CN117865708A - Preparation method of whisker reinforced ceramic matrix composite connecting fastener - Google Patents
Preparation method of whisker reinforced ceramic matrix composite connecting fastener Download PDFInfo
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- CN117865708A CN117865708A CN202311788952.XA CN202311788952A CN117865708A CN 117865708 A CN117865708 A CN 117865708A CN 202311788952 A CN202311788952 A CN 202311788952A CN 117865708 A CN117865708 A CN 117865708A
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Abstract
The invention discloses a preparation method of a whisker reinforced ceramic matrix composite connecting fastener, which relates to the technical field of connecting fastener preparation and sequentially comprises the following steps: (1) After cleaning the fiber preform, removing the fiber surface glue coating, and preparing a uniform and compact BN interface; (2) Adopting a CVD/CVI method to prepare a compact SiC matrix and a coating; (3) Cutting and rounding the pre-densified fiber preform according to a size standard; (4) Dipping a pre-processed sample by using SiC whisker slurry by adopting a vacuum dipping method, and then sequentially carrying out heating solidification, thread processing and high-temperature cracking; and (5) finally, depositing a SiC protective layer on the surface by adopting a CVI method. According to the preparation method, the SiC whisker reinforced layer is prepared on the surface layer of the ceramic bolt by adopting Dip-coating and CVI processes, so that the thread tooth shape is optimized, the compactness, the extrusion resistance and the engagement precision of the thread tooth are effectively improved, and the thread tooth is obviously reinforced.
Description
Technical Field
The invention relates to the technical field of connecting fastener preparation, in particular to a preparation method of a whisker reinforced ceramic matrix composite connecting fastener.
Background
The ceramic matrix composite is a novel thermal structure/function integrated material with the performance advantages of metal materials, ceramic materials and carbon materials, and is widely applied to various fields such as aerospace, tip military use, emerging civilian use and the like. According to the preparation process and application requirements of ceramic matrix composite materials, CMC-SiC components are mostly large complex thin-wall components, such as wings, rudders, cabin sections and the like in hypersonic aircrafts are connected by adopting thin-wall tubular, box-shaped or skin-like components. Studies have shown that the strength of the joint is the weakest link in the integrated assembly member. Thus, this places higher performance demands on the joining fasteners of the ceramic matrix composite components.
In the development process of the component, the existing fastener with the structure of the plate cutting two-dimensional laminated preform or the three-dimensional needling preform gradually shows a fatigue state, is influenced by the fracture energy of a matrix, the bridging stress of fibers and the porosity, is easy to crush and damage, and has lower shearing resistance and strength. Therefore, in order to improve the shearing or stretching bearing capacity of the ceramic matrix composite material fastener, on one hand, the porosity of the ceramic matrix composite material fastener needs to be reduced, and the shearing modulus and the cracking stress of a matrix are improved, and on the other hand, the surface layer of the preform is optimized through micro-nano toughening technology, so that the high-performance fastener is prepared. The interaction mechanism of the fiber and the matrix microcracks is optimized, and the fiber bridging stress and the toughness of the composite material are improved.
Therefore, in order to ensure the reliability of the assembly of ceramic matrix composite components, there is an urgent need to develop a ceramic matrix composite fastener with high connection strength, shear resistance and tensile properties, which provides a powerful support for the integrated assembly and manufacture of large complex thin-walled components of ceramic matrix composites.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of a whisker reinforced ceramic matrix composite connecting fastener, which adopts a Dip-coating and CVI process to prepare a SiC whisker reinforced layer on the surface layer of a ceramic bolt, optimizes thread teeth, effectively improves thread tooth compactness, extrusion resistance and engagement precision, remarkably strengthens the thread teeth, and solves the problems of insufficient strength, high mechanical property dispersibility, no thread reinforcing process, easy thread tooth breakage, insufficient thread tooth pulling and bearing performance and the like of the conventional ceramic matrix composite connecting fastener.
The technical scheme for solving the technical problems is as follows: the preparation method of the whisker reinforced ceramic matrix composite connecting fastener comprises the following steps in sequence:
(1) And (3) preparation interface: firstly, cleaning a fiber preform by using acetone, then heating to 400-600 ℃, preserving heat for 2-4 hours to remove a fiber surface glue coating, cooling along with a furnace, and preparing uniform and compact BN interface in the fiber preform and on the surface;
(2) Pre-densification: preparing a compact SiC matrix and a coating on the inner part and the surface of the fiber preform by adopting a CVD/CVI method;
(3) Preprocessing: cutting and rounding the pre-densified fiber preform according to the size standards of various fasteners to obtain a pre-processed sample;
(4) Dip-coating method for preparing coating: dipping the pre-processed sample obtained in the step (3) by using SiC whisker slurry by adopting a vacuum dipping method, and then sequentially carrying out heating curing, thread processing and high-temperature cracking;
(5) And finally, depositing a SiC protective layer on the surface by adopting a CVI method to obtain the whisker reinforced ceramic matrix composite connecting fastener.
Further, the connecting fastener is a pin, a screw rod, a stud or a nut.
Further, in the step (1), the fibers of the fiber preform are C fibers, siC fibers or Si 3 N 4 A fiber; the fiber preform is a two-dimensional fiber cloth laminate, a three-dimensional woven preform or a three-dimensional needled woven preform.
Further, in the step (1), the preparation method of the BN interface is a CVD/CVI method, and when the BN interface is prepared: simultaneously introducing boron trichloride and ammonia gas, wherein the diluent gas is argon, the catalytic gas is hydrogen, the flow rate of the boron trichloride is 0.15-0.3L/min, the flow rate of the ammonia gas is 0.25-0.5L/min, the flow rate of the argon gas is 0.6-2L/min, the flow rate of the hydrogen gas is 0.5-1L/min, the pressure in the furnace is 2-5kPa, and the deposition is carried out for 10-50h at the temperature of 650-900 ℃.
Further, in the step (1), BN interface is 200-1500nm; preferably 1000nm.
Further, in step (2), when pre-densification: the precursor is silicon tetrachloride, the diluent gas is argon, the catalytic gas is hydrogen, the flow of the argon is 2.5-10L/min, the flow of the hydrogen carrier gas is 1.5-5L/min, the flow of the hydrogen diluent gas is 2.5-5L/min, the reaction temperature is 700-1100 ℃, the heat preservation time is 20-100h, and the pressure in the furnace is 1-5kPa.
Further, the density of the material after pre-densification reaches 1.3-1.6g/cm 3 。
Further, in the step (4), the SiC whisker slurry is prepared by the following steps:
(1) Mixing SiC whisker and solvent at room temperature, and ball milling for 5-8 hours at 200r/min to prepare SiC whisker solution with volume fraction of 5-20%;
(2) The adhesive is added into ethanol under water bath at 50-70 ℃ and stirring to prepare adhesive solution with the mass fraction of 6-10%;
(3) Adding 30-40% of the binder solution obtained in the step (2) into the SiC whisker solution obtained in the step (1), then adding 3-5% of dispersing agent and 2-3% of plasticizer, continuing ball milling for 5-8h at 200r/min, and then removing bubbles in vacuum to obtain stable slurry;
(4) Mixing a precursor polymer and a crosslinking agent according to a mass percentage of 1:3 to obtain a precursor solution;
(5) And (3) mixing the precursor solution obtained in the step (4) with the stable slurry obtained in the step (5) according to the volume ratio of 5-20:100 to obtain SiC whisker slurry.
Still further, the SiC whiskers may be replaced with one of a and b:
a. the mass ratio is 2.5-1:1 and a mixture of SiC whiskers and SiC particles;
b. the mass ratio is 2-1:0.5:0.5 SiC whisker, si powder and C powder mixture.
Still further, the SiC whisker has a diameter of 600nm and a length of 10-50 μm; the particle size of the SiC particles is 1.5-2 mu m; the grain size of Si powder is 200-300 μm. The method comprises the steps of carrying out a first treatment on the surface of the The particle size of the powder C is 30nm.
Still further, the solvent for preparing the SiC whisker slurry is ethanol, acetone or water.
Still further, the dispersant used to prepare the SiC whisker slurry is polyvinylpyrrolidone (PVP), triethyl phosphate, tetramethylammonium hydroxide (TMAH), or Polyethylenimine (PEI).
Still further, the binder for preparing the SiC whisker slurry is polyvinyl butyral (PVB), polyvinyl alcohol (PVA), or silica sol.
Still further, the plasticizer for preparing the SiC whisker slurry was glycerol, a collar phthalate (DOP, DBP, DIDP), a phosphate ester (tricresyl phosphate TCP, cresyl diphenyl phosphate CDP) or a polymeric plasticizer (propylene glycol polyester adipate).
Still further, the precursor polymer is one or more of silicon-based or ultra-high temperature-based precursor solutions such as polycarbosilane, polysilazane, polyzirconocarbonane, polyborozirconane, and the like.
Still further, the crosslinking agent is dicumyl peroxide (DCP) or Divinylbenzene (DVB).
Further, in the step (4), when heating and curing: under the protection of argon or nitrogen atmosphere and under the condition of vacuum degree of 0.09MPa, heating to 100-300 ℃ at 3-10 ℃/min, preserving heat for 1-3h, and then cooling to room temperature at 3-5 ℃/min.
Further, in the step (4), at the time of pyrolysis: under the protection of argon or nitrogen atmosphere and under the condition of 0.09MPa of vacuum degree, heating to 1200-1500 ℃ at 3-10 ℃/min, preserving heat for 2-4h, cooling to 600 ℃ at 3-10 ℃/min, and cooling along with a furnace.
Further, in step (5), when depositing the SiC protective layer: the precursor is silicon tetrachloride, the diluent gas is argon, the catalytic gas is hydrogen, the flow of the argon is 2.5-10L/min, the flow of the hydrogen carrier gas is 1.5-5L/min, the flow of the hydrogen diluent gas is 2.5-5L/min, the reaction temperature is 700-1100 ℃, the heat preservation time is 8-20h, and the pressure in the furnace is 1-5kPa.
The friendship effect of the technical scheme of the invention is as follows: the Dip-coating technology is adopted to realize the strengthening of the surface layer of the whisker reinforced fastener, so that the integrity of threads after the fasteners such as pins, screws, screw rods, studs and nuts are processed is improved, and the pull-out resistance of thread teeth is improved; the thickness of the whisker reinforced layer and the connection strength between the whisker reinforced layer and the matrix can be regulated and optimized by controlling the volume fraction and the viscosity of the SiC whisker slurry; the whisker reinforced ceramic matrix composite fastener prepared by the method comprises fibers, interfaces, siC whiskers and a ceramic matrix, and a global load sharing mechanism is established, so that the connection efficiency of the CMC-SiC fastener can be effectively improved.
The invention also provides the whisker reinforced ceramic matrix composite connecting fastener prepared by the preparation method of the whisker reinforced ceramic matrix composite connecting fastener.
The invention has the following beneficial effects:
1. the ceramic matrix composite material after SiC whisker reinforcement is connected with a fastener to form evenly distributed reinforcements in the thread teeth, so that the tensile property is improved by 38.28%;
2. the ceramic matrix composite material after SiC whisker reinforcement is connected with the fastener, so that the compactness and the toughness of the stud are obviously enhanced, and the shearing performance is improved by 36.37%;
3. the ceramic matrix composite material connecting fastener reinforced by the SiC whiskers optimizes teeth, effectively improves the compactness, the extrusion resistance and the engagement precision of the thread teeth, and remarkably strengthens the thread teeth;
4. the SiC whisker reinforced layer is prepared on the surface layer of the ceramic bolt by adopting a Dip-coating process and a CVI process, so that the residual pore of the preform structure and the pore caused by the CVI process can be filled, the compactness of the ceramic matrix composite bolt is improved, the modulus mismatch between the C/SiC composite material and the SiC protective layer can be effectively relieved, and the toughness of the C/SiC matrix composite bolt is improved.
Drawings
FIG. 1 is a flow chart of the preparation of a whisker reinforced ceramic matrix composite attachment fastener (bolt) of example 1;
FIG. 2 is a process route diagram for the preparation of a ceramic matrix composite bolt of comparative example 1;
FIG. 3 is a schematic view of the thread form CT of a ceramic matrix composite bolt of comparative example 1;
FIG. 4 is a schematic view of the thread form CT of a whisker reinforced ceramic matrix composite attachment fastener (bolt) of example 1;
FIG. 5 is a schematic view of a cross section and a surface SEM of a ceramic matrix composite bolt of comparative example 1;
FIG. 6 is a schematic cross-sectional and surface SEM of a whisker reinforced ceramic matrix composite tie-down fastener (bolt) of example 1;
FIG. 7 is a schematic illustration of SEM of the surface and interior of a whisker reinforced ceramic matrix composite attachment fastener (bolt) of example 1.
Detailed Description
The principles and features of the present invention are described below with examples given for the purpose of illustration only and are not intended to limit the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The preparation flow chart of the whisker reinforced ceramic matrix composite connecting fastener (bolt) is shown in fig. 1, and the preparation method sequentially comprises the following steps:
(1) And (3) preparation interface: firstly, cleaning a three-dimensional needling weaving preform by using acetone, then heating to 500 ℃, preserving heat for 3 hours to remove a fiber surface glue coating, cooling along with a furnace, and preparing uniform and compact BN interfaces in and on the three-dimensional needling preform; the preparation method of BN interface is CVD/CVI method, when BN interface is prepared: simultaneously introducing boron trichloride and ammonia gas, wherein the diluent gas is argon, the catalytic gas is hydrogen, the flow rate of the boron trichloride is 0.2L/min, the flow rate of the ammonia gas is 0.3L/min, the flow rate of the argon gas is 1L/min, the flow rate of the hydrogen gas is 0.8L/min, the pressure in the furnace is 3kPa, and the deposition is carried out at 800 ℃ for 24 hours;
(2) Pre-densification: preparing a compact SiC matrix and a coating on the inner part and the surface of the fiber preform by adopting a CVD/CVI method; when pre-densification: the precursor is silicon tetrachloride, the diluent gas is argon, the catalytic gas is hydrogen, the argon flow is 5L/min, the hydrogen carrier gas flow is 3L/min, the hydrogen diluent gas flow is 3L/min, the reaction temperature is 1000 ℃, the heat preservation time is 48h, and the pressure in the furnace is 3kPa;
(3) Preprocessing: cutting and rounding the pre-densified fiber preform according to the size standards of various fasteners to obtain a pre-processed sample;
(4) Dip-coating method for preparing coating: dipping the pre-processed sample obtained in the step (3) by using SiC whisker slurry by adopting a vacuum dipping method, and then sequentially carrying out heating curing, thread processing and high-temperature cracking; and (3) heating and curing: under the protection of nitrogen atmosphere and under the condition of 0.09MPa of vacuum degree, heating to 200 ℃ at 5 ℃/min, preserving heat for 2 hours, and then cooling to room temperature at 4 ℃/min; when high temperature cracking: under the protection of nitrogen atmosphere and under the condition of 0.09MPa of vacuum degree, 8 ℃/min is heated to 1400 ℃ and is kept for 3 hours, then 8 ℃/min is cooled to 600 ℃, and then the furnace is cooled;
(5) Finally, depositing a SiC protective layer on the surface by adopting a CVI method to obtain the whisker reinforced ceramic matrix composite connecting fastener; when depositing the SiC protective layer: the precursor is silicon tetrachloride, the diluent gas is argon, the catalytic gas is hydrogen, the argon flow is 5L/min, the hydrogen carrier gas flow is 3L/min, the hydrogen diluent gas flow is 3L/min, the reaction temperature is 1000 ℃, the heat preservation time is 15h, and the pressure in the furnace is 4kPa.
In the step (4), the SiC whisker slurry is prepared by the following steps:
(1) Mixing SiC whisker and ethanol at room temperature, and ball-milling for 6 hours at 200r/min to prepare a SiC whisker solution with the volume fraction of 10%;
(2) Polyvinyl butyral is added into ethanol in a water bath at 60 ℃ with stirring to prepare binder solution with the mass fraction of 8%;
(3) Adding 35% of the binder solution obtained in the step (2) into the SiC whisker solution obtained in the step (1), then adding 4% of polyvinylpyrrolidone and 2.5% of glycerol, continuing ball milling for 6 hours at 200r/min, and then removing bubbles in vacuum to obtain stable slurry;
(4) Mixing polycarbosilane and dicumyl peroxide according to a mass percentage of 1:3 to obtain a precursor solution;
(5) And (3) mixing the precursor solution obtained in the step (4) with the stable slurry obtained in the step (5) according to the volume ratio of 15:100 to obtain SiC whisker slurry.
Example 2
The preparation method of the whisker reinforced ceramic matrix composite connecting fastener (bolt) sequentially comprises the following steps:
(1) And (3) preparation interface: firstly, cleaning a three-dimensional needling weaving preform by using acetone, then heating to 400 ℃, preserving heat for 2 hours to remove a fiber surface glue coating, cooling along with a furnace, and preparing uniform and compact BN interfaces in and on the three-dimensional needling preform; the preparation method of BN interface is CVD/CVI method, when BN interface is prepared: simultaneously introducing boron trichloride and ammonia gas, wherein the diluent gas is argon, the catalytic gas is hydrogen, the flow rate of the boron trichloride is 0.15L/min, the flow rate of the ammonia gas is 0.25L/min, the flow rate of the argon gas is 0.6L/min, the flow rate of the hydrogen gas is 0.5L/min, the pressure in the furnace is 2kPa, and the deposition is carried out for 10 hours at 650 ℃;
(2) Pre-densification: preparing a compact SiC matrix and a coating on the inner part and the surface of the fiber preform by adopting a CVD/CVI method; when pre-densification: the precursor is silicon tetrachloride, the diluent gas is argon, the catalytic gas is hydrogen, the flow of the argon is 2.5L/min, the flow of the hydrogen carrier gas is 1.5L/min, the flow of the hydrogen diluent gas is 2.5L/min, the reaction temperature is 700 ℃, the heat preservation time is 20h, and the pressure in the furnace is 1kPa;
(3) Preprocessing: cutting and rounding the pre-densified fiber preform according to the size standards of various fasteners to obtain a pre-processed sample;
(4) Dip-coating method for preparing coating: dipping the pre-processed sample obtained in the step (3) by using SiC whisker slurry by adopting a vacuum dipping method, and then sequentially carrying out heating curing, thread processing and high-temperature cracking; and (3) heating and curing: under the protection of argon atmosphere and under the condition of 0.09MPa of vacuum degree, 3 ℃/min is heated to 100 ℃ and is kept for 1h, and then 3 ℃/min is cooled to room temperature; when high temperature cracking: under the protection of argon atmosphere and under the condition of 0.09MPa of vacuum degree, 3 ℃/min is heated to 1200 ℃ and is kept for 2 hours, then 3 ℃/min is cooled to 600 ℃, and then the furnace is cooled;
(5) Finally, depositing a SiC protective layer on the surface by adopting a CVI method to obtain the whisker reinforced ceramic matrix composite connecting fastener; when depositing the SiC protective layer: the precursor is silicon tetrachloride, the diluent gas is argon, the catalytic gas is hydrogen, the argon flow is 2.5L/min, the hydrogen carrier gas flow is 1.5L/min, the hydrogen diluent gas flow is 2.5L/min, the reaction temperature is 700 ℃, the heat preservation time is 8h, and the pressure in the furnace is 1kPa.
In the step (4), the SiC whisker slurry is prepared by the following steps:
(1) The mass ratio is 2.5:1, mixing the SiC whisker and SiC particle mixture with ethanol at room temperature, and ball-milling for 5 hours at 200r/min to prepare a SiC whisker solution with the volume fraction of 5%;
(2) Polyvinyl alcohol is added into ethanol in a water bath at 50 ℃ and stirred to prepare a binder solution with the mass fraction of 6%;
(3) Adding 30% of the binder solution obtained in the step (2) into the SiC whisker solution obtained in the step (1), then adding 3% of polyethyleneimine and 2% of collar phthalate, continuing ball milling for 5h at 200r/min, and then removing bubbles in vacuum to obtain stable slurry;
(4) Mixing polysilazane and dicumyl peroxide according to a mass percentage of 1:3 to obtain a precursor solution;
(5) And (3) mixing the precursor solution obtained in the step (4) with the stable slurry obtained in the step (5) according to the volume ratio of 5:100 to obtain SiC whisker slurry.
Example 3
The preparation method of the whisker reinforced ceramic matrix composite connecting fastener (bolt) sequentially comprises the following steps:
(1) And (3) preparation interface: firstly, cleaning a three-dimensional needling weaving preform by using acetone, then heating to 600 ℃, preserving heat for 4 hours to remove a fiber surface glue coating, cooling along with a furnace, and preparing uniform and compact BN interfaces in and on the three-dimensional needling preform; the preparation method of BN interface is CVD/CVI method, when BN interface is prepared: simultaneously introducing boron trichloride and ammonia gas, wherein the diluent gas is argon, the catalytic gas is hydrogen, the flow rate of the boron trichloride is 0.3L/min, the flow rate of the ammonia gas is 0.5L/min, the flow rate of the argon gas is 2L/min, the flow rate of the hydrogen gas is 1L/min, the pressure in the furnace is 5kPa, and the deposition is carried out for 50 hours at 900 ℃;
(2) Pre-densification: preparing a compact SiC matrix and a coating on the inner part and the surface of the fiber preform by adopting a CVD/CVI method; when pre-densification: the precursor is silicon tetrachloride, the diluent gas is argon, the catalytic gas is hydrogen, the argon flow is 10L/min, the hydrogen carrier gas flow is 5L/min, the hydrogen diluent gas flow is 5L/min, the reaction temperature is 1100 ℃, the heat preservation time is 100h, and the pressure in the furnace is 5kPa;
(3) Preprocessing: cutting and rounding the pre-densified fiber preform according to the size standards of various fasteners to obtain a pre-processed sample;
(4) Dip-coating method for preparing coating: dipping the pre-processed sample obtained in the step (3) by using SiC whisker slurry by adopting a vacuum dipping method, and then sequentially carrying out heating curing, thread processing and high-temperature cracking; and (3) heating and curing: under the protection of argon atmosphere and under the condition of 0.09MPa of vacuum degree, heating to 300 ℃ at 10 ℃/min, preserving heat for 3 hours, and then cooling to room temperature at 5 ℃/min; when high temperature cracking: under the protection of argon atmosphere and under the condition of 0.09MPa of vacuum degree, heating to 1500 ℃ at 10 ℃/min, preserving heat for 4 hours, cooling to 600 ℃ at 10 ℃/min, and cooling along with a furnace;
(5) Finally, depositing a SiC protective layer on the surface by adopting a CVI method to obtain the whisker reinforced ceramic matrix composite connecting fastener; when depositing the SiC protective layer: the precursor is silicon tetrachloride, the diluent gas is argon, the catalytic gas is hydrogen, the argon flow is 10L/min, the hydrogen carrier gas flow is 5L/min, the hydrogen diluent gas flow is 5L/min, the reaction temperature is 1100 ℃, the heat preservation time is 20h, and the pressure in the furnace is 5kPa.
In the step (4), the SiC whisker slurry is prepared by the following steps:
(1) The mass ratio is 2:0.5: mixing the mixture of the SiC whisker, the Si powder and the C powder of 0.5 with ethanol at room temperature, and ball-milling for 8 hours at 200r/min to prepare a SiC whisker solution with the volume fraction of 20%;
(2) The silica sol is added into ethanol under water bath at 70 ℃ and stirring to prepare binder solution with the mass fraction of 6-10%;
(3) Adding 40% of the binder solution obtained in the step (2) into the SiC whisker solution obtained in the step (1), then adding 5% of triethyl phosphate and 3% of polymeric plasticizer (propylene glycol polyester adipate) in volume, continuing ball milling for 8 hours at 200r/min, and then removing bubbles in vacuum to obtain stable slurry;
(4) Mixing the poly-zirconium-carbon alkane and divinylbenzene according to the mass percentage of 1:3 to obtain a precursor solution;
(5) And (3) mixing the precursor solution obtained in the step (4) with the stable slurry obtained in the step (5) according to the volume ratio of 20:100 to obtain SiC whisker slurry.
Comparative example 1
The preparation process route diagram of the ceramic matrix composite bolt is shown in fig. 2, and the preparation method sequentially comprises the following steps:
the preparation method of the whisker reinforced ceramic matrix composite connecting fastener (bolt) sequentially comprises the following steps:
(1) And (3) preparation interface: firstly, cleaning a three-dimensional needling weaving preform by using acetone, then heating to 400-600 ℃, preserving heat for 2-4 hours to remove a fiber surface glue coating, cooling along with a furnace, and preparing uniform and compact BN interface inside and on the surface of the three-dimensional needling preform; the preparation method of BN interface is a CVD/CVI method, and the preparation conditions are as follows: simultaneously introducing boron trichloride and ammonia gas, wherein the diluent gas is argon, the catalytic gas is hydrogen, the flow rate of the boron trichloride is 0.15-0.3L/min, the flow rate of the ammonia gas is 0.25-0.5L/min, the flow rate of the argon gas is 0.6-2L/min, the flow rate of the hydrogen gas is 0.5-1L/min, the pressure in the furnace is 2-5kPa, and the deposition is carried out for 10-50h at 650-900 ℃;
(2) Pre-densification: preparing a compact SiC matrix and a coating on the inner part and the surface of the fiber preform by adopting a CVD/CVI method; the preparation conditions are as follows: the precursor is silicon tetrachloride, the diluent gas is argon, the catalytic gas is hydrogen, the flow rate of the argon is 2.5-10L/min, the flow rate of the hydrogen carrier gas is 1.5-5L/min, the flow rate of the hydrogen diluent gas is 2.5-5L/min, the reaction temperature is 700-1100 ℃, the heat preservation time is 20-100h, and the pressure in the furnace is 1-5kPa;
(3) Cutting and rounding the pre-densified fiber preform according to the size standards of various fasteners to obtain the ceramic matrix composite bolt.
Test example 1
1. The basic information and mechanical properties of the whisker reinforced ceramic matrix composite joint fastener (bolt) prepared in example 1 and the ceramic matrix composite bolt prepared in comparative example 1 are shown in table 1.
Table 1 basic information and mechanical properties of bolts prepared in example 1 and comparative example 1
| Preparation method | Comparative example 1 | Example 1 |
| Density (g/cm) 3 ) | 2.15-2.21 | 2.25-2.30 |
| Porosity (%) | 14.60-17.99 | 12.03-14.49 |
| Tensile Property (MPa) | 121.08 | 167.43 |
| Double shear performance (MPa) | 60.58 | 82.61 |
As can be seen from Table 1, the porosity of the bolts reinforced by the whiskers is reduced, the density is increased, and the tensile property and the double shear property are improved.
2. Schematic views of thread teeth CT of the whisker reinforced ceramic matrix composite connection fastener (bolt) prepared in example 1 and the ceramic matrix composite bolt prepared in comparative example 1 are shown in fig. 3 and 4, respectively.
As can be seen from the comparison of FIG. 3 and FIG. 4, the thread teeth in FIG. 4 are brighter, which shows that the density is higher, thus proving that the bolt reinforced by the whisker prepared by the method is denser, the thread teeth are complete and sharp, and the density and strength of the thread teeth are also greatly improved.
3. SEM examination was performed on the cross section and the surface of the whisker-reinforced ceramic matrix composite joint fastener (bolt) obtained in example 1 and the ceramic matrix composite bolt obtained in comparative example 1, and the results are shown in fig. 5 and 6, respectively.
As can be seen from the comparison between the figures 5 and 6, the whisker exists on the surface layer and in the interior of the bolt after the preparation method of the invention, the appearance of the thread tooth after whisker reinforcement is better as the appearance of the surface of the bolt is known, the whole bolt is more compact, and the tensile and shearing performances of the bolt are improved.
4. A schematic of the surface and interior SEM of the whisker reinforced ceramic matrix composite tie fasteners (bolts) prepared in example 1 is shown in FIG. 7.
As can be seen from FIG. 7, the whisker reinforced layer prepared by the preparation method of the present invention has a thickness of 120-160 μm; the surface layer of the sample shines to prove that the whisker reinforced layer exists on the surface of the bolt; whiskers were found in the cross-sectional scan near the center of the sample, indicating that whiskers not only enhanced the thread, but also the screw strength.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (10)
1. The preparation method of the whisker reinforced ceramic matrix composite connecting fastener is characterized by comprising the following steps in sequence:
(1) And (3) preparation interface: firstly, cleaning a fiber preform by using acetone, then heating to 400-600 ℃, preserving heat for 2-4 hours to remove a fiber surface glue coating, cooling along with a furnace, and preparing uniform and compact BN interface in the fiber preform and on the surface;
(2) Pre-densification: preparing a compact SiC matrix and a coating on the inner part and the surface of the fiber preform by adopting a CVD/CVI method;
(3) Preprocessing: cutting and rounding the pre-densified fiber preform according to the size standards of various fasteners to obtain a pre-processed sample;
(4) Dip-coating method for preparing coating: dipping the pre-processed sample obtained in the step (3) by using SiC whisker slurry by adopting a vacuum dipping method, and then sequentially carrying out heating curing, thread processing and high-temperature cracking;
(5) And finally, depositing a SiC protective layer on the surface by adopting a CVI method to obtain the whisker reinforced ceramic matrix composite connecting fastener.
2. The method of making a whisker reinforced ceramic matrix composite attachment fastener according to claim 1, wherein the attachment fastener is a pin, screw, stud or nut.
3. The method of producing a whisker reinforced ceramic matrix composite joint fastener according to claim 1, wherein in step (1), the fibers of the fiber preform are C fibers, siC fibers or Si fibers 3 N 4 A fiber; the fiber preform is a two-dimensional fiber cloth lamination, a three-dimensional weaving preform or a three-dimensional needling weaving preform.
4. The method of claim 1, wherein in step (1), the method of preparing the BN interface is a CVD/CVI method, and the BN interface is prepared by: simultaneously introducing boron trichloride and ammonia gas, wherein the diluent gas is argon, the catalytic gas is hydrogen, the flow rate of the boron trichloride is 0.15-0.3L/min, the flow rate of the ammonia gas is 0.25-0.5L/min, the flow rate of the argon gas is 0.6-2L/min, the flow rate of the hydrogen gas is 0.5-1L/min, the pressure in the furnace is 2-5kPa, and the deposition is carried out for 10-50h at the temperature of 650-900 ℃.
5. The method of making a whisker reinforced ceramic matrix composite joint fastener according to claim 1, wherein in step (2), the pre-densification is performed by: the precursor is silicon tetrachloride, the diluent gas is argon, the catalytic gas is hydrogen, the flow of the argon is 2.5-10L/min, the flow of the hydrogen carrier gas is 1.5-5L/min, the flow of the hydrogen diluent gas is 2.5-5L/min, the reaction temperature is 700-1100 ℃, the heat preservation time is 20-100h, and the pressure in the furnace is 1-5kPa.
6. The method of making a whisker reinforced ceramic matrix composite joint fastener according to claim 1, wherein in step (4), the SiC whisker slurry is obtained by:
(1) Mixing SiC whisker and solvent at room temperature, and ball milling for 5-8 hours at 200r/min to prepare SiC whisker solution with volume fraction of 5-20%;
(2) The adhesive is added into ethanol under water bath at 50-70 ℃ and stirring to prepare adhesive solution with the mass fraction of 6-10%;
(3) Adding 30-40% of the binder solution obtained in the step (2) into the SiC whisker solution obtained in the step (1), then adding 3-5% of dispersing agent and 2-3% of plasticizer, continuing ball milling for 5-8h at 200r/min, and then removing bubbles in vacuum to obtain stable slurry;
(4) Mixing a precursor polymer and a crosslinking agent according to a mass percentage of 1:3 to obtain a precursor solution;
(5) And (3) mixing the precursor solution obtained in the step (4) with the stable slurry obtained in the step (5) according to the volume ratio of 5-20:100 to obtain SiC whisker slurry.
7. The method of making a whisker reinforced ceramic matrix composite joint fastener according to claim 1, wherein, in step (4), upon heat curing: under the protection of argon or nitrogen atmosphere and under the condition of vacuum degree of 0.09MPa, heating to 100-300 ℃ at 3-10 ℃/min, preserving heat for 1-3h, and then cooling to room temperature at 3-5 ℃/min.
8. The method of making a whisker reinforced ceramic matrix composite joint fastener according to claim 1, wherein in step (4), at high temperature cracking: under the protection of argon or nitrogen atmosphere and under the condition of 0.09MPa of vacuum degree, heating to 1200-1500 ℃ at 3-10 ℃/min, preserving heat for 2-4h, cooling to 600 ℃ at 3-10 ℃/min, and cooling along with a furnace.
9. The whisker reinforced ceramic matrix composite joint fastener according to claim 1, wherein in step (5), the SiC protective layer is deposited: the precursor is silicon tetrachloride, the diluent gas is argon, the catalytic gas is hydrogen, the flow of the argon is 2.5-10L/min, the flow of the hydrogen carrier gas is 1.5-5L/min, the flow of the hydrogen diluent gas is 2.5-5L/min, the reaction temperature is 700-1100 ℃, the heat preservation time is 8-20h, and the pressure in the furnace is 1-5kPa.
10. A whisker reinforced ceramic matrix composite tie fastener made by the method of making a whisker reinforced ceramic matrix composite tie fastener of any one of claims 1 to 9.
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