CN112479718A

CN112479718A - Ti3SiC2MAX phase interface layer modified SiC/SiC composite material and preparation method thereof

Info

Publication number: CN112479718A
Application number: CN202011314136.1A
Authority: CN
Inventors: 宋环君; 于艺; 金鑫; 刘伟; 李晓东; 于新民; 刘俊鹏; 裴雨辰
Original assignee: Aerospace Research Institute of Materials and Processing Technology
Current assignee: Aerospace Research Institute of Materials and Processing Technology
Priority date: 2020-11-20
Filing date: 2020-11-20
Publication date: 2021-03-12
Anticipated expiration: 2040-11-20
Also published as: CN112479718B

Abstract

The invention relates to a Ti₃SiC₂A preparation method of MAX phase interface layer modified SiC/SiC composite material belongs to the field of aerospace material preparation process. The invention adopts a chemical vapor deposition method to deposit Ti on the surface of the fiber in the SiC fiber preform₃SiC₂And the thickness of the MAX phase interface layer is 200-1200 nm. Then, chemical vapor deposition is carried out on Ti₃SiC₂Depositing a SiC interface layer outside the MAX phase interface layer, wherein the thickness of the SiC interface layer is 3-5 mu m, and completely coating Ti₃SiC₂A MAX phase interface layer. Then selectAnd (3) taking a proper resin precursor for repeated dipping-curing-cracking treatment to obtain a green body containing the porous carbon matrix. And finally, carrying out liquid silicon melting reaction in a high-temperature infiltration furnace to obtain the SiC/SiC composite material. Due to Ti₃SiC₂The MAX phase has excellent chemical stability, heat conductivity and friction performance, and can effectively improve the performance of the SiC/SiC composite material under high temperature.

Description

Ti3SiC2MAX phase interface layer modified SiC/SiC composite material and preparation method thereof

Technical Field

The invention relates to the technical field of aerospace material preparation processes, in particular to Ti₃SiC₂A preparation method of MAX phase interface layer modified SiC/SiC composite material.

Background

At present, the most advanced material for the turbine blade of the engine in aviation is mainly the third generation single crystal superalloy with the density of about 8-9g/cm³The ultimate use temperature is 1100 ℃. In order to further increase the temperature before the turbine and reduce the weight of the engine, a novel ultra-light high-temperature material must be developed. The SiC/SiC ceramic matrix composite has the characteristics of low density, good high-temperature performance, high use temperature and the like, wherein the density is only about 1/3 of the current nickel-based high-temperature alloy, and the use temperature can reach more than 1500 ℃, so the SiC/SiC ceramic matrix composite is considered as a key material of a future high-performance engine and is a fundamental guarantee for realizing the engine with high thrust-weight ratio.

The SiC/SiC composite material generally comprises a fiber preform, a fiber interface layer, a ceramic matrix and the like. The SiC fiber preform plays a role of a framework and is responsible for bearing the stress of the material; the ceramic matrix is effective against thermal shock and oxidation at high temperatures. Due to the unique layered structure of the fiber interface layer, slippage can occur between layers under the action of stress, and the effects of crack deflection and energy release can be effectively realized. The interface layers commonly used at present are a pyrolytic carbon (PyC) interface layer and a Boron Nitride (BN) interface layer, wherein the performance of the PyC interface layer is obviously reduced at 400 ℃ in an oxidation environment; the BN interface layer has strict requirements on the crystal phase, but the crystal phase of the BN interface layer is easy to change at high temperature, and the BN interface layer is easy to be corroded by water environment, so that the use of the composite material is limited. With the improvement of the requirements of the aeroengine on the temperature resistance, the oxidation resistance and the mechanical property of the high-temperature oxidation environment of the material, a new SiC fiber interface layer needs to be developed to improve the performance of the composite material.

Disclosure of Invention

Technical problem to be solved

The invention aims to solve the technical problem that the mechanical property of the composite material in a high-temperature air environment is insufficient due to poor temperature resistance and oxidation resistance of the conventional fiber interface layer.

(II) technical scheme

In order to solve the above-mentioned problems, the present invention provides, in a first aspect, a Ti₃SiC₂A preparation method of MAX phase interface layer modified SiC/SiC composite material comprises the following steps:

(1) preparing a SiC fiber preform by using SiC fibers to obtain a first sample;

(2) depositing Ti on the surface of the SiC fibers of the first sample by chemical vapor deposition₃SiC₂MAX phase interface layer to obtain a second sample;

(3) depositing and preparing a SiC interface layer on the outer side of the second sample by adopting a chemical vapor deposition method to obtain a third sample;

(4) putting the third sample into the precursor solution for dipping to obtain a fourth sample;

(5) carrying out curing reaction on the fourth sample to obtain a fifth sample;

(6) carrying out cracking reaction on the fifth sample to obtain a sixth sample;

(7) repeating the steps (4) to (6) at least once to obtain a seventh sample containing porous matrix carbon;

(8) and performing liquid silicon infiltration on the seventh sample to obtain the final SiC/SiC composite material.

The present invention provides, in a second aspect, a Ti₃SiC₂MAX phaseAn interface layer modified SiC/SiC composite material, wherein the composite material is prepared according to the preparation method of the first aspect of the invention; preferably, the composite material comprises SiC fibers, Ti₃SiC₂MAX phase layer, SiC deposition layer and SiC ceramic matrix; more preferably, the Ti is₃SiC₂MAX phase is Ti₃SiC₂。

(III) advantageous effects

The technical scheme of the invention has the following advantages:

the invention has the advantages of adopting Ti₃SiC₂The MAX phase interface layer covers the SiC fibers. Ti obtained by chemical vapor deposition of the invention₃SiC₂The MAX phase interface layer has a layered structure similar to PyC and is a hexagonal lattice, W atoms and C atoms in the layer interact by virtue of covalent bonds, and Van der Waals acting forces interact among the layers, and the Van der Waals strength is weaker than that of chemical bonds and hydrogen bonds, so that relative sliding is easy to occur among the layers.

Ti of the invention₃SiC₂The MAX phase interface layer is made of Ti with the thickness of tens of nanometers₃SiC₂MAX phase micro-particles, therefore, the fiber can play a good stress releasing role such as crack deflection and fiber extraction. Ti prepared by the invention₃SiC₂The MAX phase interface layer has thermal conductivity of about 110W/(m.K), has higher thermal conductivity than the BN interface layer, can transfer heat in time, prevents local overheating from damaging fibers at the contact position of the fibers and a matrix due to the difference of the thermal conductivity, and can better play a role in toughening the fibers. Ti of the invention₃SiC₂The MAX phase material has a lower coefficient of friction than the BN interface layer and achieves crack deflection more easily than the latter. Ti of the invention₃SiC₂The MAX phase interface layer has better high-temperature oxidation resistance than a PyC interface layer under the high-temperature condition, and meanwhile, the stability of a crystal phase is higher than that of a BN interface layer, so that the mechanical property of the SiC/SiC composite material in a high-temperature air environment can be obviously improved.

Drawings

FIG. 1 is a schematic view of a SiC/SiC composite material according to the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, 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 obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

The present invention provides, in a first aspect, a Ti₃SiC₂A preparation method of MAX phase interface layer modified SiC/SiC composite material comprises the following steps:

(1) preparing a SiC fiber preform by using SiC fibers to obtain a first sample;

(5) carrying out curing reaction on the fourth sample to obtain a fifth sample;

The inventor researches and discovers that Ti is deposited by chemical vapor deposition₃SiC₂MAX phase (e.g. Ti)₃SiC₂) The laminated structure is provided, the Ti atomic layer and the Si atomic layer in the layer are combined pairwise by weak bonds, and the material can realize the slippage between the layers under the condition of not damaging the structure. This property is such that Ti₃SiC₂MAX phases can be regarded as good moisturesThe sliding material can realize crack deflection and energy release under the action of stress when being used as an interface layer of the SiC/SiC composite material, and ensures the toughness of the composite material. At the same time, Ti₃SiC₂Can exist stably at 1600 ℃, has excellent thermal shock resistance and oxidation resistance, and is expected to serve in the harsher thermal environment of future aircraft engines.

According to some preferred embodiments, in step (1), the SiC fibers are primary or secondary fibers;

the mode for preparing the SiC fiber preform is a weaving mode;

the weaving mode is sewing, 2.5D and/or three-dimensional four-way weaving; and/or

More preferably, the fiber volume fraction of the SiC fiber preform is 25% to 50%.

According to some preferred embodiments, in the step (2), the chemical vapor deposition method is performed in a chemical vapor deposition furnace;

the precursor adopted by the chemical vapor deposition method is selected from one or more of the group consisting of titanium tetrachloride, silicon tetrachloride, carbon tetrachloride and hydrogen;

the chemical vapor deposition method has the deposition temperature of 1000-1200 ℃ (such as 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃ and 1200 ℃), the vacuum degree of-0.09-0.02 MPa (such as-0.09 MPa, -0.08MPa, -0.07MPa, -0.06MPa, -0.05MPa, -0.04MPa, -0.03MPa and-0.02 MPa), and the deposition time of 0.5-10 h (such as 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h and 10 h); and/or

The Ti₃SiC₂The thickness of the MAX phase interface layer is 200-1200 nm (for example, 200nm, 400nm, 600nm, 800nm, 1000nm, 1200 nm).

According to some preferred embodiments, in step (3), the chemical vapor deposition process is performed in a chemical vapor deposition furnace;

the precursor adopted by the chemical vapor deposition method is selected from the group consisting of chloromethylsilane, silane, methylsilane and fluoromethylsilane;

the chemical vapor deposition method has a deposition temperature of 800 to 1200 ℃ (for example 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃, 1050 ℃, 1100 ℃, 1150 ℃, 1200 ℃), a vacuum degree of-0.09 to-0.01 MPa (for example-0.09 MPa, -0.08MPa, -0.07MPa, -0.06MPa, -0.05MPa, -0.04MPa, -0.03MPa, -0.02MPa, -0.01MPa), and a deposition time of 10 to 80 hours; and/or

The thickness of the SiC interface layer is 3-5 mu m.

According to some preferred embodiments, in step (4), the solute of the precursor solution is selected from the group consisting of phenolic resin, conone, furfural, ethanol, and the solvent of the precursor solution is selected from the group consisting of ethylene glycol, xylene, toluene;

preferably, a pore-forming agent is added into the precursor solution;

more preferably, the pore-forming agent is selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polyvinyl butyral;

the impregnation temperature of the precursor solution is 25-80 ℃, the impregnation pressure is 1-5 MPa, and the impregnation time is 0.5-4 h; and/or

The fourth sample contained a matrix carbon precursor.

According to some preferred embodiments, in step (5), the curing reaction is carried out in a high pressure tank; and/or

The curing temperature of the curing reaction is 100-350 ℃, the curing time is 1-5 h, and the curing pressure is 0.5-5 MPa.

According to some preferred embodiments, in step (6), the cracking reaction is carried out in a pyrolysis furnace; and/or

The cracking temperature is 700-1200 ℃, the cracking vacuum is-0.09-0.01 MPa, and the cracking time is 2-4 h.

According to some preferred embodiments, in step (7), the number of repetitions is 1 to 5.

According to some preferred embodiments, in step (8), the liquid silicon infiltration is performed in a high temperature infiltration furnace; and/or

The reaction temperature of infiltration is 1500-1700 ℃, the vacuum degree is-0.09-0.02 MPa, and the infiltration time is 0.1-2 hours.

The second aspect of the present invention provides a Ti₃SiC₂A MAX phase interface layer modified SiC/SiC composite material, wherein the composite material is prepared according to the preparation method of the first aspect of the invention;

preferably, the composite material comprises SiC fibers, Ti₃SiC₂MAX phase layer, SiC deposition layer and SiC ceramic matrix; more preferably, the Ti is₃SiC₂MAX phase is Ti₃SiC₂。

Example 1

(1) Weaving the second-generation SiC fibers into a 2.5D preform to obtain a first sample with the fiber volume fraction of 32%, the warp density of 7 pieces/cm and the weft density of 3 pieces/cm.

(2) Titanium tetrachloride and hydrogen are selected as precursors, and a chemical vapor deposition furnace is used for depositing for 1h on the fiber surface of a sample under the conditions of 1000 ℃ and-0.04 MPa to obtain Ti with the thickness of 500nm₃SiC₂MAX phase interface layer to obtain a second sample.

(3) And moving the second sample to a chemical vapor deposition furnace, and depositing for 45 hours at 1200 ℃ and under the vacuum degree of-0.05 MPa by using trichloromethylsilane as a precursor to obtain a third sample containing a SiC interface layer with the thickness of 3.5 microns.

(4) And (3) selecting a conone xylene solution as an impregnation precursor, and putting the third sample into the precursor to be impregnated for 1.5h at the temperature of 70 ℃ and under the high pressure of 2MPa to obtain a fourth sample.

(5) And (3) placing the fourth sample into a high-pressure tank for curing for 3 hours at the temperature of 150 ℃ under the vacuum condition of 2.5MPa to obtain a fifth sample.

(6) And putting the fifth sample into a pyrolysis furnace to be pyrolyzed for 2 hours under the vacuum conditions of 850 ℃ and-0.03 MPa to obtain a sixth sample.

(7) And (5) repeating the steps (4) to (6) for 3 times to obtain a seventh sample containing the porous matrix carbon.

(8) And putting the seventh sample into a high-temperature infiltration furnace for liquid silicon infiltration for 0.2h under the vacuum conditions of 1520 ℃ and-0.05 MPa to obtain the final SiC/SiC composite material.

And (4) processing a bending test sample strip on the sample piece obtained in the step (8), and measuring the bending strength of 334MPa and the tensile strength of 220MPa at 1300 ℃ under the air atmosphere condition.

Example 2

(1) Weaving the second-generation SiC fibers into a 2.5D preform to obtain a first sample with the fiber volume fraction of 39%, the warp density of 8 pieces/cm and the weft density of 3.5 pieces/cm.

(2) Titanium tetrachloride and hydrogen are selected as precursors, and a chemical vapor deposition furnace is used for depositing for 1.5h on the fiber surface of a sample under the conditions of 1000 ℃ and-0.04 MPa to obtain Ti with the thickness of 800nm₃SiC₂MAX phase interface layer to obtain a second sample.

(3) And moving the second sample to a chemical vapor deposition furnace, and depositing for 80 hours at 1200 ℃ and under the vacuum degree of-0.05 MPa by using trichloromethylsilane as a precursor to obtain a third sample containing a SiC interface layer with the thickness of 4 mu m.

(4) And (3) selecting a furfural dimethylbenzene solution as an impregnation precursor, and putting the third sample into the precursor to be impregnated for 1.5h at the temperature of 70 ℃ and under the high pressure of 2MPa to obtain a fourth sample.

(5) And (3) placing the fourth sample into a high-pressure tank for curing for 5 hours at the temperature of 150 ℃ under the vacuum condition of 3MPa to obtain a fifth sample.

(6) And putting the fifth sample into a pyrolysis furnace to be pyrolyzed for 4 hours at 850 ℃ and under the vacuum condition of-0.04 MPa, and taking out the fifth sample to obtain a sixth sample.

(7) Repeating the steps (4) to (6) for 3 times to obtain a seventh sample containing porous matrix carbon.

(8) And putting the seventh sample into a high-temperature infiltration furnace for liquid silicon infiltration for 0.5h under vacuum conditions of 1470 ℃ and-0.02 MPa to obtain the final SiC/SiC composite material.

And (4) processing a bending test sample strip on the sample piece obtained in the step (8), and measuring the bending strength of 343MPa and the tensile strength of 235MPa at 1300 ℃ under the air atmosphere condition.

Example 3

(1) The first generation of SiC fibers are woven in three-dimensional four-direction to obtain a first sample with the fiber volume fraction of 42%, the warp density is 7 pieces/cm, and the weft density is 3 pieces/cm.

(2) Selecting silicon tetrachloride as a precursor, and depositing for 10 hours on the fiber surface of a sample by using a chemical vapor deposition furnace under the conditions of 1200 ℃ and-0.09 MPa to obtain Ti with the thickness of 1000nm₃SiC₂MAX phase interface layer to obtain a second sample.

(3) And moving the second sample to a chemical vapor deposition furnace, and depositing for 45 hours at 800 ℃ and under the vacuum degree of-0.09 MPa by using silane as a precursor to obtain a third sample containing a SiC interface layer with the thickness of 5 mu m.

(4) And (3) selecting a phenolic resin toluene solution as an impregnation precursor, and putting the third sample into the precursor to be impregnated for 4 hours at the temperature of 25 ℃ and under the high pressure of 5MPa to obtain a fourth sample.

(5) And (3) putting the fourth sample into a high-pressure tank for curing for 3 hours at 350 ℃ under the vacuum condition of 1MPa to obtain a fifth sample.

(6) And putting the fifth sample into a pyrolysis furnace to be pyrolyzed for 4 hours under the vacuum conditions of 1200 ℃ and-0.09 MPa to obtain a sixth sample.

(7) Repeating the steps (4) to (6) 5 times to obtain a seventh sample containing porous matrix carbon.

(8) And putting the seventh sample into a high-temperature infiltration furnace for liquid silicon infiltration for 2 hours under the vacuum conditions of 1700 ℃ and-0.02 MPa to obtain the final SiC/SiC composite material.

And (4) processing a bending test sample strip on the sample piece obtained in the step (8), and measuring the bending strength of 357MPa and the tensile strength of 241MPa under the air atmosphere condition at 1300 ℃.

Example 4

(1) The second-generation SiC fibers were stitched to obtain a first sample having a fiber volume fraction of 48%, a warp density of 7 pieces/cm, and a weft density of 3 pieces/cm.

(2) Selecting carbon tetrachloride as a precursor, and depositing for 1h on the fiber surface of a sample by using a chemical vapor deposition furnace at 1100 ℃ and-0.04 MPa to obtain Ti with the thickness of 1000nm₃SiC₂MAX phase interface layer to obtain a second sample.

(3) And moving the second sample into a chemical vapor deposition furnace, and depositing for 65 hours at 900 ℃ and under the vacuum degree of-0.02 MPa by using fluoromethylsilane as a precursor to obtain a third sample containing a SiC interface layer with the thickness of 4.5 mu m.

(4) And (3) selecting a furfural ethanol solution as an impregnation precursor, and putting the third sample into the precursor to be impregnated for 2.5 hours at the temperature of 30 ℃ and under the high pressure of 3MPa to obtain a fourth sample.

(5) And (3) placing the fourth sample into a high-pressure tank for curing for 2 hours at the temperature of 250 ℃ and under the vacuum condition of 3.5MPa to obtain a fifth sample.

(6) And putting the fifth sample into a pyrolysis furnace to be pyrolyzed for 3 hours under the vacuum conditions of 1050 ℃ and-0.05 MPa to obtain a sixth sample.

(7) And (5) repeating the steps (4) to (6) for 2 times to obtain a seventh sample containing the porous matrix carbon.

(8) And putting the seventh sample into a high-temperature infiltration furnace for liquid silicon infiltration for 1.2h under the vacuum conditions of 1620 ℃ and-0.07 MPa to obtain the final SiC/SiC composite material.

And (4) processing a bending test sample strip on the sample piece obtained in the step (8), and measuring the bending strength of 384MPa and the tensile strength of 261MPa under the air atmosphere condition at 1300 ℃.

Comparative example 1

In substantially the same manner as in example 1, except that a pyrolytic carbon (PyC) interfacial layer was used in place of Ti₃SiC₂A MAX phase interface layer. A pyrolytic carbon (PyC) interfacial layer was prepared as follows: and (3) taking propane and hydrogen as gas sources, and depositing for 10 hours on the fiber surface of the sample by using a chemical vapor deposition furnace under the vacuum conditions of 800 ℃ and-0.03 Mpa to obtain a PyC phase interface layer with the thickness of 500nm and obtain a second sample.

And (4) processing a bending test sample strip on the sample piece obtained in the step (8), and measuring the bending strength of 291MPa and the tensile strength of 177MPa under the air atmosphere condition at 1300 ℃.

Comparative example 2

In substantially the same manner as in example 1, except that a Boron Nitride (BN) interfacial layer was used in place of Ti₃SiC₂A MAX phase interface layer. The Boron Nitride (BN) interfacial layer was prepared as follows: boron trichloride, nitrogen, hydrogen and ammonia are used as gas sources, and a chemical vapor deposition furnace is used for depositing fibers on a sample under the vacuum condition of 900 ℃ and-0.02 MpaSurface deposition for 15h to obtain a BN phase interface layer with the thickness of 500nm to obtain a second sample

The obtained sample piece is processed into a bending test sample strip, and the bending strength and the tensile strength of the sample piece are 309MPa and 194MPa under the air atmosphere condition at 1300 ℃.

TABLE 1 Process conditions and Properties of samples obtained for the examples and comparative examples

Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims

1. Ti₃SiC₂The preparation method of the MAX phase interface layer modified SiC/SiC composite material is characterized by comprising the following steps:

(1) preparing a SiC fiber preform by using SiC fibers to obtain a first sample;

(5) carrying out curing reaction on the fourth sample to obtain a fifth sample;

2. The method of claim 1, wherein:

in the step (1), the SiC fibers are primary or secondary fibers;

the mode for preparing the SiC fiber preform is a weaving mode;

The fiber volume fraction of the SiC fiber preform is 25-50%.

3. The method of claim 1, wherein:

in the step (2), the chemical vapor deposition method is carried out in a chemical vapor deposition furnace;

the deposition temperature of the chemical vapor deposition method is 1000-1200 ℃, the vacuum degree is-0.09-0.02 MPa, and the deposition time is 0.5-10 h; and/or

The Ti₃SiC₂The thickness of the MAX phase interface layer is 200-1200 nm.

4. The method of claim 1, wherein:

in the step (3), the chemical vapor deposition method is carried out in a chemical vapor deposition furnace;

the deposition temperature of the chemical vapor deposition method is 800-1200 ℃, the vacuum degree is-0.09-0.01 MPa, and the deposition time is 10-80 h; and/or

The thickness of the SiC interface layer is 3-5 mu m.

5. The method of claim 1, wherein:

in the step (4), the solute of the precursor solution is selected from the group consisting of phenolic resin, constantan, furfural and ethanol, and the solvent of the precursor solution is selected from the group consisting of xylene, ethylene glycol and toluene;

preferably, a pore-forming agent is added into the precursor solution; more preferably, the pore-forming agent is selected from the group consisting of polyvinyl alcohol, polyethylene glycol, polyvinyl butyral;

The fourth sample contained a matrix carbon precursor.

6. The method of claim 1, wherein:

in step (5), the curing reaction is carried out in a high-pressure tank; and/or

7. The method of claim 1, wherein:

in the step (6), the cracking reaction is carried out in a pyrolysis furnace; and/or

8. The method of claim 1, wherein:

in step (7), the number of repetitions is 1 to 5.

9. The method of claim 1, wherein:

in the step (8), the liquid silicon infiltration is carried out in a high-temperature infiltration furnace; and/or

10. Ti₃SiC₂The MAX phase interface layer modified SiC/SiC composite material is characterized in that:

the composite material is prepared according to the preparation method of any one of claims 1 to 9;