CN109180186B - Preparation method of bionic pearl layer MAX phase carbide ceramic matrix composite material - Google Patents
Preparation method of bionic pearl layer MAX phase carbide ceramic matrix composite material Download PDFInfo
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Abstract
The invention relates to a MAX phase ceramic matrix composite material, in particular to a method for preparing a MAX phase carbide ceramic matrix composite material of a bionic pearl layer. The method utilizes lamellar MAX powder as a brick block for constructing a stacking composite material, utilizes the orientation of liquid medium crystal growth in temperature gradient, obtains a lamellar solidification crystal ceramic composite structure similar to that in a natural pearl shell by freezing a liquid medium at low temperature, and then removes the medium crystal to obtain a continuous lamellar hole and a ceramic macromolecule blank with a lamellar structure. In the process of pressure sintering, high molecular polymer is used as a carbon source to react in situ to generate lamellar carbide. Finally, a nanometer or micrometer MAX photo layer is obtained to form a brick, and a carbide layer growing in situ in the MAX photo layer forms a long-range ordered brick-plaster structure of plaster imitated pearl layer materials. This structure, like the natural bioceramic, is highly resistant to external loads and crack propagation.
Description
Technical Field
The invention relates to a MAX phase ceramic matrix composite material, in particular to a preparation method of a MAX phase carbide ceramic matrix composite material of a bionic pearl layer.
Background
MAX phase ceramics (e.g. Ti)3SiC2、Ti2AlC、Nb2AlC, etc.) is a class of machinable ceramics with nano-ternary layered structures and a number of unique and superior properties, which has both ceramic and metallic properties. Such as: the ceramic material has high melting point, oxidation resistance, corrosion resistance, metal conductivity, machinability, damage tolerance, thermal shock resistance and other performances, and the nano ceramic has radiation damage resistance. Due to the unique ternary nano-layered structure, the fracture toughness of the ceramic is far higher than that of common engineering ceramics such as aluminum oxide, silicon carbide and the like. However, compared with metals, the strength and fracture toughness of the ceramics are far from sufficient, so that the development of a preparation method and a technology capable of improving the strength, fracture toughness and high-temperature mechanical properties of the ceramics by a bionics method are very important.
The nature forms a plurality of efficient and reasonable material components and structures in organisms in the evolution process of hundreds of millions of years, and the shell-type natural pearl layer material is one of the materials, has a unique brick-ash structure and consists of brick materials formed by 95% of flaky calcium carbonate layers in volume and ash materials formed by 5% of flaky calcium carbonate layers in volume. Although simple in composition, has very good overall performance through the fine combination of complex structures. The structure leads the material to have excellent mechanical property, and the natural pearl layer of the shell can reach multiple times of that of common calcium carbonate. In recent years, people enlighten from natural biological research, introduce a bionic structure design concept in material design, and realize the characteristics of high strength and high toughness of the material by simulating and transplanting a material structure formed by the efficient evolution of nature.
Disclosure of Invention
The invention aims to provide a preparation method of a MAX phase carbide ceramic matrix composite material of a bionic pearl layer, which solves the problems that the existing MAX phase carbide ceramic has poor strength and toughness and does not have a biological bionic structure and the like.
The technical scheme of the invention is as follows:
a preparation method of a bionic pearl layer MAX phase carbide ceramic matrix composite material comprises the steps of utilizing lamellar MAX powder as a brick block for building a stacked composite material, utilizing the orientation of liquid medium crystal growth in temperature gradient, obtaining a lamellar solidified crystal ceramic composite structure similar to that in a natural pearl shell by freezing a liquid medium at low temperature, and then removing the medium crystal to obtain a ceramic polymer blank with continuous lamellar holes and a lamellar structure; carbonizing the ceramic macromolecule blank, and generating lamellar carbide by in-situ reaction by using a macromolecule polymer as a carbon source; and (4) performing pressure sintering on the carbonized blank to obtain the MAX-phase carbide ceramic matrix composite material of the bionic pearl layer.
According to the preparation method of the bionic nacreous layer MAX phase carbide ceramic matrix composite material, the specification size of the lamellar MAX powder is 0.02-10 micrometers in thickness and 0.1-50 micrometers in width, the liquid medium crystal is water, tert-butyl alcohol or camphene, and the structure of the ceramic polymer blank with the continuous lamellar holes and the lamellar structure is as follows: the MAX powder is glued to form an oriented lamellar skeleton, and continuous lamellar holes are left between MAX powder lamellar layers after sublimation of liquid medium crystals.
The preparation method of the bionic pearl layer MAX phase carbide ceramic matrix composite material comprises the steps that the ceramic matrix composite material has a long-range ordered brick-plaster structure imitating a pearl layer material, a nanoscale or micron-sized MAX photo layer in the structure forms a brick, and a carbide layer growing in situ in the middle of the MAX photo layer forms plaster; wherein the MAX phase plate layer has the specification size of 0.02-10 microns in thickness and 0.1-50 microns in width; the specification and size of the carbide layer are 0.02-1 micron in thickness, and the weight ratio of the MAX phase sheet layer to the carbide layer is 5-50: 1.
the preparation method of the bionic nacre MAX phase carbide ceramic matrix composite material comprises the following steps:
(1) adding nanometer or micrometer lamellar MAX phase powder, organic glue and dispersant into solvent, mixing uniformly to form slurry, wherein the mixing method comprises ultrasonic dispersion, mechanical stirring or ball milling mixing;
(2) the mixed slurry is put into a mould, the mould is put into refrigeration equipment which can cause low gradient temperature for directional solidification, and the refrigeration temperature and the temperature gradient are determined by the physical and chemical solidification characteristics of the composite slurry;
(3) after solidification, drying the ceramic polymer blank after directional growth in a dryer, wherein the drying parameters are determined by the physical and chemical properties of the solvent;
(4) taking out the dried blank body and carrying out a carbonization process, wherein the carbonization is carried out in a vacuum furnace at the temperature of 400-600 ℃ and in the atmosphere of 10 DEG C-4Pa～10-2The carbonization time is 0.5-4 hours in a Pa vacuum environment;
(5) and (3) performing pressure sintering on the carbonized blank, wherein the sintering temperature is determined by the granularity of the adopted raw material powder and the type of the MAX phase.
In the preparation method of the MAX phase carbide ceramic matrix composite material of the bionic pearl layer, the solvent is water or other solvents which have a liquid state, can be solid when the temperature is reduced and can realize solid-state physical sublimation transformation; the organic glue is polyvinyl alcohol, polyethylene glycol or carboxymethyl cellulose, and the dispersant is sodium alkyl aryl sulfonate, alkylphenol polyethenoxy ether or ammonium polyacrylate.
The preparation method of the MAX phase carbide ceramic matrix composite material of the bionic pearl layer comprises the following steps of 30-60% of MAX phase powder, 2-10% of organic glue, 0.5-5% of dispersing agent and the balance of solvent in percentage by weight.
The preparation method of the bionic pearl layer MAX phase carbide ceramic matrix composite material adopts a hot pressing sintering method, a hot isostatic pressing sintering method or a discharge plasma sintering method.
According to the preparation method of the MAX-phase carbide ceramic matrix composite material of the bionic pearl layer, a hot pressing sintering method is that a blank body is directly placed into a graphite mold, hot pressing sintering is carried out in the graphite mold, the sintering temperature is 500-2000 ℃, the sintering pressure is 1-200 MPa, the heat preservation time is 10-3600 minutes, the heating rate is 1-100 ℃/minute, and sintering is carried out in a vacuum or argon atmosphere.
The hot isostatic pressing sintering method is that the blank is directly loaded into a hot isostatic pressing sheath, and then the sheath is vacuumized and sealed; and hot isostatic pressing sintering is carried out in the sheath, the sintering temperature is 500-2000 ℃, the sintering pressure is 1-800 MPa, the heat preservation time is 10-3600 minutes, the heating rate is 1-100 ℃/minute, and the sintering is carried out in a vacuum or argon atmosphere.
The preparation method of the MAX phase carbide ceramic matrix composite material of the bionic pearl layer is characterized in that a discharge plasma sintering method is to directly place a blank body into a sintering mold, and perform sintering under vacuum or argon atmosphere at the sintering temperature of 300-1800 ℃, the sintering pressure of 1-400 MPa, the heat preservation time of 5-600 minutes and the heating rate of 1-500 ℃/minute under the condition of applying large pulse current.
The design idea of the invention is as follows:
the preparation method disclosed by the invention is used for preparing the bionic nacreous layer MAX phase carbide ceramic matrix composite material by a simple and environment-friendly method, lamellar MAX powder is used as a brick block for constructing a stacking material, a liquid medium is frozen at a low temperature, a lamellar solidified crystal ceramic composite structure similar to that in a natural pearl shell is obtained by utilizing the orientation of the growth of a liquid medium crystal in a temperature gradient, and then the medium crystal is removed, so that a ceramic polymer blank with continuous lamellar holes and a lamellar structure is obtained. In the process of pressure sintering, high molecular polymer (namely organic glue, polyvinyl alcohol, polyethylene glycol or carboxymethyl cellulose and the like) is used as a carbon source to react in situ to generate lamellar carbide, and finally, a nanoscale or micron-sized MAX photo layer in the structure is obtained to form a brick, and a nano carbide layer growing in situ in the MAX photo layer forms a brick-plaster structure of a plaster imitated pearl layer material. This structure, like the natural bioceramic, is highly resistant to external loads and crack propagation.
The invention has the advantages and beneficial effects that:
(1) the invention has simple process route and preparation method, green, environment-friendly and pollution-free used raw materials and preparation method, and is easy to popularize in large area.
(2) The method of the invention is suitable for all MAX phase systems, and all MAX phase types of the bionic ceramic matrix composite materials can be prepared.
(3) The ceramic prepared by the invention is designed by adopting a bionics principle, the mechanical property is greatly improved, and the ceramic has excellent performance due to the bionic structure.
Drawings
FIG. 1 shows the microstructure of the sample obtained after freeze-drying.
FIG. 2 shows the sintered nacreous layer Ti3AlC2Fracture pictures of the/TiC nano composite material in the direction vertical to the sheet layer.
Detailed Description
For the purpose of promoting a further understanding of the objects, aspects and advantages of the present disclosure, reference should be made to the following detailed description and specific examples, which are to be read in connection with the accompanying drawings. It should also be noted that the examples described below are intended as illustrations of some of the operations and embodiments only, and not all of the possible embodiments. All technical methods which are within the scope of the claims of the invention are used and should belong to the protection scope of the invention.
Example 1
In this embodiment, the preparation method of the ceramic matrix composite of the MAX phase carbide of the bionic nacreous layer is as follows:
lamellar Ti with the particle size of 200 nm3AlC2100 g of powder, 5 g of polyvinyl alcohol with the molecular weight of 4000 and 2 g of dispersant ammonium polyacrylate are added into 200 g of deionized water, and the mixture is mechanically stirred and uniformly mixed. The slurry after simple mixing was placed in a 500mL polyurethane ball mill jar and 200 grams of polyurethane coated iron balls were added. And (3) mounting the ball milling tank on a planetary ball mill for ball milling, wherein the ball milling rotation speed is 380 r/min, taking out the slurry after ball milling for 10 hours, and sorting out ball milling beads for later use. And (3) putting the obtained slurry into a polytetrafluoroethylene mold, placing a copper plate at the bottom of the mold, introducing liquid nitrogen from the bottom of the copper plate at the flow rate of 5L/h, and finally completely freezing and molding the slurry and taking out. Putting the frozen and formed solid mixture into a freeze dryer, setting the freeze drying temperature at minus 50 ℃ and the vacuum degree at 10Pa, and taking out after freeze drying for 50 hours.
As shown in FIG. 1, the microstructure of the sample obtained after freeze-drying is a solid mixture of nano Ti3AlC2Powder and organic matter composition for curing and forming, wherein the nano Ti3AlC2The powder is agglomerated to form a lamella and an oriented tissue, the middle of the lamella is formed by continuous lamella holes, and the size of the holes continuously penetrating through the blank is 10-30 microns. Sintering the solid mixture in a vacuum hot-pressing sintering furnace at 1250 ℃ under 40MPa in a sintering atmosphere of 10-3And Pa vacuum condition. After sintering, a dense nacreous layer Ti is obtained3AlC2A TiC nano composite material.
As shown in FIG. 2, the nacreous layer Ti after sintering3AlC2The picture of the fracture of the/TiC nano composite material in the direction vertical to the sheet layer can be known as Ti3AlC2Has good orientation and is piled up in bricks, and the nano granular TiC is distributed on Ti3AlC2The brick space is in the shape of mud and ash, Ti3AlC2The specification size of the photo layer is 100-300 nanometers in thickness and 1-3 microns in width, and the specification size of the TiC layer is 100300 nm, Ti3AlC2And TiC in a weight ratio of 6: 1.
the room temperature material of the material has the compression strength of 2500MPa and the fracture toughness of 18-21 MPa1/2Much higher than that of common Ti3AlC27 to 8MPa.m1/2The fracture toughness value is that the high-temperature performance of the high-temperature-resistant Ti reaches 200MPa at 1100 ℃, and is far higher than that of common Ti3AlC2Strength of 100 MPa.
Example 2
In this embodiment, the preparation method of the ceramic matrix composite of the MAX phase carbide of the bionic nacreous layer is as follows:
lamellar Nb with the grain size of 220 nm2200 g of AlC powder, 6 g of polyvinyl alcohol with the molecular weight of 4000 and 3 g of ammonium polyacrylate serving as a dispersing agent are added into 250 g of camphene, and the mixture is mechanically stirred and uniformly mixed. The slurry after simple mixing was placed in a 500mL polyurethane ball mill jar and 250 grams of polyurethane coated iron balls were added. And (3) mounting the ball milling tank on a planetary ball mill for ball milling, wherein the ball milling rotation speed is 400 r/min, taking out the slurry after ball milling for 10 hours, and sorting out ball milling beads for later use. And (3) putting the obtained slurry into a polytetrafluoroethylene mold, placing a copper plate at the bottom of the mold, introducing liquid nitrogen from the bottom of the copper plate at the flow rate of 1L/h, and finally completely freezing and molding the slurry and taking out. Putting the frozen and formed solid mixture into a drying machine, setting the drying temperature at 25 ℃, setting the environment at one atmospheric pressure, taking out the solid mixture after drying for 10 hours, and obtaining the nano Nb2The AlC powder is agglomerated to form a lamella and an oriented structure, the middle of the lamella is formed by continuous lamella holes, and the size of the holes of the lamella is 20-50 microns. Sintering the solid mixture in a vacuum hot-pressing sintering furnace at 1350 deg.C and 40MPa in a sintering atmosphere of 10-3And Pa vacuum condition. After sintering, obtaining a compact pearl layer Nb2AlC/NbC nano composite material. Nb2The AlC has good orientation and is piled up in bricks, and the NbC in the form of nano particles is distributed in the Nb2The AlC bricks are in the shape of mud and ash, Nb2The specification size of the AlC phase layer is 150-320 nanometers in thickness and 1-3 micrometers in width, the specification size of the NbC layer is 100-300 nanometers, and Nb is2Weight of AlC and NbCThe proportion is 8: 1.
the room temperature material of the material has the compression strength of 260MPa and the fracture toughness of 18-21 MPa1/2Far higher than that of common Nb27-8 MPa.m of AlC1/2The fracture toughness value is that the high-temperature performance of the material reaches 450MPa at 1400 ℃, which is much higher than that of the common Nb2300MPa strength of AlC.
Claims (8)
1. A preparation method of a bionic pearl layer MAX phase carbide ceramic matrix composite material is characterized in that lamellar MAX powder is used as a brick block for constructing a stacked composite material, the orientation of liquid medium crystal growth in temperature gradient is utilized, a lamellar solidified crystal ceramic composite structure similar to that in a natural pearl shell is obtained by freezing a liquid medium at low temperature, and then the medium crystal is removed, so that a ceramic polymer blank with continuous lamellar holes and a lamellar structure is obtained; carbonizing the ceramic macromolecule blank, and generating lamellar carbide by in-situ reaction by using a macromolecule polymer as a carbon source; the carbonized blank is pressed and sintered to obtain the MAX phase carbide ceramic matrix composite material of the bionic pearl layer, and the composite material is Ti3AlC2TiC nano composite material or Nb2AlC/NbC nanocomposites;
the method comprises the following steps:
(1) adding nanometer or micrometer lamellar MAX phase powder, organic glue and dispersant into a liquid medium, and uniformly mixing to form slurry, wherein the mixing method is ultrasonic dispersion, mechanical stirring or ball milling mixing;
(2) the mixed slurry is put into a mould, the mould is put into refrigeration equipment which can cause low gradient temperature for directional solidification, and the refrigeration temperature and the temperature gradient are determined by the physical and chemical solidification characteristics of the composite slurry;
(3) after solidification, drying the ceramic polymer blank after directional growth in a dryer, wherein the drying parameters are determined by the physical and chemical properties of the liquid medium;
(4) taking out the dried blank body and carrying out a carbonization process, wherein the carbonization is carried out in a vacuum furnace at the temperature of 400-600 ℃ and in the atmosphere of 10 DEG C-4Pa～10-2The carbonization time is 0.5-4 hours in a Pa vacuum environment;
(5) carrying out pressure sintering on the carbonized blank body, wherein the sintering temperature is determined by the granularity of the adopted raw material powder and the type of the MAX phase;
the liquid medium is water, tert-butyl alcohol or camphene, the organic glue is polyvinyl alcohol, polyethylene glycol or carboxymethyl cellulose, and the dispersant is sodium alkyl aryl sulfonate, alkylphenol polyethenoxy ether or ammonium polyacrylate.
2. The method for preparing a MAX phase carbide ceramic matrix composite material of a bionic nacre layer according to claim 1, wherein the specification and size of the lamellar MAX powder are 0.02-10 microns in thickness and 0.1-50 microns in width, and the structure of the ceramic polymer blank of the continuous lamellar hole and lamellar structure is as follows: the MAX powder is glued to form an oriented lamellar skeleton, and continuous lamellar holes are left between MAX powder lamellar layers after sublimation of liquid medium crystals.
3. The method of claim 1, wherein the ceramic matrix composite has a long range ordered brick-mortar structure of a material like a pearl layer, wherein the nano or micro grade MAX photo layers form bricks and the in-situ grown carbide layer in the middle of the MAX photo layers forms mortar; wherein the MAX phase plate layer has the specification size of 0.02-10 microns in thickness and 0.1-50 microns in width; the specification and size of the carbide layer are 0.02-1 micron in thickness, and the weight ratio of the MAX phase sheet layer to the carbide layer is 5-50: 1.
4. the method for preparing a MAX phase carbide ceramic matrix composite material of a bionic nacre layer according to claim 1, wherein the weight percentage of MAX phase powder in the raw material is 30-60%, the weight percentage of organic glue is 2-10%, the weight percentage of dispersant is 0.5-5%, and the balance is liquid medium.
5. The method of making a biomimetic nacre MAX phase carbide ceramic matrix composite as recited in claim 1 wherein the pressure sintering is a hot pressing sintering process, a hot isostatic pressing sintering process, or a spark plasma sintering process.
6. The method for preparing a MAX phase carbide ceramic matrix composite material of a bionic nacre layer according to claim 5, wherein the hot pressing sintering method is to directly load the blank into a graphite mold, and to perform hot pressing sintering in the graphite mold, wherein the sintering temperature is 500-2000 ℃, the sintering pressure is 1-200 MPa, the heat preservation time is 10-3600 minutes, the heating rate is 1-100 ℃/minute, and the sintering is performed in a vacuum or argon atmosphere.
7. The process for preparing a bionic nacre MAX phase carbide ceramic matrix composite as claimed in claim 5 wherein the hot isostatic pressing sintering process is carried out by directly placing the green body in a hot isostatic pressing capsule, then evacuating the capsule and sealing; and hot isostatic pressing sintering is carried out in the sheath, the sintering temperature is 500-2000 ℃, the sintering pressure is 1-800 MPa, the heat preservation time is 10-3600 minutes, the heating rate is 1-100 ℃/minute, and the sintering is carried out in a vacuum or argon atmosphere.
8. The method for preparing a MAX phase carbide ceramic matrix composite material of a bionic nacre layer according to claim 5, wherein the spark plasma sintering method is to directly put the blank into a sintering mold, and sinter the blank under the condition of applying a large pulse current, wherein the sintering temperature is 300-1800 ℃, the sintering pressure is 1-400 MPa, the heat preservation time is 5-600 minutes, the heating rate is 1-500 ℃/minute, and the sintering is carried out under the vacuum or argon atmosphere.
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