CN109467450B

CN109467450B - Ti-containing alloy3SiC2SiC of the interface layerfPreparation method of/SiC composite material

Info

Publication number: CN109467450B
Application number: CN201811524818.8A
Authority: CN
Inventors: 黄小忠; 王春齐; 唐云; 彭立华
Original assignee: Hunan Zerui New Material Co ltd
Current assignee: Hunan Zerui New Material Co., Ltd
Priority date: 2018-12-13
Filing date: 2018-12-13
Publication date: 2021-09-24
Anticipated expiration: 2038-12-13
Also published as: CN109467450A

Abstract

The invention discloses a Ti-containing alloy₃SiC₂SiC of the interface layer_fThe preparation method of the/SiC composite material adopts a magnetron sputtering method to deposit Ti on a SiC fiber woven part₃SiC₂To obtain a titanium-containing alloy₃SiC₂Weaving SiC fiber at interface layer, and impregnating and carbonizing resin to obtain SiC_fPorous body of/C and SiC obtained by gas phase siliconizing_fa/SiC composite material; the magnetron sputtering is to firstly adopt a TiC target to carry out magnetron sputtering, obtain a 0.1-0.2 mu m TiC overplate on the surface of the SiC fiber bundle or the SiC fiber weaving piece, and then adopt a TiC target and a Si target to carry out co-sputtering to obtain Ti₃SiC₂Said Ti₃SiC₂The thickness of the film is controlled to be 0.6-1.0 μm; the Ti-containing alloy is obtained by adopting a magnetron sputtering method for the first time₃SiC₂SiC of the interface layer_fthe/SiC composite material effectively reduces the deposition temperature, avoids the damage of fibers, and the obtained interface layer is superior to the interface layers such as C, BN and the like commonly used in the prior art in the aspect of oxidation resistance. Meanwhile, the ceramic is formed by adopting a non-contact gas-phase siliconizing method, so that the density gradient is effectively reduced, and the qualification rate of 100 percent can be ensured.

Description

Ti-containing alloy3SiC2SiC of the interface layerfPreparation method of/SiC composite material

Technical Field

The invention relates to the field of ceramic matrix composite materials, in particular to a Ti-containing composite material₃SiC₂A preparation method of SiCf/SiC composite material of an interface layer.

Background

Continuous silicon carbide fiber reinforced ceramic matrix composite (SiC)_fSiC) is a high-temperature structural material which is developed in the beginning of the century and is paid attention to, compared with other materials, the high-temperature structural material has the advantages of low density, high temperature resistance, corrosion resistance, high strength, high modulus and the like, and the development is very rapid along with the continuous improvement of preparation technology, so that the high-temperature structural material is mainly applied to various high-precision fields of hypersonic aircrafts, aero-engines, nuclear fusion reactors, high-temperature wave absorption and the like.

In SiC_fIn the SiC composite material, the interface layer is a bridge for transferring load between the braided body fiber and the matrix material and is also a key factor for preparing the continuous SiC fiber reinforced composite material with excellent performance. In SiC_fIn the case of the/SiC composite material, the ideal interface layer mainly functions in the following ways. (1) Protecting SiC fibers and inhibiting composite materialsDamage to the fibers during the preparation of the material. (2) The bonding strength between the SiC fibers and the SiC matrix is adjusted so that SiC is obtained_fThe energy dissipation mechanisms such as fiber extraction, crack deflection and the like play roles in the fracture process of the SiC composite material, so that the toughness of the composite material is enhanced.

Most commonly used SiC at present_fThe interface layer in the/SiC composite material is Pyrolytic Carbon (PyC) and Hexagonal boron nitride (Hexagonal-BN), but in use, the interface layer is found to be easily oxidized, and thus the service stability of the composite material under irradiation and oxidation environments is insufficient.

In recent years, one kind of Ti₃SiC₂A ternary transition metal compound MAX phase as a representative is receiving wide attention (M: transition group metal element; a: main group element; X is C or N; and N is 1 to 3). The MAX phase has a crystal structure of a hexagonal layered structure, MX sheet layers and A atomic layers are alternately stacked in the c-axis direction, and the unique crystal structure endows the MAX phase with special chemical bond characteristics, so that the MAX phase ceramic material gives consideration to the excellent characteristics of a metal material and a ceramic material, and on one hand, has good heat conduction/electrical property like metal and excellent thermal shock resistance and plasticity at high temperature. On the other hand, the characteristics of ceramics such as high melting point and high hardness are also aggregated. Unlike common carbide, the machinability of the material is beneficial to large-scale application in engineering, so that the MAX phase ceramic has wide application prospect. Not only can be used independently, but also has very important influence as a reinforcing toughening body in the composite material. . However, Ti on the surface of the fiber is not available at present₃SiC₂And (4) reporting related interface layers.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a Ti-containing material₃SiC₂SiC of the interface layer_fA preparation method of a/SiC composite material.

The invention relates to a Ti-containing alloy₃SiC₂SiC of the interface layer_fThe preparation method of the/SiC composite material comprises the following steps: ti deposition is carried out on SiC fiber woven piece by adopting magnetron sputtering method₃SiC₂To obtain a titanium-containing alloy₃SiC₂Of interfacial layersWeaving SiC fiber, and impregnating and carbonizing resin to obtain SiC_fPorous body of/C and SiC obtained by gas phase siliconizing_fa/SiC composite material.

In a preferred scheme, the magnetron sputtering method is a double-target magnetron sputtering method, and the double targets are respectively a TiC target and a Si target.

Preferably, the magnetron sputtering is performed by adopting a TiC target to perform magnetron sputtering, a 0.1-0.2 mu m TiC overplate is obtained on the surface of the SiC fiber bundle or the SiC fiber weaving piece, and then a TiC target and a Si target are co-sputtered to obtain Ti₃SiC₂Said Ti₃SiC₂The thickness of the film is controlled to be 0.6 to 1.0 μm.

The inventor finds that the SiC fiber is better coated and combined by depositing a layer of TiC, and the corrosion of Si gas to the SiC fiber woven piece can be completely avoided.

Further preferably, the deposition process of the TiC overplate is as follows: placing the SiC fiber woven piece into a magnetron sputtering vacuum chamber, and firstly sputtering by using a TiC target, wherein the vacuum degree before sputtering is 1-5 multiplied by 10 < -3 > Pa, the distance between the target and the fiber is 80-120 mm, the argon flow is 30-50 sccm, the sputtering temperature is room temperature, the sputtering power is 2200-2800W, the deposition rate is 10-20 nm/min, and the sputtering time is 5-20 mim.

Further preferably, the Ti₃SiC₂The deposition process comprises the following steps: co-sputtering with TiC target and Si target, wherein the vacuum degree before sputtering is 1-5 multiplied by 10^-3Pa, the distance between the target and the fiber is 80-120 mm, the argon flow is 30-50 sccm, the sputtering temperature is room temperature, the sputtering power is 1500-2000W, the deposition rate is 5-10 nm/min, and the sputtering time is 80-200 mim.

Preferably, the resin impregnation carbonization process comprises the following steps: will contain Ti₃SiC₂Placing the SiC fiber woven piece of the interface layer into an impregnating solution, carrying out vacuum impregnation, curing and cracking after the impregnation is finished, repeating the impregnation-curing-cracking process for 3-5 times, and finally preparing the SiC fiber woven piece with the density of 1.6-1.8 g/cm³Of SiC_fThe impregnating solution comprises the following components in percentage by mass: m-phenylenediPhenol, formaldehyde and absolute ethyl alcohol according to the mass ratio (4-6): (8-10): (20-26).

In a preferable scheme, the vacuum degree of the vacuum impregnation is less than or equal to 0.001MPa, and the vacuum impregnation time is 1-3 h.

In a preferable scheme, the curing temperature is 160-220 ℃, and the curing time is 2-3 h.

In the preferable scheme, the cracking temperature is 800-1000 ℃, and the cracking time is 1-2 h.

Preferably, the gas phase siliconizing process comprises the following steps: mixing SiC_fthe/C porous material is placed in a graphite mold paved with silicon powder, and the SiC_fThe graphite block is padded under the/C porous material, so that SiC_fthe/C porous material is not directly contacted with the silicon powder, the temperature is raised to 1900-2000 ℃ under the vacuum condition, and the temperature is preserved for 30-60 min, so that SiC is obtained_fa/SiC composite material.

Preferably, the graphite block is a hollow graphite block.

In a preferred scheme, the vacuum degree is 800-1200 pa.

In the preferable scheme, the temperature rise speed is 5-20 ℃/min.

In the invention, the silicon vapor and SiC are obtained by adopting a non-contact gas-phase siliconizing method_fC in the/C porous material reacts to form a compact and uniform silicon carbide matrix, and silicon powder in the mold reacts with SiC through siphoning in a non-contact process_fThe reaction of the/C porous material can obtain better siphonage effect in the process of preferably adopting the hollow graphite block, and the SiC_fThe surface of the/SiC composite material is clean, the situation that silicon powder is crusted frequently in the silicon melting process can not occur, the product percent of pass is 100%, and the density gradient formed by the silicon melting method in the prior art is greatly reduced.

In a preferred scheme, the mesh number of the silicon powder is 80-120 meshes.

The inventor finds that the reaction effect is very important in the gas-phase siliconizing process, and the particle size of the silicon powder is too large or too small, so that the gas-phase silicon is not favorably formed.

Has the advantages that:

1) the invention adopts double-target magnetron sputtering to obtain the MAX phase interface layer on the SiC fiber surface for the first time, the deposition temperature is effectively reduced by adopting magnetron sputtering, the fiber damage is avoided, and the obtained interface layer is superior to the interface layers such as C, BN and the like commonly used in the prior art in oxidation resistance. Meanwhile, the interface layer has the characteristic of neutron radiation resistance and can be used in the field of nuclear radiation.

2) The invention is used for preparing SiC_fIn the process of preparing the/C porous material, resorcinol and formaldehyde are subjected to polycondensation reaction to generate phenolic resin, and absolute ethyl alcohol is added as a solvent, so that a better impregnation effect can be obtained in a solution system, and meanwhile, due to volatilization in the curing process of the absolute ethyl alcohol, a plurality of pores are formed, and a porous C/C composite material with high specific surface area and high porosity is obtained after cracking.

3) In the invention, the silicon vapor and SiC are obtained by adopting a non-contact gas-phase siliconizing method_fC in the/C porous material reacts to form a compact and uniform silicon carbide matrix, and silicon powder in the mold reacts with SiC through siphoning in a non-contact process_fA better siphoning effect can be obtained by the reaction of the/C porous material, and the SiC_fThe surface of the/SiC composite material is clean, the product percent of pass is 100 percent, and the density gradient formed by a silicon melting method in the prior art is greatly reduced.

Detailed Description

The following examples are intended to further illustrate the present disclosure, but not to limit the scope of the claims.

Example 1

Placing the SiC fiber woven piece into a magnetron sputtering vacuum chamber, firstly sputtering by adopting a TiC target, wherein the vacuum degree before sputtering is 2 multiplied by 10 < -3 > Pa, the distance between the target and the fiber is 80mm, the argon flow is 30sccm, the sputtering temperature is room temperature, the sputtering power is 2200W, the deposition rate is 10nm/min, and the sputtering time is 10 mim. Obtaining a silicon carbide fiber weaving piece in the TiC-containing transition layer, and then adopting a TiC target and a Si target for co-sputtering, wherein the vacuum degree before sputtering is 1 multiplied by 10-3Pa, the distance between the target and the fiber is 90mm, the argon flow is 40sccm, the sputtering temperature is room temperature, the sputtering power is 1500W, the deposition rate is 5nm/min, and the sputtering time is 100 mim. Thereby obtaining Ti-containing₃SiC₂The silicon carbide fiber weaving piece of the interface layer,

then containing Ti₃SiC₂Putting the SiC fiber of the interface layer into an impregnating solution, carrying out vacuum impregnation, controlling the vacuum degree of the vacuum impregnation to be less than or equal to 0.001MPa, impregnating for 2h, then curing at 160 ℃, wherein the curing time is 3h, then cracking at 800 ℃, wherein the cracking time is 2h, repeating the impregnation-curing-cracking process for 4 times to obtain the SiC fiber with the density of 1.68g/cm³Of SiC_fThe impregnating solution comprises the following components in percentage by mass: resorcinol, formaldehyde and absolute ethyl alcohol according to a mass ratio of 4: 8: 26.

mixing the above SiC_fthe/C porous material is placed in a graphite mold paved with 80-mesh silicon powder, and the SiC_fThe hollow graphite block is padded under the/C porous material, so that SiC_fthe/C porous material is not directly contacted, the temperature is increased to 1900 ℃ under the vacuum condition, the vacuum degree is 800Pa, and the temperature is preserved for 60min, thus obtaining the SiC_fa/SiC composite material.

Example 2

Placing the SiC fiber woven piece in a magnetron sputtering vacuum chamber, firstly sputtering by adopting a TiC target, wherein the vacuum degree before sputtering is 3 multiplied by 10^-3Pa, the distance between the target and the fiber was 100mm, the argon flow was 40sccm, the sputtering temperature was room temperature, the sputtering power was 2400W, the deposition rate was 15nm/min, and the sputtering time was 15 mim. Obtaining a silicon carbide fiber weaving piece in the TiC-containing transition process, and then co-sputtering by adopting a TiC target and a Si target, wherein the vacuum degree before sputtering is 3 multiplied by 10^-3Pa, a distance between the target and the fiber of 80mm, an argon flow of 30sccm, a sputtering temperature of room temperature, a sputtering power of 1700W, a deposition rate of 7nm/min, and a sputtering time of 90 mim. Thereby obtaining Ti-containing₃SiC₂The silicon carbide fiber weaving piece of boundary layer.

Then containing Ti₃SiC₂Placing the SiC fibers of the interface layer into an impregnating solution, carrying out vacuum impregnation, and controlling the vacuum degree of the vacuum impregnationSoaking at 0.001MPa or below for 2 hr, curing at 200 deg.C for 2.5 hr, cracking at 900 deg.C for 1.5 hr, repeating the soaking-curing-cracking process for 5 times to obtain a density of 1.79g/cm³Of SiC_fThe impregnating solution comprises the following components in percentage by mass: resorcinol, formaldehyde and absolute ethyl alcohol according to a mass ratio of 5: 9: 26.

mixing the above SiC_fthe/C porous material is placed in a graphite mold paved with 90-mesh silicon powder, and the SiC_fThe hollow graphite block is padded under the/C porous material, so that SiC_fthe/C porous material is not directly contacted, the temperature is increased to 2000 ℃ under the vacuum condition, the vacuum degree is 800Pa, and the temperature is preserved for 40min, thus obtaining the SiC_fa/SiC composite material.

Example 3

Placing the SiC fiber woven piece into a magnetron sputtering vacuum chamber, firstly sputtering by adopting a TiC target, wherein the vacuum degree before sputtering is 5 multiplied by 10 < -3 > Pa, the distance between the target and the fiber is 120mm, the argon flow is 40sccm, the sputtering temperature is room temperature, the sputtering power is 2600W, the deposition rate is 10nm/min, and the sputtering time is 20 mim. Obtaining a silicon carbide fiber weaving piece in the TiC-containing transition process, and co-sputtering by adopting a TiC target and a Si target, wherein the vacuum degree before sputtering is 2 multiplied by 10 < -3 > Pa, the distance between the target and the fiber is 110mm, the argon flow is 50sccm, the sputtering temperature is room temperature, the sputtering power is 1800W, the deposition rate is 10nm/min, and the sputtering time is 150 mim. Thereby obtaining Ti-containing₃SiC₂The silicon carbide fiber weaving piece of boundary layer.

Then containing Ti₃SiC₂Putting the SiC fiber of the interface layer into an impregnating solution, carrying out vacuum impregnation, controlling the vacuum degree of the vacuum impregnation to be less than or equal to 0.001MPa, impregnating for 2h, then curing at 200 ℃, curing for 2h, then cracking at 1000 ℃, cracking for 1h, repeating the impregnation-curing-cracking process for 3 times to obtain the SiC fiber with the density of 1.64g/cm³Of SiC_fThe impregnating solution comprises the following components in percentage by mass: resorcinol, formaldehyde and absolute ethyl alcohol according to a mass ratio of 6: 10: 20.

mixing the above SiC_fporous/CThe bulk material is placed in a graphite mould paved with 80-mesh silicon powder, and the SiC_fThe hollow graphite block is padded under the/C porous material, so that SiC_fHeating to 1950 deg.C under vacuum condition without direct contact with/C porous material, keeping the vacuum degree at 1000Pa, and keeping the temperature for 50min to obtain SiC_fa/SiC composite material.

Comparative example 1

Otherwise, SiC was obtained without first depositing a TiC transition layer, as in example 1_fa/SiC composite material.

Comparative example 2

SiC was obtained by using a phenol resin as the impregnating solution under the same conditions as in example 2_fa/SiC composite material. The porous property is poor, and the density gradient is large after the silicon infiltration in the later period.

Comparative example 3

SiC was obtained by using 800 mesh silicon powder under the same conditions as in example 2_fa/SiC composite material.

Comparative example 4

The ceramization process was the same as example 3, except that the C interface layer was obtained by CVI method and then SiC was obtained by ceramization_fSiC composite material

Performance testing

SiC prepared by the above examples and comparative examples_fThe performance of the/SiC composite material after processing was tested, and the performance results are shown in Table 1.

TABLE 1 SiC_fPerformance test meter for/SiC composite material

Mechanical property tests were performed after oxidizing the samples prepared in the above examples and comparative examples at 1200 c in air, and the results are shown in table 2.

TABLE 2 SiC_fMechanical property of the/SiC composite material after being oxidized at 1200 ℃ in air

Claims

1. Ti-containing alloy₃SiC₂SiC of the interface layer_fThe preparation method of the/SiC composite material is characterized by comprising the following steps: ti deposition is carried out on SiC fiber woven piece by adopting magnetron sputtering method₃SiC₂To obtain a titanium-containing alloy₃SiC₂Weaving SiC fiber at interface layer, and impregnating and carbonizing resin to obtain SiC_fPorous body of/C and SiC obtained by gas phase siliconizing_fa/SiC composite material;

the magnetron sputtering method comprises the steps of firstly adopting a TiC target to carry out magnetron sputtering, obtaining a TiC transition layer with the thickness of 0.1-0.2 mu m on the surface of the SiC fiber bundle or the SiC fiber woven piece, and then adopting a TiC target and a Si target to carry out co-sputtering to obtain Ti₃SiC₂Said Ti₃SiC₂The thickness of the film is controlled to be 0.6-1.0 μm;

the deposition process of the TiC transition layer comprises the steps of placing the SiC fiber woven piece into a magnetron sputtering vacuum chamber, firstly sputtering by adopting a TiC target, wherein the vacuum degree before sputtering is 1-5 multiplied by 10^-3Pa, the distance between the target and the fiber is 80-120 mm, the argon flow is 30-50 sccm, the sputtering temperature is room temperature, the sputtering power is 2200-2800W, the deposition rate is 10-20 nm/min, the sputtering time is 5-20 min,

the Ti₃SiC₂The deposition process of the interface layer is that a TiC target and a Si target are co-sputtered, and the vacuum degree before sputtering is 1-5 multiplied by 10^-3Pa, the distance between the target and the fiber is 80-120 mm, the argon flow is 30-50 sccm, the sputtering temperature is room temperature, the sputtering power is 1500-2000W, the deposition rate is 5-10 nm/min, and the sputtering time is 80-200 min.

2. A Ti-containing alloy according to claim 1₃SiC₂SiC of the interface layer_fThe preparation method of the/SiC composite material is characterized by comprising the following steps: the resin impregnation carbonization process comprises the following steps: will contain Ti₃SiC₂Placing the SiC fiber woven piece of the interface layer into an impregnating solution, carrying out vacuum impregnation, curing and cracking after the impregnation is finished, and repeating the impregnation, curing and crackingThe decomposing process is carried out for 3-5 times, and the final prepared density is 1.6-1.8 g/cm³Of SiC_fThe impregnating solution comprises the following components in percentage by mass: resorcinol, formaldehyde and absolute ethyl alcohol in a mass ratio of (4-6): (8-10): (20-26).

3. A Ti-containing alloy according to claim 2₃SiC₂SiC of the interface layer_fThe preparation method of the/SiC composite material is characterized by comprising the following steps: the vacuum degree of the vacuum impregnation is less than or equal to 0.001MPa, and the vacuum impregnation time is 1-3 h; the curing temperature is 160-220 ℃, and the curing time is 2-3 h; the cracking temperature is 800-100 ℃, and the cracking time is 1-2 h.

4. A Ti-containing alloy according to claim 1₃SiC₂SiC of the interface layer_fThe preparation method of the/SiC composite material is characterized by comprising the following steps: the gas phase siliconizing process comprises the following steps of_fthe/C porous material is placed in a graphite mold paved with silicon powder, and the SiC_fThe graphite block is padded under the/C porous material, so that SiC_fthe/C porous material is not directly contacted with the silicon powder, the temperature is raised to 1900-2000 ℃ under the vacuum condition, and the temperature is preserved for 30-60 min, so that SiC is obtained_fa/SiC composite material.

5. A Ti-containing composition according to claim 4₃SiC₂SiC of the interface layer_fThe preparation method of the/SiC composite material is characterized by comprising the following steps: the graphite block is a hollow graphite block.

6. A Ti-containing composition according to claim 4₃SiC₂SiC of the interface layer_fThe preparation method of the/SiC composite material is characterized by comprising the following steps: the mesh number of the silicon powder is 80-120 meshes.