CN108385087B - Method for continuously and rapidly preparing BN coating on surface of SiC fiber - Google Patents

Method for continuously and rapidly preparing BN coating on surface of SiC fiber Download PDF

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CN108385087B
CN108385087B CN201810144054.3A CN201810144054A CN108385087B CN 108385087 B CN108385087 B CN 108385087B CN 201810144054 A CN201810144054 A CN 201810144054A CN 108385087 B CN108385087 B CN 108385087B
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vapor deposition
heat treatment
coating
gas
filament
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CN108385087A (en
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阳海棠
黄小忠
陆子龙
彭立华
黎尧
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Central South University
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/34—Nitrides
    • C23C16/342—Boron nitride
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/54—Apparatus specially adapted for continuous coating
    • C23C16/545—Apparatus specially adapted for continuous coating for coating elongated substrates
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/56—After-treatment

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  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

The invention discloses a method for rapidly and continuously preparing a BN coating on the surface of SiC fibers; the invention utilizes the yarn winding and unwinding device to ensure that the SiC fiber can be directly converted into the crystalline BN coating after the amorphous BN interface deposition is finished under the movement of the SiC fiber, thereby effectively avoiding the decomposition problem of the amorphous BN in the conversion process of deposition and heat treatment in the prior art.

Description

Method for continuously and rapidly preparing BN coating on surface of SiC fiber
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a method for continuously and rapidly preparing a BN coating on the surface of SiC fibers.
Background
With the change of science and technology, the number of composite materials is also infinite. Ceramic matrix composites are receiving increasing attention due to their excellent properties of high temperature resistance, corrosion resistance, wear resistance, and low relative density. Among them, SiC fiber reinforced composites have been widely used in the aerospace field, and fiber reinforcement is one of the main methods for improving the performance of composites.
The BN coating has the following advantages as a coating capable of improving the performance of SiC fibers:
1. the toughness is obvious, BN and PyC both belong to weak coatings, the bending strength of SiC fibers with high brittleness can be greatly improved, and the fracture form of the SiC fibers is shown as ductile fracture;
2. the oxidation resistance is strong, compared with PyC, the oxidation resistance temperature of the BN modified SiC fiber is greatly increased, and the oxidation product is B2O3The fiber has a self-healing function and can prevent the further oxidation of the fiber;
3. the thermal property is good, the thermal expansion property and the thermal conductivity are low, the thermal expansion coefficient of BN is similar to that of SiC, the thermal shock resistance is excellent, and the high temperature resistant service temperature of the modified SiC fiber is improved by 100-200 ℃ compared with that of the fiber before modification;
4. good resistance to molten metal erosion, strong resistance to chemical corrosion, and the like;
at present, a plurality of methods for preparing BN coatings on the surfaces of SiC fibers exist, however, the method for preparing the BN coatings on the surfaces of the SiC fibers by adopting a vapor deposition method is the method with the greatest industrial prospect. However, the deposition process of the BN coating in the prior art still has the following disadvantages:
on one hand, the existing method for depositing the BN coating on the SiC fibers by the vapor deposition method is to weave and form the SiC fibers firstly and then deposit the coating, so that the formed coating is uneven and has low deposition speed, and the problem that the deposition in the woven body is insufficient and defects are formed because the woven body has a certain thickness, the distance between the fibers is relatively close and the permeability of the deposition is continuously reduced along with the deposition time; finally, the formed coating is not uniform, and in addition, in order to ensure that the inside and the outside of the woven body are uniformly deposited, the deposition speed outside the woven body needs to be controlled to prevent surface crusting or pore blocking; the deposition rate is slow;
on the other hand, the BN coating formed during vapor deposition is amorphous, poor in stability, easy to decompose and easy to react in air, and the BN coating which is subjected to later heat treatment and is converted into a crystalline form has stability only by being subjected to later heat treatment, however, the deposition and high-temperature heat treatment are required to be carried out in different equipment, so that the BN formed by deposition is extremely easy to decompose in the equipment conversion process, and the stable crystalline form cannot be finally obtained by the BN formed by deposition.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for continuously and rapidly preparing a BN coating on the surface of SiC fibers.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for continuously and rapidly preparing a BN coating on the surface of SiC fibers comprises the following steps:
in the integrated equipment, under the protection of inert gas, the SiC fibers or the SiC fiber bundles are subjected to vapor deposition to form an amorphous BN coating, and the SiC fibers or the SiC fiber bundles with the amorphous BN coating are directly subjected to heat treatment to form a crystalline BN coating;
the integrated equipment comprises a vapor deposition device, a heat treatment device, a wire releasing device and a wire collecting device; the filament-releasing device and the heat treatment device are positioned at two sides of the vapor deposition device and are communicated with the vapor deposition device;
the SiC fibers or the SiC fiber bundles are discharged from the filament discharging device, move through the vapor deposition device to finish vapor deposition to form an amorphous BN coating, then directly enter heat treatment equipment to finish heat treatment to form a crystalline BN coating, and finally are collected by the filament collecting device;
the temperature of the vapor deposition is 800-1200 ℃, and preferably 900-1100 ℃; the pressure of the vapor deposition is 3000-80000 Pa, preferably 5000-50000 Pa; the wire moving speed of the SiC fiber or the SiC fiber is 0.1-2m/min, preferably 0.1-1.5 m/min; the temperature of the heat treatment is 1200-2000 ℃, preferably 1250-1800 ℃, and further preferably 1300-1600 ℃; the thickness of the obtained BN coating of the SiC fiber is 100-4000nm, and preferably, the thickness of the obtained BN coating of the SiC fiber is 400-3000 nm; as a further preference, the thickness of the obtained BN coating of the SiC fiber is 400-2000 nm.
The wire traveling speed of the SiC fibers or the SiC fiber bundles refers to the linear speed of the moving single SiC fibers or single-bundle SiC fibers under the guidance of the wire unwinding device.
In the invention, the preparation of the BN coating is completed in the filament traveling process of the SiC fibers or the SiC fiber bundles, thereby realizing continuous production. In the industrial production process, the yarn collecting device can be externally connected with a weaving device, and continuous production from coating to weaving is realized.
According to the preferable scheme, the filament discharging device comprises a filament discharging machine, a roller group A and a sealable chamber, wherein the filament discharging machine and the roller group A are positioned in the sealable chamber, and the sealable chamber is communicated with the vapor deposition device;
the wire releasing device comprises a wire collecting machine and a roller set B; and placing in a heat treatment device;
the heat treatment device is provided with a constant temperature area, and the roller group B and the wire collecting machine are arranged on two sides of the constant temperature area of the heat treatment device;
the SiC fibers or SiC fiber bundles come out of the filament releasing machine, are turned by the roller set A, move from the roller set A to the roller set B, are subjected to vapor deposition by the vapor deposition device, are turned by the roller set B, move to the filament releasing machine and pass through a constant temperature area of the heat treatment device to complete heat treatment.
In a preferable scheme, a constant-temperature reaction zone is arranged in the vapor deposition device; the vapor deposition device is provided with a first air inlet, a second air inlet and a third air inlet; the first gas inlet is an inert gas inlet, the second gas inlet and the third gas inlet are a gas source gas and a diluent gas inlet, the second gas inlet is positioned at the front section of the vapor deposition device, and the third gas inlet is positioned in a constant-temperature reaction zone of the vapor deposition device;
during vapor deposition, non-metal boride and NH are used3As source gas, H2For diluting the gas, non-metallic borides and NH3Air is respectively fed from the second air inlet and the third air inlet; h2Intake air from the second intake port or the third intake port; the flow rate of the non-metal boride is 0.1-1.5L/min, and the NH is3The flow rate of (A) is 0.3-5.0L/min, the flow rate of (B) is H2The flow rate of (A) is 0.1-1.5L/min. Further preferably, the flow rate of the non-metal boride is 0.2 to 1.0L/min, and the NH is3The flow rate of (A) is 0.5-3.0L/min, the flow rate of (B) is H2The flow rate of (A) is 0.2-1.0L/min.
In a preferred embodiment, the non-metal boride is BCl3、BF3、BBr3、BI3Any one of them. As a further preference, the non-metal boride is BCl3、BBr3、BI3Any one of them.
The constant temperature reaction zone of vapor deposition is a section of zone with the temperature required by deposition reaction, and the section of zone is positioned in the middle section of the vapor deposition device and has uniform temperature. In the invention, two gas sources are adopted, and the reaction can be started when the two gas sources are contacted, and the invention adopts a separated gas inlet mode for the two gas sources, wherein one gas source is introduced from the front section of the vapor deposition device, and the other gas source is introduced from the constant temperature reaction zone of the vapor deposition device, so that the vapor deposition can be ensured to be generated in the constant temperature reaction zone, and the invalid deposition generated in other zones can be avoided.
In the invention, the vapor deposition device is divided into three sections, namely a front section, a middle section and a rear section, wherein the front section of the vapor deposition device is a section close to the filament discharging device, and the rear section of the vapor deposition device is a section close to the heat treatment device.
In a preferred scheme, the filament discharging device is provided with a gas inlet C and a gas outlet D, and the gas outlet D of the filament discharging device is connected with a first gas inlet in the vapor deposition device through a pipeline; during vapor deposition, continuously feeding inert gas from a gas inlet C of the filament discharging device, and then feeding the inert gas into the vapor deposition device through a gas outlet D, wherein the flow rate of the inert gas is 1-10.0L/min. As a further preference, the inert gas is nitrogen or argon.
In the preferred scheme, the vapor deposition device is provided with an air outlet E, the air outlet E of the vapor deposition device is positioned at the rear section of the vapor deposition device, and the air outlet E is provided with a pipeline which is connected with a vacuum unit and then connected with a tail gas treatment device through the vacuum unit and is also provided with a pipeline which is directly connected with the tail gas treatment device; in the vapor deposition and heat treatment processes, a vacuum unit is used for pumping negative pressure to control the required deposition pressure, and tail gas generated in deposition is pumped to a tail gas treatment device through the vacuum unit.
In the vapor deposition process, inert gas is introduced from the filament releasing device and enters the vapor deposition device, so that a carrier gas in the vapor deposition process is formed, the filament releasing device is continuously protected by the inert gas, and the filament collecting machine and the roller are prevented from being damaged by gas source gas and byproducts generated in the deposition process.
The heat treatment device is provided with a gas inlet F, the gas inlet F is an inert gas inlet, and inert gas continuously enters from the heat treatment device in the vapor deposition and heat treatment processes. As a further preference, the inert gas is nitrogen or argon. As a further preference, the flow rate of the inert gas is 1.0 to 10.0L/min.
In the invention, the heat treatment device and the vapor deposition device are in through connection, inert gas enters the vapor deposition device from the heat treatment device, and then enters the tail gas treatment device from the gas outlet of the vapor deposition device through the vacuum unit.
Preferably, the heat treatment device comprises a microwave heating system; the constant temperature area of the heat treatment device is a microwave heating area and is positioned in the middle of the heat treatment device;
and in the heat treatment process, the frequency of the microwave is 2.45 GHz.
In the invention, the temperature of the constant temperature reaction zone of the vapor deposition device is higher than that of the non-constant temperature reaction zone of the vapor deposition device, and the temperature of the constant temperature zone of the heat treatment device is higher than that of the non-constant temperature zone, so that in the movement process of the SiC fiber or the SiC fiber bundle, the SiC fiber or the SiC fiber bundle firstly passes through the front non-constant temperature zone of the vapor deposition device to be preheated and then enters the constant temperature reaction zone to be deposited, which is equivalent to that the SiC fiber is subjected to low temperature heat treatment before deposition, and subsequently, the SiC fiber or the SiC fiber bundle moves through the roller set B to pass through the constant temperature zone of the heat treatment device to complete heat treatment, and then the fiber is collected in the fiber collecting machine, and the fiber collecting machine is positioned in the non-constant temperature zone of the heat treatment device, and the temperature is.
In the preferable scheme, n rollers are correspondingly arranged in the roller group A and the roller group B, and n is more than or equal to 1. More preferably, n is 1 to 10. More preferably, n is 2 to 8.
In the invention, according to the arrangement of the roller groups from top to bottom, the rollers in the roller group A are sequentially named as a roller A1, a roller A2 and the like to a roller An, and the rollers in the roller group B are sequentially named as a roller B1, a roller B2 and the like to a roller Bn.
The SiC fibers or SiC fiber bundles from the filament releasing machine move to a roller B1 through a roller A1 to obtain a first layer of amorphous BN coating, then move to a roller A2 from a roller B1 to obtain a second layer of amorphous BN coating, and the like, and finally move to a roller Bn from a roller An to obtain (2n-1) layers of amorphous BN coating.
Preferably, the distance between two adjacent roller grooves of the roller group A and the roller group B is 10-50 mm. Preferably 18-30 mm.
In the preferred scheme, before vapor deposition, vacuum pumping is performed through a vacuum unit connected with a vapor deposition device, then inert gases are respectively introduced from a filament discharging device and a heat treatment device to perform gas replacement, and the gas replacement is performed for 3 times.
Preferably, the vapor deposition device is a tube furnace, and the tube furnace is communicated with the wire unwinding device and the heat treatment device through a furnace tube.
In a preferable scheme, the pipe diameter of a furnace pipe of the tubular furnace is 60-120 mm.
The advantages of the invention are as follows:
1) according to the invention, the SiC fibers or SiC fiber bundles are directly adopted for BN interface deposition, so that the external interference during deposition is reduced to the minimum, uniform coating can be realized, and the phenomena of surface crusting, pore plugging and the like during deposition on a woven body are avoided.
2) In the invention, vapor deposition and heat treatment are carried out in the integrated equipment comprising the filament releasing device, the vapor deposition device, the filament collecting device and the heat treatment device, namely, after the deposition of an amorphous BN interface is finished, the conversion of the crystalline BN coating can be directly carried out, thereby avoiding the decomposition problem of the amorphous BN in the conversion process of deposition and heat treatment in the prior art.
3) In the heat treatment process, a microwave heating mode is adopted, so that the microwave heating speed is high, the microwave heating is uniform, and the method is suitable for heating the SiC fibers, on one hand, the crystal form conversion of an amorphous BN interface is more uniform, the defects in the crystal form growth process are fewer, and the SiC fibers can obtain a BN coating with a stable crystal form structure; on the other hand, the rapid heat treatment enables the damage to the fiber to be minimum, is beneficial to maintaining the mechanical property of the fiber, and compared with the SiC fiber produced by the prior art, the SiC fiber obtained by compacting the SiC matrixfThe strength of the/SiC composite material is improved by 50-180 MPa; the toughness is greatly improved, which can greatly widen the SiCfThe application field of the/SiC composite material.
4) In the integrated equipment, the wire winding and unwinding device adopts a system of a plurality of rollers, SiC fibers or SiC fiber bundles are circulated repeatedly, deposition time is several times longer than that of a common unidirectional wire traveling device, wire traveling speed can be increased on the premise of obtaining sufficient deposition time, and therefore production efficiency is greatly improved.
In conclusion, the crystalline BN coating can be continuously, uniformly and quickly obtained on the surface of the SiC fiber by utilizing the integrated equipment and setting the process parameters matched with the integrated equipment.
Drawings
FIG. 1 is a schematic structural diagram of the present invention
In the figure, 1, a filament unwinding device; 2. a vapor deposition apparatus; 3. a heat treatment device; 11. an air inlet C; 12. a filament releasing machine; 13. a roller set A; 21. a second air inlet; 23. a constant temperature reaction zone; 24. a third air inlet; 31. a roller set B; 32. a silk collecting machine; 33. a constant temperature area; 34. an air inlet F;
FIG. 2 is a schematic winding diagram of SiC fibers;
in the figure, 12, a filament releasing machine; 13. a roller set A; 2. a vapor deposition apparatus; 23. a constant temperature reaction zone; 31. a roller set B; 32. a silk collecting machine;
FIG. 3 is a SEM picture of a section of a SiC fiber prepared in example 1;
FIG. 4 is a SEM picture of a section of a SiC fiber prepared in example 2;
FIG. 5 is a SEM picture of a section of a SiC fiber prepared in example 3;
FIG. 6 is a SEM picture of a section of a SiC fiber prepared in example 4;
fig. 7 is a SEM picture of a cross section of the SiC fiber prepared in comparative example 5.
Detailed description of the invention
The invention is further explained below with reference to the drawings and the embodiments.
The integrated equipment comprises the following components:
the device comprises a wire feeding device 1, a vapor deposition device 2, a wire collecting device and a heat treatment device 3, wherein the vapor deposition device 2 is a tube furnace, the diameter of the tube furnace is 100mm, the wire feeding device 1 and the heat treatment device 3 are positioned on two sides of the vapor deposition device 2, and the tube furnace, the wire feeding device 1 and the heat treatment device 3 are communicated through a furnace tube of the tube furnace. The wire collecting device is arranged in a heat treatment device 3, and the heat treatment device 3 comprises a microwave heating system; the middle part of the microwave heating system is provided with a constant temperature area 33, the filament feeding device 1 comprises a filament feeding machine 12, a roller group A13 and a sealable chamber, the filament feeding machine 12 and the roller group A13 are positioned in the sealable chamber, and the sealable chamber is communicated with the vapor deposition device 2; the wire collecting device comprises a wire collecting machine 32 and a roller group B31; the roller group A13 and the roller group B31 are respectively provided with 5 rollers; the distance between two adjacent roller grooves of the roller group A13 or the roller group B31 is 20 mm. The roller group B31 and the wire collecting machine 32 are arranged at two sides of the constant temperature area 33 of the heat treatment device. A constant-temperature reaction zone 23 is arranged in the vapor deposition device 2; the vapor deposition device 2 is also provided with a first gas inlet, a second gas inlet 21, a third gas inlet 24 and a gas outlet E, the second gas inlet 21 is positioned at the front section of the vapor deposition device 2, and the third gas inlet 24 is positioned in a constant temperature reaction zone 23 of the vapor deposition device 2; the filament discharging device 1 is provided with a gas inlet C11, and a gas outlet D of the filament discharging device is connected with a first gas inlet in the vapor deposition device through a pipeline; and the gas outlet E of the vapor deposition device 2 is connected with a vacuum unit through a pipeline and then connected with a tail gas treatment device through the vacuum unit or directly connected with the tail gas treatment device through a pipeline. The heat treatment apparatus has a gas inlet F34 for inert gas.
The following examples were operated using the above equipment:
example 1:
the vapor deposition device 2 and the heat treatment device 3 were first evacuated by the evacuation system, and since the filament feeding device 1 and the vapor deposition device 2 were in a through state, evacuation was performed, and then argon gas was introduced from the gas inlet C11 of the filament feeding device 1, and nitrogen gas was introduced from the gas inlet F34 of the heat treatment device 3, respectively, to perform gas replacement 3 times.
And after the gas replacement is finished, performing a deposition stage, continuously introducing argon into a gas inlet C11 of the filament discharging device 1, controlling the flow of the argon to be 1.0L/min, and continuously introducing nitrogen into the filament discharging device 3 from a gas inlet F34, wherein the flow of the nitrogen is 1.0L/min.
Using BI in the deposition process3And NH3As source gas, H2As a diluent gas, NH3In the deposition furnace, BI is performed from a second gas inlet 21 of the vapor deposition apparatus 23Gasified and then H2In the deposition furnace from the third air inlet 24, the deposition temperature of the constant temperature reaction zone 23 is controlled to be 900 ℃, the deposition pressure is controlled to be 5000Pa, and the BI3The flow of (2) is 0.2L/min, the flow of ammonia gas is 0.5L/min, the flow of hydrogen gas is 0.2L/min, and the wire moving speed is 0.8 m/min. The temperature of the constant temperature zone 23 of the heat treatment apparatus 2 was set to 1800 ℃ and a microwave heating method was used, the microwave frequency being 2.45 GHz. The single-beam SiC fiber comes out of the filament releasing machine 1, is wound back and forth between the roller group A13 and the roller group B31 and passes through a deposition furnace tube, 9 BN deposition reactions are carried out when the single-beam SiC fiber passes through the constant temperature reaction zone 23, the crystal form conversion of the single-beam SiC fiber is carried out when the single-beam SiC fiber passes through the constant temperature zone 33 of the heat treatment device 3 after the cycle deposition is completed to form a crystalline BN interface, and finally the filament collecting machine 32 finishes filament collection. And treating tail gas and waste gas by a tail gas treatment device.
After 500min time, the deposition of the BN coating of the 250mSiC fibers was complete, giving a BN coating thickness of 110 nm.
Fig. 3 is a SEM picture of a cross section of the SiC fiber prepared in example 1.
Example 2:
the vapor deposition apparatus 2 and the heat treatment apparatus 3 were first evacuated by a vacuum evacuation system, and since the filament feeding apparatus 1 and the vapor deposition apparatus 2 were in a through state, evacuation was performed, and then argon gas was fed from the gas inlet C11 of the filament feeding apparatus 1 and nitrogen gas was fed from the gas inlet F34 of the heat treatment apparatus 3, respectively, to perform gas replacement 3 times.
And after the gas replacement is finished, performing a deposition stage, continuously introducing argon into a gas inlet C11 of the filament discharging device 1, controlling the flow of the argon to be 4.0L/min, and continuously introducing nitrogen into the filament discharging device from a gas inlet F34 of the heat treatment device 3, wherein the flow of the nitrogen is 1.0L/min.
BCl is adopted in the deposition process3And NH3As source gas, H2As a diluent gas, NH3In the deposition furnace from the second gas inlet 21 of the vapor deposition apparatus 2, BCl3And H2In the deposition furnace from the third air inlet 24, the deposition temperature of the constant temperature reaction zone 23 is controlled to be 900 ℃, the deposition pressure is controlled to be 5000Pa, and the BCl3The flow rate of (2) is 0.2L/min, the NH3The flow rate of (2) is 0.5L/min, the said H2The flow rate of (A) is 0.2L/min, and the wire-moving speed is 0.5 m/min. The temperature of the constant temperature zone 23 of the heat treatment apparatus 2 was set to 1300 ℃ and the microwave frequency was set to 2.45 GHz. The single-beam SiC fiber comes out of the filament releasing machine 1, is wound back and forth between the roller group A13 and the roller group B31 and passes through a deposition furnace tube, 9 BN deposition reactions are carried out when the single-beam SiC fiber passes through the constant temperature reaction zone 23, the crystal form conversion of the single-beam SiC fiber is carried out when the single-beam SiC fiber passes through the constant temperature zone 33 of the heat treatment device 3 after the cycle deposition is completed to form a crystalline BN interface, and finally the filament collecting machine 32 finishes filament collection. And treating tail gas and waste gas by a tail gas treatment device.
After 500min time, the deposition of the BN coating of the 250mSiC fibers was complete, resulting in a BN coating thickness of 400 nm.
Fig. 4 is a SEM picture of a section of the SiC fiber prepared in example 2.
Example 3:
the vapor deposition device 2 and the heat treatment device 3 were first evacuated by the evacuation system, and since the filament feeding device 1 and the vapor deposition device 2 were in a through state, evacuation was performed, and then argon gas was introduced from the gas inlet C11 of the filament feeding device 1, and nitrogen gas was introduced from the gas inlet F34 of the heat treatment device 3, respectively, to perform gas replacement 3 times.
And after the gas replacement is finished, performing a deposition stage, continuously introducing argon into a gas inlet C11 of the filament discharging device 1, controlling the flow of the argon to be 10.0L/min, and continuously introducing nitrogen into the filament discharging device 3 from a gas inlet F34 of the heat treatment device 3, wherein the flow of the nitrogen is 4.0L/min.
BCl is adopted in the deposition process3And NH3As source gas, H2As a diluent gas, NH3In the deposition furnace from the second gas inlet 21 of the vapor deposition apparatus 2, BCl3And H2In the deposition furnace from the third air inlet 24, the deposition temperature of the thermostatic reaction zone is controlled to be 1100 ℃, the deposition pressure is controlled to be 20000Pa, and the BCl3The flow rate of (2) is 0.5L/min, the NH3The flow rate of (A) is 1.0L/min, the flow rate of (B) is H2The flow rate of (A) is 0.5L/min, and the wire-moving speed is 0.3 m/min. The temperature of the constant temperature zone 23 of the heat treatment apparatus 2 was set at 1450 ℃ and the microwave frequency was set at 2.45 GHz. The single-beam SiC fiber comes out of the filament pay-off machine 12, is wound back and forth between the roller group a13 and the roller group B31 and passes through the deposition furnace tube, 9 times of BN deposition reaction are performed while passing through the constant temperature reaction zone 23, the crystal form conversion performed by the single-beam SiC fiber after the circulation deposition is completed while passing through the constant temperature zone 33 of the heat treatment device 3 forms a crystalline BN interface, and finally the filament take-up machine 32 completes filament take-up. And treating tail gas and waste gas by a tail gas treatment device.
After 500min, the deposition of the BN coating to 150mSiC fibers was complete, and the thickness of the resulting BN coating was 1200 nm.
FIG. 5 is a SEM picture of a section of a SiC fiber prepared in example 3.
Example 4:
the vapor deposition device 2 and the heat treatment device 3 were first evacuated by the evacuation system, and since the filament feeding device 1 and the vapor deposition device 2 were in a through state, evacuation was performed, and then argon gas was introduced from the gas inlet C11 of the filament feeding device 1, and nitrogen gas was introduced from the gas inlet F34 of the heat treatment device 3, respectively, to perform gas replacement 3 times.
And after the gas replacement is finished, performing a deposition stage, continuously introducing argon into a gas inlet C11 of the filament discharging device 1, controlling the flow of the argon to be 3.0L/min, and continuously introducing nitrogen into the filament discharging device from a gas inlet F34 of the heat treatment device 3, wherein the flow of the nitrogen is 10.0L/min.
BBr is adopted in the deposition process3And NH3As source gas, H2As a diluent gas, NH3In the deposition furnace from the second gas inlet 21 of the vapor deposition apparatus 2, BBr3Is gasified and then reacts with H2The deposition temperature of the constant temperature reaction zone 23 is controlled to be 1000 ℃, the deposition pressure is controlled to be 50000Pa, and the BBr is controlled in the deposition furnace from the third air inlet 243The flow of the ammonia gas is 1.0L/min, the flow of the ammonia gas is 3.0L/min, the flow of the hydrogen gas is 1.0L/min, and the wire moving speed is 0.1 m/min. The temperature of the constant temperature zone 23 of the heat treatment apparatus 2 was set to 1600 ℃ and the microwave frequency was set to 2.45 GHz. The single-beam SiC fiber comes out of the filament releasing machine 1, is wound back and forth between the roller group A13 and the roller group B31 and passes through a deposition furnace tube, 9 BN deposition reactions are carried out when the single-beam SiC fiber passes through the constant temperature reaction zone 23, the crystal form conversion of the single-beam SiC fiber is carried out when the single-beam SiC fiber passes through the constant temperature zone 33 of the heat treatment device 3 after the cycle deposition is completed to form a crystalline BN interface, and finally the filament collecting machine 32 finishes filament collection. And treating tail gas and waste gas by a tail gas treatment device.
After 500min time, deposition of a BN coating of 50mSiC fibers was complete, resulting in a BN coating thickness of about 2000 nm.
Fig. 6 is a SEM picture of a section of the SiC fiber prepared in example 4.
Comparative example 1
The rest conditions are the same as those of the example 2, but the heat treatment device is not carried out in the operation process, and the drawn wire is taken out and then is placed in equipment for heat treatment. On one hand, part of amorphous BN coating is decomposed in the process of taking out the fiber, and on the other hand, the temperature difference exists between the inside and the outside of the fiber mass in the heat treatment process, and the more inward the fiber surface, the poorer the crystal form of the BN coating is.
Comparative example 2
The rest conditions are the same as those of the example 1, and the microwave heating mode is not adopted in the heat treatment process, but the resistance heating mode is adopted. As a result, it was found that the crystallization was incomplete.
Comparative example 3
The other conditions were the same as in example 3, and the microwave heating method was not used but the resistance heating method was used in the heat treatment. Since there was a case where crystallization was incomplete at 1600 ℃, the heat treatment temperature was adjusted to 2100 ℃. As a result, there is greater damage to the fibers.
Comparative example 4
The other conditions are the same as those of example 1, but the flow rate of argon is 0.2L/min, the flow rate of boron trichloride is 0.1L/min, the flow rate of ammonia is 0.3L/min, the flow rate of hydrogen is 0.1L/min, the flow rate of nitrogen is 5L/min, the pressure in the deposition furnace is 20000pa, and the thickness of the obtained BN coating is extremely thin and cannot be accurately measured, and is about 20 nm.
Comparative example 5
The other conditions were the same as in example 1, the running speed was 1.0m/min, and the thickness of the obtained BN coating was 50 nm.
Fig. 7 is a SEM picture of a cross section of the SiC fiber prepared in comparative example 5.
Performance testing
After weaving the BN-containing coatings of the examples and comparative examples, SiC was obtained by vapor depositionfThe performance of the/SiC composite material after processing is tested, and the performance results are shown in Table 1.
TABLE 1 SiCfPerformance test of/SiC composite material
Density g/cm3 Tensile strength/MPa Strong bendingdegree/MPa Fracture toughness/MPa.m1/2
Example 1 2.51 355 217 23.2
Example 2 2.56 412 285 28.5
Example 3 2.66 432 295 33.5
Example 4 2.45 406 283 26.7
Comparative example 1 2.43 357 236 24.1
Comparative example 2 2.41 329 213 20.3
Comparative example 3 2.45 256 133 13.4
Comparative example 4 2.40 280 198 16.5
Comparative example 5 2.38 295 205 18.4
From the comparison of the performance of the above examples with that of the comparative example, it can be seen that: the SiC fiber with the 400-plus-2000 nmBN coating obtained by the preparation method is woven and the SiC matrix is densified to obtain SiCfCompared with the traditional mode of depositing, taking out and then carrying out heat treatment, a sample piece with insufficient BN thickness and a sample piece not adopting microwave treatment, the strength and the toughness of the/SiC composite material are improved by 50-180MPa, and more importantly, the SiC composite material has the advantages thatfThe toughness of the/SiC composite material is also greatly improved.

Claims (9)

1. A method for continuously and rapidly preparing a BN coating on the surface of SiC fibers is characterized by comprising the following steps:
in the integrated equipment, under the protection of inert gas, the SiC fibers are subjected to vapor deposition to form an amorphous BN coating, and then the SiC fibers with the amorphous BN coating are directly subjected to heat treatment to form a crystalline BN coating;
the integrated equipment comprises a vapor deposition device, a heat treatment device, a wire releasing device and a wire collecting device; the filament-releasing device and the heat treatment device are positioned at two sides of the vapor deposition device and are communicated with the vapor deposition device;
the filament discharging device comprises a filament discharging machine, a roller group A and a sealable chamber, wherein the filament discharging machine and the roller group A are positioned in the sealable chamber, and the sealable chamber is communicated with the vapor deposition device;
the wire releasing device comprises a wire collecting machine and a roller set B; and placing in a heat treatment device;
the heat treatment device is provided with a constant temperature area, and the roller group B and the wire collecting machine are arranged on two sides of the constant temperature area of the heat treatment device;
the SiC fibers come out of the filament releasing machine, are turned by the roller set A, move from the roller set A to the roller set B, are subjected to vapor deposition by the vapor deposition device to form an amorphous BN coating, are turned by the roller set B, move to the filament releasing machine, are subjected to heat treatment in a constant temperature area of the heat treatment device to form a crystalline BN coating, and are finally taken up by the filament collecting device;
the vapor deposition temperature is 800-1200 ℃, and the vapor deposition pressure is 3000-80000 Pa; the filament traveling speed of the SiC fibers is 0.1-2 m/min; the temperature of the heat treatment is 1200-2000 ℃, and the thickness of the obtained SiC fiber BN crystalline coating is 100-4000 nm.
2. The method for continuously and rapidly preparing the BN coating on the surface of the SiC fiber according to claim 1, is characterized in that: a constant-temperature reaction zone is arranged in the vapor deposition device; the vapor deposition device is provided with a first air inlet, a second air inlet and a third air inlet; the first gas inlet is an inert gas inlet, the second gas inlet and the third gas inlet are a gas source gas and a diluent gas inlet, the second gas inlet is positioned at the front section of the vapor deposition device, and the third gas inlet is positioned in a constant-temperature reaction zone of the vapor deposition device;
during vapor deposition, non-metal boride and NH are used3As source gas, H2Is a diluent gas; is notMetal boride and NH3Air is respectively fed from the second air inlet and the third air inlet; h2Intake air from the second intake port or the third intake port; the flow rate of the non-metal boride is 0.1-1.5L/min, and the NH is3The flow rate of (A) is 0.3-5.0L/min, the flow rate of (B) is H2The flow rate of (A) is 0.1-1.5L/min.
3. The method for continuously and rapidly preparing the BN coating on the surface of the SiC fiber according to claim 1, wherein the filament discharging device is provided with a gas inlet C and a gas outlet D, and the gas outlet D of the filament discharging device is connected with a first gas inlet in a gas phase deposition device through a pipeline; during vapor deposition, continuously introducing inert gas from a gas inlet C of the filament discharging device, and introducing the inert gas into the vapor deposition device through a gas outlet D, wherein the flow rate of the inert gas is 1.0-10.0L/min;
the heat treatment device is provided with a gas inlet F, the gas inlet F is an inert gas inlet, and inert gas is continuously fed from the heat treatment device in the vapor deposition and heat treatment processes; the flow rate of the inert gas is 1.0-10.0L/min.
4. The method for continuously and rapidly preparing the BN coating on the surface of the SiC fiber according to claim 1, wherein the vapor deposition device is provided with an air outlet E, the air outlet E of the vapor deposition device is positioned at the rear section of the vapor deposition device, and is provided with a pipeline which is connected with a vacuum unit and then connected with a tail gas treatment device through the vacuum unit, and is also provided with a pipeline which is directly connected with the tail gas treatment device; in the vapor deposition and heat treatment processes, a vacuum unit is used for pumping negative pressure to control the required deposition pressure, and tail gas generated in deposition is pumped to a tail gas treatment device through the vacuum unit.
5. The continuous and rapid method for preparing BN coating on the surface of SiC fiber according to claim 1 or 3, characterized in that the heat treatment device comprises a microwave heating system; the constant temperature area of the heat treatment device is a microwave heating area and is positioned in the middle of the heat treatment device;
and in the heat treatment process, the frequency of the microwave is 2.45 GHz.
6. The method for continuously and rapidly preparing BN coating on the surface of SiC fiber as claimed in claim 2, wherein the temperature of the vapor deposition is 900-1100 ℃, and the pressure of the vapor deposition is 5000-50000 Pa; the filament running speed of the SiC fiber is 0.1-2 m/min; the temperature of the heat treatment is 1250-3The flow rate of (A) is 0.5-3.0L/min, the flow rate of (B) is H2The flow rate of (A) is 0.2-1.0L/min.
7. The method for continuously and rapidly preparing the BN coating on the surface of the SiC fiber according to claim 1, wherein n rollers are respectively arranged in the roller group A and the roller group B; n is more than or equal to 1;
the SiC fibers from the filament releasing machine move to a roller B1 through a roller A1 to obtain a first layer of amorphous BN coating, then move to a roller A2 from a roller B1 to obtain a second layer of amorphous BN coating, and the like, and finally move to a roller Bn from a roller An to obtain (2n-1) layers of amorphous BN coatings.
8. The method for continuously and rapidly preparing the BN coating on the surface of the SiC fiber according to claim 1, wherein the distance between two adjacent roller grooves of the roller group A and the roller group B is 10-50 mm.
9. The method for continuously and rapidly preparing the BN coating on the surface of the SiC fiber according to claim 1, is characterized in that: the vapor deposition device is a tubular furnace, and the tubular furnace is communicated with the wire feeding device and the heat treatment device through a furnace tube; the pipe diameter of the furnace pipe of the pipe furnace is 60-120 mm.
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