CN111393167B

CN111393167B - MAX phase composite material and preparation method thereof

Info

Publication number: CN111393167B
Application number: CN202010216651.XA
Authority: CN
Inventors: 宋育杰; 张健宁; 黄庆; 陈科; 何流; 黄政仁
Original assignee: Hangzhou Bay Research Institute Of Ningbo Institute Of Materials; Ningbo Institute of Material Technology and Engineering of CAS
Current assignee: Hangzhou Bay Research Institute Of Ningbo Institute Of Materials; Ningbo Institute of Material Technology and Engineering of CAS
Priority date: 2020-03-25
Filing date: 2020-03-25
Publication date: 2022-04-19
Anticipated expiration: 2040-03-25
Also published as: CN111393167A

Abstract

The invention discloses a MAX phase composite material and a preparation method thereof. The preparation method of the MAX phase composite material comprises the following steps: mixing the MAX phase and the ceramic precursor, curing and molding, sintering at 500-1300 ℃ in an inert atmosphere, and performing post-treatment to obtain the MAX phase composite material. The method provided by the invention firstly uses the ceramic precursor to form the MAX phase, realizes the sintering of the MAX phase under the conditions of low temperature and normal pressure, and the obtained MAX phase composite material has the characteristics of near-net-shape forming, easy processing, high strength, corrosion resistance, oxidation resistance and the like, and meanwhile, the composite material has wide application prospects in the fields of nuclear energy, aviation, high-energy-consumption industries and environments, national defense and the like.

Description

MAX phase composite material and preparation method thereof

Technical Field

The invention belongs to the technical field of composite materials, and particularly relates to a MAX phase composite material and a preparation method thereof.

Background

The MAX phase material is a new type of machinable ceramic material and is called cermet material due to its combination of some of the respective good properties of both metal and ceramic materials. MAX phase is a nano-layered ternary compound with a hexagonal lattice structure and a molecular formula of M_n+1AX_nWherein M is an early transition metal element of groups III B, IV B, V B and VI B, A is mainly an element of groups IIIA and IVA, X is carbon and/or nitrogen, and n is 1-3. The unit cell of MAX phase is formed by M_n+1X_nThe units are stacked alternately with the a atom plane, n is 1, 2 or 3, usually abbreviated as 211, 312 and 413 phases, and there are about 70 more MAX phases synthesized at present. The material has a special nano-layered crystal structure, and therefore, the material has the performances of good conductivity, higher toughness, good self-lubricating property and the like; and the material also begins to be widely applied to the aspects of electrode materials, high-temperature structural materials, high-temperature heating materials, chemical anticorrosive materials and the like. The series of excellent properties of the MAX phase make the ceramic material have a very wide prospect in future use, and meanwhile, the ceramic material also attracts the extensive attention of researchers all over the world to the MAX phase. The conventional MAX phase sintering method adopts a hot isostatic pressing method (HIP), a hot pressing sintering method (HP), a spark plasma sintering method (SPS) and the like, and the preparation methods generally need to be carried out under high temperature and high pressure.

Disclosure of Invention

The invention mainly aims to provide a MAX phase composite material and a preparation method thereof, so as to overcome the defects of the prior art.

The method provided by the invention does not need high temperature and high pressure, and can improve the mechanical properties such as hardness of the material.

In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:

the embodiment of the invention provides a preparation method of an MAX phase composite material, which comprises the following steps:

mixing the MAX phase and the ceramic precursor, curing and molding, sintering at 500-1300 ℃ in an inert atmosphere, and performing post-treatment to obtain the MAX phase composite material.

The embodiment of the invention also provides the MAX phase composite material prepared by the method.

Compared with the prior art, the invention has the beneficial effects that:

(1) the method realizes the mixing molding of the MAX phase and the ceramic precursor for the first time, and has simple synthetic method and universality;

(2) the MAX sintering method is realized under the conditions of low temperature and normal pressure for the first time, and the synthesis method is simple and has universality;

(3) the invention realizes the mixing of the MAX phase and the ceramic precursor for the first time, has fluidity and viscosity of 10-250000 cp, and realizes the molding of the MAX phase in a complex shape;

(4) the MAX phase composite material prepared by the method has the characteristics of metal and ceramic, and has the characteristics of high strength, corrosion resistance, oxidation resistance and the like.

Drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.

FIG. 1 is an XRD pattern of a MAX phase composite material in example 1 of the present invention;

FIG. 2 is an SEM photograph of a MAX phase composite material in example 1 of the present invention;

FIGS. 3a-3c are line scans of MAX phase composites in example 1 of the present invention;

FIGS. 4a-4f are elemental distribution diagrams of MAX phase composite materials in example 1 of the present invention;

FIG. 5 is an XRD pattern of a MAX phase composite material in example 2 of the present invention;

FIG. 6 is an SEM photograph of a MAX phase composite material in example 2 of the present invention;

FIGS. 7a 7c are the MAX phase low temperature sintering method Ti in example 2 of the present invention₃AlC₂A line scan of (a);

figures 8a-8f are elemental distribution diagrams of a MAX phase composite according to example 2 of the present invention.

Detailed Description

In view of the defects of the prior art, the inventor of the present invention has long studied and largely practiced to propose the technical solution of the present invention, which will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

One aspect of an embodiment of the present invention provides a method for preparing a MAX-phase composite material, including: mixing the MAX phase and the ceramic precursor, curing and molding, sintering at 500-1300 ℃ in an inert atmosphere, and performing post-treatment to obtain the MAX phase composite material.

Further, the sintering treatment temperature is 500-1200 ℃, and the time is 0-6 h.

Further, the inert atmosphere includes an argon atmosphere, and is not limited thereto.

In some more specific embodiments, the mass ratio of the MAX phase to the ceramic precursor is 1-19: 1-19.

In some more specific embodiments, the ceramic precursor includes any one or a combination of two or more of an organosilicon ceramic precursor, an organoboron ceramic precursor, and an organonitrogen ceramic precursor, without limitation.

Further, the ceramic precursor includes any one or a combination of two or more of polycarbosilane, polysilazane, polysiloxane, polysilaborocarbane, and polysilane, but is not limited thereto.

Further, the polysiloxane includes any one or a combination of two or more of SiOC ceramic precursor polysiloxane, SiC precursor polycarbosilane, SiBCN precursor polyborosilazane, and is not limited thereto.

Further, the ceramic precursor includes a liquid or solid ceramic precursor, and is not limited thereto.

In some more specific embodiments, the MAX phase is of the formula M_n+1AX_nWherein M is selected from any one or the combination of more than two of III B, IV B, V B and VI B group elements, A is selected from any one or the combination of more than two of IIIA and IVA group elements, X is any one or the combination of more than two of C, N, and n is 1, 2, 3 or 4.

Further, X is C_xN_yWherein x + y is 1, 2, 3 or 4.

Further, the MAX phase comprises Ti₂AlC、Ti₃SiC₂、V₂AlC、Ti₃AlC₂、Cr₂AlC、Nb₄AlC₃、V₂A_sAny one or a combination of two or more of C, and is not limited thereto.

Further, the MAX phase has a hexagonal structure with a space group of P63/mmc (194) and a unit cell consisting of M_n+1X_nThe unit and the A layer atoms are alternately stacked.

Further, the MAX phase is a powder material, and is not limited thereto.

Furthermore, the particle size of the MAX phase powder is 10 nm-200 μm.

In some more specific embodiments, the post-treatment comprises: and after the sintering treatment is finished, performing coarse grinding and polishing treatment on the surface of the obtained product, and performing ultrasonic treatment and drying treatment to obtain the MAX phase composite material.

Further, the rough grinding process is performed using a sand cloth, but is not limited thereto.

Further, the rough grinding process is performed using a polishing cloth, and is not limited thereto.

Further, the ultrasonic treatment comprises ultrasonic treatment in water and ultrasonic treatment in ethanol.

The technical solutions of the present invention are further described in detail below with reference to several preferred embodiments and the accompanying drawings, which are implemented on the premise of the technical solutions of the present invention, and a detailed implementation manner and a specific operation process are provided, but the scope of the present invention is not limited to the following embodiments.

The experimental materials used in the examples used below were all available from conventional biochemical reagents companies, unless otherwise specified.

Example 1

In this embodiment, the selected MAX phase material is Ti₃AlC₂The powder material, the ceramic precursor is SiOC ceramic precursor polysiloxane, the MAX phase composite material preparation method is as follows:

(1) mixing Ti₃AlC₂Mixing the powder and SiOC ceramic precursor polysiloxane according to the mass ratio of 4: 6, and fully stirring and mixing the materials to obtain a mixed product;

(2) placing the mixture into a polytetrafluoroethylene mold, placing the polytetrafluoroethylene mold into a drying oven for curing, taking out the polytetrafluoroethylene mold, and placing the polytetrafluoroethylene mold into a tubular furnace for sintering, wherein the reaction conditions are as follows: at 700 ℃, 240min under the protection of argon, and taking out a sample after the temperature of the tube furnace is reduced to room temperature;

(3) the samples were initially coarsely ground with sandpaper, then polished with a polishing cloth, washed with deionized water and ethanol: putting the sample into a beaker, adding deionized water, carrying out ultrasonic cleaning for 15min, pouring the deionized water, pouring ethanol, carrying out ultrasonic cleaning for 15min, taking out the sample, putting the sample into a 50 ℃ oven, and taking out the sample after 12h to obtain the MAX phase composite material.

And (3) performance characterization: FIG. 1 is the XRD pattern of the MAX phase composite material of example 1, from which it can be seen that the resulting phase again appears as Ti₃AlC₂Characteristic peaks typical of the phases, indicating whether the sintered sample is predominantly Ti or not₃AlC₂(ii) a FIG. 2 is an SEM photograph of the MAX phase composite material of example 1, in which Ti can be seen₃AlC₂The particles of (a) are bonded together, indicating that the MAX phase has been bonded together and shaped; FIGS. 3a-3c are line scans of the MAX phase composite material of example 1, in which Ti can be seen₃AlC₂The material is combined with SiOC ceramic to form an intermediate phase, which shows that the MAX phase is not formed by pure physical forming; figures 4a-4f are elemental distribution diagrams of the MAX phase composite of example 1,in the figure, there is a phenomenon that Ti element and Si element are diffused into each other, which is an explanation of Ti₃AlC₂Formation of an intermediate phase with the SiOC ceramic; the Vickers hardness is 478.

Example 2

(1) mixing Ti₃AlC₂Mixing the powder and SiOC ceramic precursor polysiloxane according to the mass ratio of 5: 5, and fully stirring and mixing the materials to obtain a mixed product;

(2) placing the mixture into a polytetrafluoroethylene mold, placing the polytetrafluoroethylene mold into a drying oven for curing, taking out the polytetrafluoroethylene mold, and placing the polytetrafluoroethylene mold into a tubular furnace for sintering, wherein the reaction conditions are as follows: at 700 ℃, 240min under the protection of argon, and taking out a reaction product after the temperature of the tube furnace is reduced to room temperature;

And (3) performance characterization: FIG. 5 is the XRD pattern of the MAX phase composite material of example 2, from which it can be seen that the resulting phase again appears as Ti₃AlC₂Characteristic peaks typical of the phases, indicating whether the sintered sample is predominantly Ti or not₃AlC₂(ii) a FIG. 6 is an SEM photograph of the MAX phase composite material of example 2, in which Ti can be seen₃AlC₂The particles of (a) are bonded together, indicating that the MAX phase has been bonded together and shaped; FIGS. 7a-7c show the low temperature sintering method of MAX phase Ti in example 2₃AlC₂Line scan of (A), in which Ti can be seen₃AlC₂The material is combined with SiOC ceramic to form an intermediate phase, which shows that the MAX phase is not formed by pure physical forming; FIGS. 8a-8f are the elemental distribution diagrams of the MAX phase composite of example 2, from which T can be seenThe fact that the i element and the Si element have an interdiffusion phenomenon indicates that Ti is present₃AlC₂Formation of an intermediate phase with the SiOC ceramic; the Vickers hardness is 352.

Example 3

In this embodiment, the selected MAX phase material is Ti₃SiC₂The preparation method of the MAX phase composite material comprises the following steps:

(1) mixing Ti₃SiC₂Mixing the powder and SiC precursor polycarbosilane according to the mass ratio of 1: 19, and fully stirring and mixing the materials to obtain a mixed product;

(2) placing the mixture into a polytetrafluoroethylene mold, placing the polytetrafluoroethylene mold into an oven to be cured at 100 ℃, taking out the polytetrafluoroethylene mold and placing the polytetrafluoroethylene mold into a tubular furnace to be sintered, wherein the reaction conditions are as follows: at 1000 ℃ for 6h, under the protection of argon, taking out a reaction product after the temperature of the tube furnace is reduced to room temperature;

Example 4

In this embodiment, the selected MAX phase material is Cr₂The preparation method of the MAX phase composite material comprises the following steps:

(1) mixing Cr₂Mixing AlC powder and SiBCN precursor polyborocarbone according to the mass ratio of 1: 10, and fully stirring and mixing the materials to obtain a mixed product;

(2) placing the mixture into a polytetrafluoroethylene mold, placing the polytetrafluoroethylene mold into an oven for curing at 200 ℃, taking out the polytetrafluoroethylene mold, and placing the polytetrafluoroethylene mold into a tubular furnace for sintering, wherein the reaction conditions are as follows: at 800 ℃ for 60min, under the protection of argon, taking out a reaction product after the temperature of the tube furnace is reduced to room temperature;

Example 5

In this embodiment, the MAX phase material is V₂The preparation method of the MAX phase composite material comprises the following steps:

(1) will V₂Mixing AlC powder and SiC precursor polycarbosilane according to the mass ratio of 19: 1, and fully stirring and mixing the materials to obtain a mixed product;

(2) placing the mixture into a polytetrafluoroethylene mold, placing the polytetrafluoroethylene mold into a drying oven for curing at 150 ℃, taking out the polytetrafluoroethylene mold, and placing the polytetrafluoroethylene mold into a tubular furnace for sintering, wherein the reaction conditions are as follows: at 1200 ℃, 2 hours, under the protection of argon, and taking out a reaction product after the temperature of the tube furnace is reduced to room temperature;

In addition, the inventors of the present invention have also made experiments with other materials, process operations, and process conditions described in the present specification with reference to the above examples, and have obtained preferable results.

The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.

The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.

Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.

It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.

While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims

1. A method of preparing a MAX phase composite, comprising:

mixing the MAX phase and the ceramic precursor, placing the mixture into a polytetrafluoroethylene mold, placing the mold into an oven, curing and molding at 100-200 ℃, sintering at 700-1000 ℃ in an inert atmosphere, and performing post-treatment to obtain the MAX phase composite material;

wherein the ceramic precursor is a liquid ceramic precursor; the ceramic precursor is selected from any one or the combination of more than two of SiOC ceramic precursor polysiloxane, SiC precursor polycarbosilane and SiBCN precursor polyborosilazane; the viscosity of a mixture obtained by mixing the MAX phase and the ceramic precursor is 10-250000 cp;

the mass ratio of the MAX phase to the ceramic precursor is 1-19: 1-19;

the molecular formula of the MAX phase is M_n+1AX_nWherein M is selected from any one or the combination of more than two of III B, IV B, V B and VI B group elements, A is selected from any one or the combination of more than two of III A and IV A group elements, X is selected from C and/or N, and N is 1, 2, 3 or 4;

the MAX phase is selected from Ti₂AlC、Ti₃SiC₂、V₂AlC、Ti₃AlC₂、Cr₂AlC、Nb₄ALC₃Any one or a combination of two or more of them.

2. The method of claim 1, wherein: x is C_xN_yWherein x + y is 1, 2, 3 or 4.

3. The method of claim 1, wherein: the MAX phase is a powder material; the particle size of the MAX phase powder is 10 nm-200 μm.

4. The method of claim 1, wherein the post-treating comprises: and after the sintering treatment is finished, performing coarse grinding, polishing, ultrasonic treatment and drying treatment on the surface of the obtained product to obtain the MAX phase composite material.

5. A MAX phase composite material obtainable by the process of any one of claims 1 to 4.