 15% high density polyethylene and 5% stearic acid.
4. The ceramic-stainless steel composite material according to claim 1 or 2, wherein the ceramic powder has an average particle size of 1 to 5 μm and the stainless steel powder has an average particle size of 5 to 50 μm.
5. A method of producing a ceramic-stainless steel composite material according to any one of claims 1 to 4, comprising the steps of:
(1) Preparing granules of the thermoplastic ceramic-stainless steel composite material with high solid content and stability and uniformity by adopting an internal mixing method;
(2) Preparing a ceramic-stainless steel composite material biscuit from the particle material of the ceramic-stainless steel composite material by adopting a 3D printing technology;
(3) And (3) sequentially adopting degreasing and sintering processes to prepare the ceramic-stainless steel composite material biscuit into the ceramic-stainless steel composite material.
6. The method for preparing a ceramic-stainless steel composite material according to claim 5, wherein the step (1) comprises the following specific steps: filling micron-sized ceramic powder and metal powder into a mixing tank, and placing the mixture on a three-dimensional motion mixer for mixing for 6-12 hours to obtain a uniformly mixed ceramic-stainless steel composite powder raw material; adding paraffin into an internal mixer at a low temperature of 135-175 ℃ for melting, then adding ethylene-vinyl acetate copolymer, high-density polyethylene and stearic acid, and starting a rotor to uniformly mix the organic additives; after the temperature is raised to the initial temperature of 135-175 ℃, adding the uniformly mixed ceramic-stainless steel composite powder raw material into an organic additive in an internal mixer cavity, and banburying for 60-120 min to obtain composite slurry in a fluid state; and opening an internal mixer, cooling the slurry to room temperature, and granulating for later use.
7. The method for preparing a ceramic-stainless steel composite material according to claim 5, wherein the step (2) comprises the following specific steps: filling the thermoplastic ceramic-stainless steel composite particles prepared in the step (1) into a 3D printer charging barrel, and carrying out extrusion molding on the ceramic-stainless steel composite biscuit according to a pre-designed model, wherein the technological parameters are as follows: the temperature of the nozzle of the printer is 130-180 ℃, the temperature of the hot bed is 40-60 ℃, the thickness of the printing layer is 0.05-0.15 mm, and the moving speed of the nozzle is 15-25 mm/s.
8. The method for preparing a ceramic-stainless steel composite material according to claim 5, wherein the degreasing in the step (3) comprises a solvent degreasing process and a thermal degreasing process in sequence, wherein the solvent degreasing process is to put a ceramic-stainless steel composite material biscuit into an n-heptane solution, keep the temperature at 50-80 ℃ for 10-20 min, then take out the biscuit, and dry the biscuit at 80 ℃ for 1h; the thermal degreasing process adopts gradient heating, and comprises the following specific processes: in the first stage, heating from room temperature to 150 ℃ at a heating rate of 1-2 ℃/min, and preserving heat for 120-240 min; the second stage, heating from 150 ℃ to 250 ℃ at a heating rate of 0.5-1 ℃/min, and preserving heat for 90-180 min; third, heating from 250 ℃ to 300 ℃ at a heating rate of 1-2 ℃/min, and preserving heat for 90-180 min; a fourth stage, heating from 300 ℃ to 380 ℃ at a heating rate of 1.5-3 ℃/min, and preserving heat for 90-180 min; and fifth stage, heating from 380 ℃ to 450 ℃ at a heating rate of 1.5-3 ℃/min, and preserving heat for 120-240 min.
9. The method for preparing a ceramic-stainless steel composite material according to claim 5, wherein the sintering in the step (3) is vacuum sintering, and gradient heating is adopted, and the specific process is as follows: in the first stage, heating from room temperature to 450 ℃ at a heating rate of 2-3 ℃/min, and preserving heat for 60-90 min; a second stage, heating from 450 ℃ to 750 ℃ at a heating rate of 3-4 ℃/min, and preserving heat for 60-90 min; in the third stage, heating from 750 ℃ to 1200 ℃ at a heating rate of 4-5 ℃/min, and preserving heat for 60-90 min; and in the fourth stage, heating from 1200 ℃ to 1375 ℃ at a heating rate of 1-2 ℃/min, and preserving heat for 120-240 min.
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