CN111393167B - MAX phase composite material and preparation method thereof - Google Patents

Abstract

The invention discloses a MAX phase composite material and a preparation method thereof. The preparation method of the MAX phase composite material includes: mixing the MAX phase and a ceramic precursor, solidifying and molding, then sintering at 500-1300° C. in an inert atmosphere, and then post-processing to obtain the MAX phase composite material. The method provided by the present invention uses the ceramic precursor to shape the MAX phase for the first time, realizes the sintering of the MAX phase under the condition of low temperature and normal pressure, and the obtained MAX phase composite material has near-net shape forming, easy processing, high strength, high resistance Corrosion and oxidation resistance and other characteristics, and the composite material has broad application prospects in the fields of nuclear energy, aviation, high-energy-consuming industries and the environment, and national defense.

Description

A kind of MAX phase composite material and preparation method thereof

technical field

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

Background technique

MAX phase material is a new type of machinable ceramic material, which is called cermet material because it has some excellent properties of metal material and ceramic material. The MAX phase is a nano-layered ternary compound with a hexagonal lattice structure, and the molecular formula is M _n+1 AX _n , where M is a pre-transition metal element of III B, IV B, VB, and VI B groups, and A is mainly IIIA and Group IVA element, X is carbon and/or nitrogen, and n=1-3. The unit cell of the MAX phase is formed by alternately stacking Mn ₊₁ X _n units and A atomic planes, n=1, 2 or 3, usually abbreviated as 211, 312 and 413 phases. At present, there are more than 70 kinds of MAX phases synthesized. . Such materials have a special nano-layered crystal structure, and they also have good electrical conductivity, high toughness, good self-lubrication and other properties; and such materials are used in electrode materials, high-temperature structural materials, high-temperature Heat-generating materials and chemical anti-corrosion materials have also begun to be widely used. The series of excellent properties of the MAX phase make the ceramic material have a very broad prospect in the future use, and it has also attracted extensive attention from researchers around the world on the MAX phase. The traditional MAX phase sintering method adopts hot isostatic pressing (HIP), hot pressing sintering (HP), spark plasma sintering (SPS), etc. These preparation methods generally need to be carried out under high temperature and high pressure.

SUMMARY OF THE INVENTION

The main purpose of the present invention is to provide a MAX phase composite material and a preparation method thereof, so as to overcome the deficiencies of the prior art.

The method provided by the invention does not require high temperature and high pressure, and at the same time, the mechanical properties such as the hardness of the material can be improved.

In order to realize the foregoing invention purpose, the technical scheme adopted in the present invention includes:

The embodiment of the present invention provides a preparation method of a MAX phase composite material, which includes:

The MAX phase and the ceramic precursor are mixed and solidified to form, and then sintered at 500-1300° C. in an inert atmosphere, and then post-treated to obtain a MAX phase composite material.

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

Compared with the prior art, the beneficial effects of the present invention are:

(1) The hybrid molding of the MAX phase and the ceramic precursor is realized for the first time in the present invention, and the synthesis method is simple and universal;

(2) In the present invention, the sintering of MAX under the condition of low temperature and normal pressure is realized for the first time, and the synthesis method is simple and universal;

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

(4) The MAX phase composite material prepared by the present invention has both the characteristics of metal and ceramics, and has the characteristics of high strength, corrosion resistance, oxidation resistance and the like.

Description of drawings

In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the following briefly introduces the accompanying drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only These are some embodiments described in this application. For those of ordinary skill in the art, other drawings can also be obtained based on these drawings without any creative effort.

Fig. 1 is the XRD pattern of the MAX phase composite material in Example 1 of the present invention;

2 is a SEM image of the MAX phase composite material in Example 1 of the present invention;

3a-3c are line scan diagrams of the MAX phase composite material in Example 1 of the present invention;

4a-4f are the element distribution diagrams of the MAX phase composite material in Example 1 of the present invention;

5 is the XRD pattern of the MAX phase composite material in Example 2 of the present invention;

6 is a SEM image of the MAX phase composite material in Example 2 of the present invention;

7a-7c are line scan diagrams of the MAX phase low-temperature sintering method Ti ₃ AlC ₂ in Example 2 of the present invention;

8a-8f are the element distribution diagrams of the MAX phase composite material in Example 2 of the present invention.

Detailed ways

In view of the defects of the prior art, the inventor of the present invention has been able to propose the technical solution of the present invention after long-term research and extensive practice. The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the present invention examples, but not all examples. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

One aspect of the embodiments of the present invention provides a method for preparing a MAX phase composite material, which includes: mixing and solidifying a MAX phase and a ceramic precursor, then sintering at 500-1300° C. in an inert atmosphere, and then post-processing Processed to obtain a MAX phase composite.

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

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

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

In some specific embodiments, the ceramic precursors include any one or a combination of two or more of organosilicon ceramic precursors, organoboron ceramic precursors, and organonitrogen ceramic precursors, but are not limited thereto.

Further, the ceramic precursor includes any one or a combination of two or more of polycarbosilane, polysilazane, polysiloxane, polysilaborane, polysilaborazane, and polysilane, and not limited to this.

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

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

In some specific embodiments, the molecular formula of the MAX phase is Mn ₊₁ AX _n , wherein M is selected from any one or a combination of two or more elements of group III B, IV B, VB, and VI B , A is selected from any one or a combination of two or more elements in group IIIA and IVA, X is any one or a combination of two in C and N, and n is 1, 2, 3 or 4.

Further, the X is C _x N _y , wherein x+y=1, 2, 3 or 4.

Further, the MAX phase includes any one or two or more of Ti ₂ AlC, Ti ₃ SiC ₂ , V ₂ AlC, Ti ₃ AlC ₂ , Cr ₂ AlC, Nb ₄ AlC ₃ , and V _{2 AsC} combination, without limitation.

Further, the MAX phase has a hexagonal crystal structure, the space group is P63/mmc(194), and the unit cell is formed by alternately stacking Mn ₊₁ X _n units and A-layer atoms.

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

Further, the powder particle size of the MAX phase is 10 nm˜200 μm.

In some specific embodiments, the post-treatment includes: after the sintering treatment is completed, rough grinding and polishing the surface of the obtained product, and then ultrasonic and drying treatment to obtain the MAX phase composite material.

Further, abrasive cloth is used for the rough grinding treatment, and is not limited to this.

Further, a polishing cloth is used for the rough grinding treatment, and is not limited to this.

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

The technical solution of the present invention will be described in further detail below with reference to several preferred embodiments and accompanying drawings. The scope of protection is not limited to the following examples.

The experimental materials used in the following examples can be purchased from conventional biochemical reagent companies unless otherwise specified.

Example 1

In this embodiment, the selected MAX phase material is Ti ₃ AlC ₂ powder material, the ceramic precursor is SiOC ceramic precursor polysiloxane, and the preparation method of the MAX phase composite material is as follows:

(1) mixing Ti ₃ AlC ₂ powder and SiOC ceramic precursor polysiloxane according to a mass ratio of 4:6, fully stirring and mixing the above materials to obtain a mixed product;

(2) The mixture is placed in a polytetrafluoroethylene mold, put into an oven for curing, taken out and placed in a tube furnace for sintering, the reaction conditions are: 700 ° C, 240min, argon protection, wait for the tube furnace After the temperature has dropped to room temperature, take out the sample;

(3) Preliminary rough grinding of the sample with sandpaper, followed by polishing with a polishing cloth, and washing of the sample with deionized water and ethanol: put the sample into a beaker, add deionized water, ultrasonically clean for 15 min, and pour out the deionized water, Then poured into ethanol, and after ultrasonic cleaning for 15 minutes, the sample was taken out and put into an oven at 50° C., and taken out after 12 hours to obtain the MAX phase composite material.

Performance characterization: Figure 1 is the XRD pattern of the MAX phase composite material in Example 1. It can be seen from the XRD pattern that the typical characteristic peaks of the Ti ₃ AlC ₂ phase appear in the obtained phase, indicating that the sintered sample is mainly Ti ₃ AlC ₂ ; Fig. 2 is the SEM image of the MAX phase composite material in Example 1, it can be seen that the particles of Ti ₃ AlC ₂ are combined together, indicating that the MAX phase has been combined and formed; Figs. 3a-3c It is a line scan diagram of the MAX phase composite material in Example 1. It can be seen from the figure that Ti ₃ AlC ₂ and SiOC ceramics are combined to form an intermediate phase, indicating that the molding of the MAX phase is not a simple physical molding; Figure 4a- 4f is the element distribution diagram of the MAX phase composite material in Example 1. It can be seen from the figure that the Ti element and Si element have a phenomenon of mutual diffusion, indicating that Ti ₃ AlC ₂ and SiOC ceramics have the formation of an intermediate phase; their Vickers hardness is 478.

Example 2

In this embodiment, the selected MAX phase material is Ti ₃ AlC ₂ powder material, the ceramic precursor is SiOC ceramic precursor polysiloxane, and the preparation method of the MAX phase composite material is as follows:

(1) mixing Ti ₃ AlC ₂ powder and SiOC ceramic precursor polysiloxane according to a mass ratio of 5:5, and sufficiently stirring and mixing the above materials to obtain a mixed product;

(2) The mixture is placed in a polytetrafluoroethylene mold, put into an oven for curing, taken out and placed in a tube furnace for sintering, the reaction conditions are: 700 ° C, 240min, argon protection, wait for the tube furnace After the temperature dropped to room temperature, the reaction product was taken out;

(3) Preliminary rough grinding of the sample with sandpaper, followed by polishing with a polishing cloth, and washing of the sample with deionized water and ethanol: put the sample into a beaker, add deionized water, ultrasonically clean for 15 min, and pour out the deionized water, Then poured into ethanol, and after ultrasonic cleaning for 15 minutes, the sample was taken out and put into an oven at 50° C., and taken out after 12 hours to obtain the MAX phase composite material.

Performance characterization: Figure 5 is the XRD pattern of the MAX phase composite material in Example 2. It can be seen from the XRD pattern that the obtained phase is still the typical characteristic peak of the Ti ₃ AlC ₂ phase, indicating that the sintered sample is mainly Ti ₃ AlC ₂ ; Fig. 6 is the SEM image of the MAX phase composite material in Example 2, it can be seen from the figure that the particles of Ti ₃ AlC ₂ are combined together, indicating that the MAX phase has been combined together to form; The line scan diagram of Ti ₃ AlC ₂ in the low-temperature sintering method of MAX phase in Example 2, it can be seen from the figure that Ti ₃ AlC ₂ is combined with SiOC ceramics to form an intermediate phase, indicating that the forming of MAX phase is not a simple physical forming; Figures 8a-8f are the element distribution diagrams of the MAX phase composite material in Example 2. It can be seen from the figures that there is a phenomenon of mutual diffusion between the Ti element and the Si element, indicating that Ti ₃ AlC ₂ and SiOC ceramics have an intermediate phase formation; The Vickers hardness is 352.

Example 3

In this embodiment, the selected MAX phase material is Ti ₃ SiC ₂ powder material, the ceramic precursor is SiC precursor polycarbosilane, and the preparation method of the MAX phase composite material is as follows:

(1) mix Ti ₃ SiC ₂ powder and SiC precursor polycarbosilane according to a mass ratio of 1:19, and sufficiently stir and mix the above materials to obtain a mixed product;

(2) Put the mixture in a polytetrafluoroethylene mold, put it in an oven for curing at 100 °C, take it out and put it into a tube furnace for sintering, the reaction conditions are: 1000 °C, 6h, argon protection, wait for After the temperature of the tube furnace is lowered to room temperature, the reaction product is taken out;

(3) Preliminary rough grinding of the sample with sandpaper, followed by polishing with a polishing cloth, and washing of the sample with deionized water and ethanol: put the sample into a beaker, add deionized water, ultrasonically clean for 15 min, and pour out the deionized water, Then poured into ethanol, and after ultrasonic cleaning for 15 minutes, the sample was taken out and put into an oven at 50° C., and taken out after 12 hours to obtain the MAX phase composite material.

Example 4

In this embodiment, the selected MAX phase material is Cr ₂ AlC powder material, and the ceramic precursor is SiBCN precursor polysilaborane. The preparation method of the MAX phase composite material is as follows:

(1) mixing Cr ₂ AlC powder and SiBCN precursor polysilaborane according to a mass ratio of 1:10, and sufficiently stirring and mixing the above materials to obtain a mixed product;

(2) Put the mixture in a polytetrafluoroethylene mold, put it in an oven for curing at 200°C, take it out and put it into a tube furnace for sintering, the reaction conditions are: 800°C, 60min, argon protection, wait for After the temperature of the tube furnace is lowered to room temperature, the reaction product is taken out;

(3) Preliminary rough grinding of the sample with sandpaper, followed by polishing with a polishing cloth, and washing of the sample with deionized water and ethanol: put the sample into a beaker, add deionized water, ultrasonically clean for 15 min, and pour out the deionized water, Then poured into ethanol, and after ultrasonic cleaning for 15 minutes, the sample was taken out and put into an oven at 50° C., and taken out after 12 hours to obtain the MAX phase composite material.

Example 5

In this embodiment, the selected MAX phase material is V ₂ AlC powder material, the ceramic precursor is SiC precursor polycarbosilane, and the preparation method of the MAX phase composite material is as follows:

(1) V ₂ AlC powder and SiC precursor polycarbosilane are mixed according to a mass ratio of 19:1, and the above materials are fully stirred and mixed to obtain a mixed product;

(2) Put the mixture in a polytetrafluoroethylene mold, put it in an oven for curing at 150°C, take it out and put it into a tube furnace for sintering, the reaction conditions are: 1200°C, 2h, argon protection, wait for After the temperature of the tube furnace is lowered to room temperature, the reaction product is taken out;

(3) Preliminary rough grinding of the sample with sandpaper, followed by polishing with a polishing cloth, and washing of the sample with deionized water and ethanol: put the sample into a beaker, add deionized water, ultrasonically clean for 15 min, and pour out the deionized water, Then poured into ethanol, and after ultrasonic cleaning for 15 minutes, the sample was taken out and put into an oven at 50° C., and taken out after 12 hours to obtain the MAX phase composite material.

In addition, the inventors of the present application also carried out experiments with other raw materials, technological operations and technological conditions mentioned in this specification with reference to the foregoing examples, and all obtained satisfactory results.

The aspects, embodiments, features, and examples of the present invention are to be considered in all respects illustrative and not intended to limit 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 sections in this application is not meant to limit the invention; each section is applicable to any aspect, embodiment or feature of the invention.

Throughout this specification, where a composition is described as having, comprising or including particular components, or where a process is described as having, comprising or including particular process steps, it is contemplated that the compositions of the present teachings will also be substantially The above consists of or consists of the recited components, and the processes taught herein also consist essentially of, or consist of, the recited process steps.

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

Although the present invention has been described with reference to illustrative embodiments, those skilled in the art will understand that various other changes, omissions and/or additions and the like may be made without departing from the spirit and scope of the invention Effects replace elements of the described embodiments. 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 not intended herein to limit the invention to the particular embodiments disclosed for carrying out the invention, but it is intended that this invention include all embodiments falling within the scope of the appended claims. Furthermore, unless specifically stated, any use of the terms first, second, etc. does not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.

Claims (5)

1. a preparation method of MAX phase composite material, is characterized in that comprising: The MAX phase and the ceramic precursor are mixed and placed in a polytetrafluoroethylene mold, placed in an oven and cured at 100-200 °C, then sintered at 700-1000 °C in an inert atmosphere, and then post-treated to obtain MAX phase composite material; Wherein, the ceramic precursor is a liquid ceramic precursor; the ceramic precursor is selected from any one of SiOC ceramic precursor polysiloxane, SiC precursor polycarbosilane, SiBCN precursor polysilaborane or A combination of two or more types; the viscosity of the mixture obtained by mixing the MAX phase and the ceramic precursor is 10cp to 250000cp; 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+1 AX _n , wherein M is selected from any one or a combination of two or more of group III B, IV B, VB, VI B elements, and A is selected from III A, IV A Any one or a combination of two or more elements in the group, X is selected from C and/or N, and n is 1, 2, 3 or 4; The MAX phase is selected from any one or a combination of two or more of Ti ₂ AlC, Ti ₃ SiC ₂ , V ₂ AlC, Ti ₃ AlC ₂ , Cr ₂ AlC, and Nb ₄ ALC ₃ . 2 . The preparation method according to claim 1 , wherein the X is C _x N _y , wherein x+y=1, 2, 3 or 4. 3 . 3 . The preparation method according to claim 1 , wherein: the MAX phase is a powder material; and the powder particle size of the MAX phase is 10 nm˜200 μm. 4 . 4 . The preparation method according to claim 1 , wherein the post-treatment comprises: after the sintering treatment is completed, rough grinding, polishing, ultrasonication and drying are performed on the surface of the obtained product to obtain The MAX phase composite material. 5. The MAX phase composite produced by the method of any one of claims 1-4.

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