CN104609863B - Silicon carbide fiber of appearance deposition SiBCN coating and preparation method thereof - Google Patents
Silicon carbide fiber of appearance deposition SiBCN coating and preparation method thereof Download PDFInfo
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- CN104609863B CN104609863B CN201510018714.XA CN201510018714A CN104609863B CN 104609863 B CN104609863 B CN 104609863B CN 201510018714 A CN201510018714 A CN 201510018714A CN 104609863 B CN104609863 B CN 104609863B
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Abstract
The invention discloses the silicon carbide fiber of a kind of appearance deposition SiBCN coating, comprise silicon carbide fiber matrix and the SiBCN coating at substrate deposit, SiBCN coating is combined by mechanical snap and chemical bonding mode with silicon carbide fiber matrix, and SiBCN coating is for raw material is prepared by chemical vapor deposition method with boron azine and liquid Polycarbosilane; Concrete preparation method comprises: first by the ultrasonic cleaning of silicon carbide fiber body material, then put into cvd furnace after carrying out High Temperature Pre process; Air in replacement deposition stove; Preheating under the vacuum tightness and temperature of setting; Then import carrier gas and carrier gas, carry it in cvd furnace burner hearth; SiBCN coating is formed at silicon carbide fiber substrate material surface after for some time.The coating uniform of product of the present invention, densification, high-temperature stability are good, have good manufacturability, the resistance of oxidation of silicon carbide fiber can be made to increase substantially.
Description
Technical field
The invention belongs to ceramic matric composite and preparing technical field thereof, particularly relate to silicon carbide fiber of a kind of appearance deposited coatings and preparation method thereof.
Background technology
SiC fiber is a kind of polycrystalline ceramic fiber with high specific strength, high ratio modulus, high temperature resistant, anti-oxidant, resistance to chemical attack, can be used as the high-performance compound phase of polymer-based carbon, Metal Matrix and Ceramic Matrix Composites.The SiC strengthened by it
f/ SiC high-performance ceramic based composites can be used for the leading-edge field such as space shuttle, high-performance enginer, be called as 21 century Aeronautics and Astronautics and high-technology field application novel material.SiC
fthe performance of SiC fiber and SiC matrix itself is not only depended in the performance of the performance of/SiC ceramic matrix composite material, the more important thing is interfacial phase therebetween.Interfacial phase is to SiC
fthe performance of/SiC ceramic matrix composite material plays decisive role, as the SiC prepared through chemical gas phase dipping (CVI) technique by original Niccalon-SiC fiber
f/ SiC ceramic matrix composite material flexural strength only has 85.0MPa, and fiber surface is after carbon coating deposition, SiC
f/ SiC ceramic matrix composite material interface be improved significantly, flexural strength can bring up to 420.0MPa.Suitable interfacial phase can protect fiber, makes fiber damage reduction in matrix material preparation process; The more important thing is, interfacial phase protection fiber, from the burn into oxidation in technique and use procedure, interfacial chemical reaction and physical abuse, significantly improves the mechanical property of matrix material.
Often be applied to SiC at present
finterfacial phase coating in/SiC ceramic matrix composite material mainly contains RESEARCH OF PYROCARBON (PyC) coating, boron nitride (BN) coating and compound interface phase coating etc., but due to PyC coating high-temp resistance of oxidation poor; Easily B is oxidized under the high temperature of BN
2o
3; Compound interface phase preparation technology of coating is complicated, and multiple high temp preparation process also can be aggravated the damage of fiber, is all unfavorable for SiC
fthe application of/SiC ceramic matrix composite material.SiBCN coating has good high-temperature stability, oxidation-resistance and suitable physical strength; and with multiple inorganic fibre reinforcement, ceramic matrix, there is good chemical compatibility; when being heated to 2200 DEG C under argon shield, weightlessness is less than 3%; lower than when 1700 DEG C without thermal weight loss and phase-splitting, just have crystalline transition to be SiC and Si when 2000 DEG C
3n
4and a small amount of amorphous BN.Research shows, its antioxidant property is better than Si
3n
4, SiC.These advantages become the interfacial phase coated material in a kind of extremely potential matrix material.
Up to now, the SiBCN ceramic preparation of development mainly contains: polymer conversion, reaction magnetocontrol sputtering, mechanize alloy are in conjunction with hot pressed sintering three kinds.Chemical vapour deposition (CVD) is also a kind of method preparing SiBCN pottery, coating continuity, good uniformity prepared by CVD technique, is the optimal selection preparing interfacial phase coating at fiber surface, but domestic and international research in this is less.JohannesWilden etc. adopt borazine and trimethyl silyl aminosilane or hexa methyl silazane to be raw material, have prepared the multipolymer of borazine/silazane through thermal polycondensation reaction; The people such as Riedel adopt methylvinyl-chlorosilanes and various borine to be raw material, and single bundle carbon fiber deposits SiBCN pottery, and deposit thickness is 1 μm ~ 5 μm, improves the resistance of oxidation of carbon fiber; DirkHegemann etc. are with [(CH
3)
2n]
3si-NH-B [N (CH
3)
2]
2(being called for short TDADB) is precursor source of the gas, adopts plasma-assisted chemical vapour deposition method (PACVD) to deposit SiBC at 250 DEG C
2.8n thin film; C.H.Ko etc. adopt thermal chemical vapor deposition method to deposited SiBCN film at 550 DEG C, and its specific inductivity is 5.2, but does not provide precursor source of the gas system.2013, the people such as Northwestern Polytechnical University Liu Yongsheng adopted trimethylammonium trichlorosilane (SiCH
3cl
3) be silicon source and carbon source, BCl
3for boron source, NH
3for nitrogenous source, H
2as carrier gas and carrier gas, chemical Vapor deposition process (CVD) deposited SiBCN amorphous ceramic (Chinese patent see No. 201310178800.8, application number).But in the preparation of above-mentioned SiBCN coating, adopt two classes or the above deposition gas of two classes, technique is more complicated, and produces corrosive by product in most of deposition reaction process, deposition substrate material and facility is produced and does not locate impact, and be not suitable for industrialization and prepare SiBCN.Therefore, find suitable SiBCN precursor and seem particularly important.
Summary of the invention
Technical problem to be solved by this invention is, overcome the deficiency and defect mentioned in above background technology, the silicon carbide fiber of appearance deposition SiBCN coating that a kind of coating uniform, densification, high-temperature stability are good, have good manufacturability, resistance of oxidation increased substantially simultaneously is provided, also the corresponding preparation technology of providing is simple, reproducible, equipment requirements is low, be suitable for suitability for industrialized production and be easy to the preparation method and application of the silicon carbide fiber of preparation large size complex component.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is the silicon carbide fiber of a kind of appearance deposition SiBCN coating, it is characterized in that, described silicon carbide fiber comprises silicon carbide fiber matrix and the SiBCN coating at silicon carbide fiber substrate deposit, SiBCN coating is combined by mechanical snap and chemical bonding mode with silicon carbide fiber matrix, and described SiBCN coating is for raw material is prepared by chemical vapor deposition method with boron azine and liquid Polycarbosilane.
The silicon carbide fiber of above-mentioned appearance deposition SiBCN coating, preferably, described silicon carbide fiber matrix comprises at least one in silicon carbide fiber monofilament, silicon carbide fiber synnema and silicon carbide fiber braided part, and the thickness of described SiBCN coating is 100nm ~ 450nm.
As a total technical conceive, the present invention also provides a kind of preparation method of silicon carbide fiber of above-mentioned appearance deposition SiBCN coating, comprises the following steps:
(1) silicon carbide fiber body material is placed in organic solvent for ultrasonic cleaning; Described organic solvent is preferably at least one in dehydrated alcohol, acetone, dimethylbenzene, and the time of ultrasonic cleaning preferably controls as 0.5h ~ 1.0h;
(2), after the silicon carbide fiber body material after ultrasonic cleaning being carried out High Temperature Pre process, cvd furnace burner hearth is put into; The present invention comprises for the preparation of the cvd furnace device of coating: the importing of CVD (Chemical Vapor Deposition) chamber (tube furnace), temperature controlling system, pressure control system, flow control system, vacuum pump and gas and discharge system etc.;
(3) cvd furnace burner hearth is vacuumized, then be filled with nitrogen, repeatedly carry out repeatedly, the air in replacement deposition stove burner hearth;
(4) cvd furnace burner hearth is evacuated to setting vacuum tightness, is then warming up to design temperature preheating;
(5) after temperature-stable, carrier gas and carrier gas is imported; Control boron azine and liquid Polycarbosilane volatilization temperature, maintain reactive system pressure, after mass flowmeter setting and carrier gas blending ratio, boron azine and liquid Polycarbosilane are brought into, brings in cvd furnace burner hearth after being diluted by carrier gas; SiBCN coating is formed at silicon carbide fiber substrate material surface after one section of depositing time;
(6) after deposition terminates, stop importing carrier gas and carrier gas, close heating system, cool to room temperature with the furnace, obtain the silicon carbide fiber of appearance deposition SiBCN coating.
In above-mentioned preparation method, preferably, the High Temperature Pre process in described step (2) is under air ambient, and the treatment temp of described pyroprocessing is 400 DEG C ~ 500 DEG C, and the high temperature pretreated time is 0.2h ~ 0.5h.By carrying out the High Temperature Pre process of short period of time to SiC fiber, the free carbon in SiC fiber sheath can be removed and do not affect its mechanical property, reducing the interfacial chemical reaction of fiber sheath free carbon, thus SiC fiber is protected.
In above-mentioned preparation method, preferably, in described step (3), be evacuated to 0.1Pa ~ 1.0Pa to cvd furnace burner hearth, the number of times repeatedly carried out is at least three times.Preferably, the setting vacuum degree control in described step (4) is 0.1Pa ~ 0.5Pa, and described design temperature is 1000 DEG C ~ 1400 DEG C, and the warm up time under design temperature is 1.5h ~ 2.5h.Can be there is dehydrogenation coupling reaction and form B-N, Si-N, Si-N-B key in raw material boron azine (BZ) of the present invention and liquid Polycarbosilane (LPCS), and part of boron hydrogen six-ring can be opened and form more multi-active base group by scission of link when carrying out high temperature pyrolysis under aforementioned temperature; Owing to there is impurity element in cvd furnace burner hearth, as the N in air
2, O
2, CO
2react with above active group Deng all likely, produce other impurity phase, reaction product etc., thus impact deposition SiBCN coating quality.Therefore, strict vacuumizing is carried out to cvd furnace burner hearth and takes a breath and keep preferred vacuum degree condition, be conducive to the quality promoting SiC fiber sheath deposition SiBCN product.
In above-mentioned preparation method, preferably, in described step (5), described carrier gas is hydrogen, and purity is more than or equal to 99.99%; The mass mixing ratio of described boron azine and carrier gas is 1: 2.5 ~ 3.2, and carrier gas flux is 50.0ml/min ~ 500.0ml/min; The mass mixing ratio of described liquid Polycarbosilane and carrier gas is 1: 1.5 ~ 2.2, and carrier gas flux is 30.0ml/min ~ 300.0ml/min.Because hydrogen is reactive gas, use highly purified hydrogen as carrier gas, the element reaction in cvd furnace burner hearth can be promoted, thus improve the productive rate of SiBCN pottery.Repeatedly test discovery by us, precursor concentration is high, and sedimentation rate is fast, and especially when depositing SiC fiber braid, carrier gas enters braided part and forms concentration gradient by because of too fast reactive deposition speed, causes outside uneven with coated inside of braided part; Otherwise precursor concentration is low, sedimentation rate is slow, and causing coating to deposit uneven phenomenon because reactive deposition speed is fast will weaken, but depositing time rises appreciably.Because boron azine and liquid Polycarbosilane are liquid, we are by controlling blending ratio, the gas flow of boron azine and liquid Polycarbosilane and hydrogen, thus control boron azine and liquid polycarbosilane precusor enter concentration in cvd furnace burner hearth; And the mass mixing of the mass mixing ratio of aforementioned boron azine and carrier gas, liquid Polycarbosilane and carrier gas when carrier gas flux be us and repeatedly test the comparatively figure of merit drawn.
In above-mentioned preparation method, preferably, in described step (5), the volatilization temperature of boron azine controls at-15 DEG C ~-5 DEG C, and the volatilization temperature of liquid Polycarbosilane controls at 115 DEG C ~ 125 DEG C, and described depositing time is 1.5h ~ 4.0h.
In above-mentioned preparation method, preferably, in described step (5), described carrier gas is hydrogen, and purity is more than or equal to 99.99%; Carrier gas flow is 400.0ml/min ~ 600.0ml/min; Reactive system pressure maintains 300.0Pa ~ 30000.0Pa.Because hydrogen is reactive gas, use highly purified hydrogen as carrier gas, the element reaction in cvd furnace burner hearth can be promoted, thus improve the productive rate of SiBCN pottery.
Technique scheme of the present invention is especially based on following thinking: (1) chemical Vapor deposition process of the present invention adopts boron azine (BZ) and liquid Polycarbosilane (LPCS) as precursor respectively, and it is the excellent precursor that CVD technique prepares BN, SiC coating respectively; The volatilization point of boron azine and liquid Polycarbosilane is respectively at-10 DEG C and 120 DEG C, and the formation of dehydrogenation coupling reaction B-N, Si-N, Si-N-B key can be there is when pyrolysis in B-H, N-H and Si-H key in the two, there is part of boron hydrogen six-ring can open and form more multi-active base group by scission of link in pyrolytic process, more enrich the bonding pattern in sedimentation products, can form by CVD technique the SiBCN coating that short range structure is Si-(B, C, N)-Si tetrahedron and boron nitrogen six-ring.(2) SiBCN coating has good high-temperature stability, oxidation-resistance and suitable physical strength, and has good chemical compatibility with multiple inorganic fibre reinforcement, ceramic matrix.Due in SiC fiber all containing a certain amount of free carbon, at high temperature can react with interfacial phase, fibre strength is demoted; By research, use hydrogen as carrier gas and carrier gas, can effectively remove fiber surface free carbon on the one hand, thus reduce interfacial chemical reaction, reach the object of protection fibre property; On the other hand, hydrogen, as high reactivity gas, can promote the active group reaction of reacting in burner hearth, increase the ceramic yield of SiBCN.
Compared with prior art, the invention has the advantages that:
1. propose first in the present invention to use boron azine (BZ) and liquid Polycarbosilane (LPCS) as precursor, chemical vapor deposition method is adopted to prepare SiBCN coating, especially as boron source and nitrogenous source while that boron azine being in deposition SiBCN quaternary ceramic coating, as silicon source and carbon source while of liquid Polycarbosilane, this more current chemical vapor deposition SiBCN, BCN, BN, SiC, Si
3n
4etc. carry respectively in similar coatings boron source, nitrogenous source, silicon source and carbon source technique have larger simplification, source of the gas control process is easier.In addition, boron azine as precursor source of the gas relative to conventional boron source (as halogenation boron or borine etc.) its volatilization process more easy to control.Boron azine and the non-corrosiveness of liquid Polycarbosilane own, also not containing corrosive halogens, can not form corrosive by product in deposition process, thus reduce depositing operation to the impact of base material, depositing device.
2. the SiBCN coating on silicon carbide fiber surface of the present invention adopts chemical Vapor deposition process to prepare, the SiBCN coating of preparation is not the simple mixing of SiC, BN stupalith, be form the keys such as B-N, Si-N, Si-N-B at chemical vapor deposition processes generation dehydrogenation coupling reaction, formation short range structure is the SiBCN pottery of Si-(B, C, N)-Si tetrahedron and boron nitrogen six-ring; And the high-temperature stability of coating is good, can be on active service for a long time under the temperature condition of 1600 DEG C, the resistance of oxidation of silicon carbide fiber is increased substantially.
3. adopt preparation technology of the present invention to deposit to the surface of SiC fiber braid, inside and tie up point with can making SiBCN coating uniform, especially the individual fiber surface of braided part inside all deposits SiBCN coating, coating structure evenly, fine and close, smooth surface is consistent, high-temperature stability is good, there is good manufacturability, make the resistance of oxidation of silicon carbide fiber increase substantially simultaneously, the hot environment adaptability of silicon carbide fiber and tolerable temperature are improved, extends the work-ing life under its hot environment.
4. the present invention by controlling the temperature of boron azine and liquid Polycarbosilane, can make it have suitable volatility, having good manufacturability as precursor source of the gas.By regulating depositing temperature, system pressure, carrier gas and the flow of carrier gas and the ratio of boron azine and carbon silane, the composition of regulation and control sedimentation products and structure, coating composition and thickness are designed and prepares, and preparation technology is simple, reaction process is easily controlled, reproducible, equipment requirements is low, be applicable to suitability for industrialized production, be easy to prepare large size, complex component.
5. the present invention strengthens pyroceramic based composites by the silicon carbide fiber of appearance deposition SiBCN coating, and coating performance meets SiC
fthe requirement of/SiC ceramic matrix composite material interfacial phase, is expected to solve the interfacial chemical reaction between its fiber-matrix, thus improves the high-temperature behavior of ceramic matric composite, significant in the application in high temperature and ultra-temperature ceramic-based composite material field to silicon carbide fiber.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the scanning electron microscope (SEM) photograph (high magnification) of the silicon carbide fiber of appearance deposition SiBCN coating prepared by the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph (comparatively low range) of the silicon carbide fiber of appearance deposition SiBCN coating prepared by the embodiment of the present invention 1.
Fig. 3 is the selected area electron diffraction figure under the silicon carbide fiber different multiplying of appearance deposition SiBCN coating prepared by the embodiment of the present invention 1, wherein the left figure upper right corner is the constituency schematic diagram of transmission electron microscope, there is not electron diffraction striped in hot spot, illustrate that the SiBCN coating of deposition is non-crystalline state.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Unless otherwise specified, the various starting material, reagent, instrument and equipment etc. used in the present invention are all bought by market and are obtained or prepare by existing method.
Embodiment 1:
A kind of silicon carbide fiber of appearance deposition SiBCN coating of the present invention, comprise silicon carbide fiber matrix and the SiBCN coating at silicon carbide fiber substrate deposit, SiBCN coating is combined by mechanical snap and chemical bonding mode with silicon carbide fiber matrix, and SiBCN coating is for raw material is prepared by chemical vapor deposition method with boron azine and liquid Polycarbosilane.In the present embodiment, silicon carbide fiber matrix is silicon carbide fiber monofilament, and the thickness of SiBCN coating is 450nm.
The preparation method of the silicon carbide fiber of the appearance deposition SiBCN coating that the present embodiment is above-mentioned, comprises the following steps:
(1) silicon carbide fiber monofilament is placed in organic solvent-acetone ultrasonic cleaning, the time controling of ultrasonic cleaning is 0.5h;
(2) the silicon carbide fiber monofilament after ultrasonic cleaning is placed in air, at 400 DEG C of temperature, carries out High Temperature Pre process 0.2h, then put into cvd furnace burner hearth; Cvd furnace device for the preparation of coating comprises: the importing of CVD (Chemical Vapor Deposition) chamber (tube furnace), temperature controlling system, pressure control system, flow control system, vacuum pump and gas and discharge system etc.;
(3) 0.1Pa is evacuated to cvd furnace burner hearth, then is filled with nitrogen, repeatedly carry out more than three times, the air in replacement deposition stove burner hearth;
(4) cvd furnace burner hearth is evacuated to setting vacuum tightness 0.1Pa, is then warming up to design temperature 1000 DEG C of preheatings, insulation 1.5h;
(5) after temperature-stable, importing purity is that the hydrogen of 99.99% is as carrier gas and carrier gas; Set the volatilization temperature of boron azine as-15 DEG C, the mass mixing ratio of boron azine and hydrogen is 1: 2.5, and carrier gas flux is 50.0ml/min; The volatilization temperature setting liquid Polycarbosilane is 115 DEG C, and the mass mixing ratio of Polycarbosilane and hydrogen is 1: 1.5, and carrier gas flux is 30.0ml/min; Setting carrier gas hydrogen flowing quantity is 400.0ml/min, and system pressure maintains 300.0Pa, brings in cvd furnace burner hearth by boron azine and liquid Polycarbosilane; SiBCN coating is formed on silicon carbide fiber monofilament material surface after deposition 1.5h;
(6) after deposition terminates, stop importing carrier gas and carrier gas, close heating system, cool to room temperature with the furnace, obtain the silicon carbide fiber of appearance deposition SiBCN coating.
By scanning electron microscopic observation, SiBCN coat-thickness prepared by the present embodiment is 450nm, and as shown in Figure 1 and Figure 2, scanning electron microscope display coating uniform is intactly coated on SiC fiber peripheral surface, and coating is combined with fiber surface closely, without defects such as holes.Uniform coating thickness, surface is comparatively smooth.
The transmission electron microscope picture of silicon carbide fiber top coat is visible as shown in Figure 3, and the coating of the SiC fiber surface of gained is amorphous state at the process conditions, Stability Analysis of Structures.
The SiC fiber containing SiBCN coating obtained by above-mentioned the present embodiment method is compared with the tensile strength of uncoated SiC fiber, as shown in table 1, tensile strength is without obvious reduction, and this shows that the tensile strength of this coating on SiC fiber is without impact, is good fiber coat.
Table 1: the tensile strength after the silicon carbide fiber oxidation of appearance deposition SiBCN coating prepared by embodiment 1
Be incubated 1.5h at 1600 DEG C of the SiBCN coating obtained by above-mentioned the present embodiment method, coming off does not appear in coating, ftracture and the obvious phenomenon such as ablation, reach the object of protection silicon carbide fiber.
Embodiment 2:
A kind of silicon carbide fiber of appearance deposition SiBCN coating of the present invention, comprise silicon carbide fiber matrix and the SiBCN coating at silicon carbide fiber substrate deposit, SiBCN coating is combined by mechanical snap and chemical bonding mode with silicon carbide fiber matrix, and SiBCN coating is for raw material is prepared by chemical vapor deposition method with boron azine and liquid Polycarbosilane.In the present embodiment, silicon carbide fiber matrix is silicon carbide fiber synnema, and the thickness of SiBCN coating is 350nm.
The preparation method of the silicon carbide fiber of the appearance deposition SiBCN coating that the present embodiment is above-mentioned, comprises the following steps:
(1) silicon carbide fiber synnema is placed in organic solvent-acetone ultrasonic cleaning, the time controling of ultrasonic cleaning is 0.5h;
(2) the silicon carbide fiber synnema after ultrasonic cleaning is placed in air, at 450 DEG C of temperature, carries out High Temperature Pre process 0.4h, then put into cvd furnace burner hearth; Cvd furnace device for the preparation of coating comprises: the importing of CVD (Chemical Vapor Deposition) chamber (tube furnace), temperature controlling system, pressure control system, flow control system, vacuum pump and gas and discharge system etc.;
(3) 0.7Pa is evacuated to cvd furnace burner hearth, then is filled with nitrogen, repeatedly carry out more than three times, the air in replacement deposition stove burner hearth;
(4) cvd furnace burner hearth is evacuated to setting vacuum tightness 0.3Pa, is then warming up to design temperature 1200 DEG C of preheatings, insulation 2.0h;
(5) after temperature-stable, importing purity is that the hydrogen of 99.999% is as carrier gas and carrier gas; Set the volatilization temperature of boron azine as-10 DEG C, the mass mixing ratio of boron azine and hydrogen is 1: 2.8, and carrier gas flux is 300.0ml/min; The volatilization temperature setting liquid Polycarbosilane is 120 DEG C, and the mass mixing ratio of Polycarbosilane and hydrogen is 1: 1.8, and carrier gas flux is 200.0ml/min; Setting carrier gas hydrogen flowing quantity is 500.0ml/min, and system pressure maintains 3000.0Pa, brings in cvd furnace burner hearth by boron azine and liquid Polycarbosilane; SiBCN coating is formed at silicon carbide fiber synnema material surface after deposition 2.5h;
(6) after deposition terminates, stop importing carrier gas and carrier gas, close heating system, cool to room temperature with the furnace, obtain the silicon carbide fiber of appearance deposition SiBCN coating.
By detecting, coat-thickness prepared by the present embodiment is 350.0nm, and the SiBCN coating obtained by aforesaid method is incubated 2.5h at 1600 DEG C, and coming off does not appear in coating, ftracture and the obvious phenomenon such as ablation, reaches the object protecting silicon carbide fiber.
Embodiment 3:
A kind of silicon carbide fiber of appearance deposition SiBCN coating of the present invention, comprise silicon carbide fiber matrix and the SiBCN coating at silicon carbide fiber substrate deposit, SiBCN coating is combined by mechanical snap and chemical bonding mode with silicon carbide fiber matrix, and SiBCN coating is for raw material is prepared by chemical vapor deposition method with boron azine and liquid Polycarbosilane.In the present embodiment, silicon carbide fiber matrix is silicon carbide fiber braided part, and the thickness of SiBCN coating is 100nm.
The preparation method of the silicon carbide fiber of the appearance deposition SiBCN coating that the present embodiment is above-mentioned, comprises the following steps:
(1) silicon carbide fiber braided part is placed in organic solvent-acetone ultrasonic cleaning, the time controling of ultrasonic cleaning is 0.5h;
(2) the silicon carbide fiber braided part after ultrasonic cleaning is placed in air, at 500 DEG C of temperature, carries out High Temperature Pre process 0.5h, then put into cvd furnace burner hearth; Cvd furnace device for the preparation of coating comprises: the importing of CVD (Chemical Vapor Deposition) chamber (tube furnace), temperature controlling system, pressure control system, flow control system, vacuum pump and gas and discharge system etc.;
(3) 1.0Pa is evacuated to cvd furnace burner hearth, then is filled with nitrogen, repeatedly carry out more than three times, the air in replacement deposition stove burner hearth;
(4) cvd furnace burner hearth is evacuated to setting vacuum tightness 0.5Pa, is then warming up to design temperature 1400 DEG C of preheatings, insulation 2.5h;
(5) after temperature-stable, importing purity is that the hydrogen of 99.99% is as carrier gas and carrier gas; Set the volatilization temperature of boron azine as-5 DEG C, the mass mixing ratio of boron azine and hydrogen is 1: 3.2, and carrier gas flux is 500.0ml/min; The volatilization temperature setting liquid Polycarbosilane is 125 DEG C, and the mass mixing ratio of Polycarbosilane and hydrogen is 1: 2.2, and carrier gas flux is 300.0ml/min; Setting carrier gas hydrogen flowing quantity is 600.0ml/min, and system pressure maintains 30000.0Pa, brings in cvd furnace burner hearth by boron azine and liquid Polycarbosilane; SiBCN coating is formed on silicon carbide fiber braided part surface after deposition 4.0h;
(6) after deposition terminates, stop importing carrier gas and carrier gas, close heating system, cool to room temperature with the furnace, obtain the silicon carbide fiber of appearance deposition SiBCN coating.
By detecting, coat-thickness prepared by the present embodiment is 100.0nm, and the SiBCN coating obtained by aforesaid method is incubated 4.0h at 1600 DEG C, and coming off does not appear in coating, ftracture and the obvious phenomenon such as ablation, reaches the object protecting silicon carbide fiber.
Claims (10)
1. the silicon carbide fiber of an appearance deposition SiBCN coating, it is characterized in that, described silicon carbide fiber comprises silicon carbide fiber matrix and the SiBCN coating at silicon carbide fiber substrate deposit, SiBCN coating is combined by mechanical snap and chemical bonding mode with silicon carbide fiber matrix, and described SiBCN coating is for raw material is prepared by chemical vapor deposition method with boron azine and liquid Polycarbosilane.
2. the silicon carbide fiber of appearance deposition SiBCN coating according to claim 1, it is characterized in that, described silicon carbide fiber matrix comprises at least one in silicon carbide fiber monofilament, silicon carbide fiber synnema and silicon carbide fiber braided part, and the thickness of described SiBCN coating is 100nm ~ 450nm.
3. appearance deposits a preparation method for the silicon carbide fiber of SiBCN coating as claimed in claim 1, it is characterized in that, comprises the following steps:
(1) silicon carbide fiber body material is placed in organic solvent for ultrasonic cleaning;
(2), after the silicon carbide fiber body material after ultrasonic cleaning being carried out High Temperature Pre process, cvd furnace burner hearth is put into;
(3) cvd furnace burner hearth is vacuumized, then be filled with nitrogen, repeatedly carry out repeatedly, the air in replacement deposition stove burner hearth;
(4) cvd furnace burner hearth is evacuated to setting vacuum tightness, is then warming up to design temperature preheating;
(5) after temperature-stable, carrier gas and carrier gas is imported; Control boron azine and liquid Polycarbosilane volatilization temperature, maintain reactive system pressure, after mass flowmeter setting and carrier gas blending ratio, boron azine and liquid Polycarbosilane are loaded into, bring in cvd furnace burner hearth after being diluted by carrier gas; SiBCN coating is formed at silicon carbide fiber substrate material surface after one section of depositing time;
(6) after deposition terminates, stop importing carrier gas and carrier gas, close heating system, cool to room temperature with the furnace, obtain the silicon carbide fiber of appearance deposition SiBCN coating.
4. preparation method according to claim 3, is characterized in that, the High Temperature Pre process in described step (2) is under air ambient, and the treatment temp of described pyroprocessing is 400 DEG C ~ 500 DEG C, and the high temperature pretreated time is 0.2h ~ 0.5h.
5. preparation method according to claim 3, is characterized in that, in described step (3), be evacuated to 0.1Pa ~ 1.0Pa to cvd furnace burner hearth, the number of times repeatedly carried out is at least three times.
6. preparation method according to claim 3, is characterized in that, the setting vacuum degree control in described step (4) is 0.1Pa ~ 0.5Pa, and described design temperature is 1000 DEG C ~ 1400 DEG C, and the warm up time under design temperature is 1.5h ~ 2.5h.
7. the preparation method according to any one of claim 3 ~ 6, is characterized in that, in described step (5), described carrier gas is hydrogen, and purity is more than or equal to 99.99%.
8. preparation method according to claim 7, is characterized in that, in described step (5), the mass mixing ratio of described boron azine and carrier gas is 1: 2.5 ~ 3.2, and carrier gas flux is 50.0ml/min ~ 500.0ml/min; The mass mixing ratio of described liquid Polycarbosilane and carrier gas is 1: 1.5 ~ 2.2, and carrier gas flux is 30.0ml/min ~ 300.0ml/min.
9. the preparation method according to any one of claim 3 ~ 6, it is characterized in that, in described step (5), the volatilization temperature of boron azine controls at-15 DEG C ~-5 DEG C, the volatilization temperature of liquid Polycarbosilane controls at 115 DEG C ~ 125 DEG C, and described depositing time is 1.5h ~ 4.0h.
10. the preparation method according to any one of claim 3 ~ 6, is characterized in that, in described step (5), described carrier gas is hydrogen, and purity is more than or equal to 99.99%; Carrier gas flow is 400.0ml/min ~ 600.0ml/min; Reactive system pressure maintains 300.0Pa ~ 30000.0Pa.
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| CN107353025B (en) * | 2017-06-27 | 2020-10-20 | 中航复合材料有限责任公司 | Preparation method of 1200-DEG C-resistant and oxidation-resistant ceramic matrix composite |
| CN107814590A (en) * | 2017-11-07 | 2018-03-20 | 中国科学院山西煤炭化学研究所 | A kind of preparation method of fusedsalt reactor graphite surface SiC coatings |
| CN108892521B (en) * | 2018-07-06 | 2021-04-02 | 东华大学 | Preparation method of wave-transparent ceramic matrix composite material containing silicon-boron-nitrogen interface |
| CN108947552A (en) * | 2018-07-30 | 2018-12-07 | 西北工业大学 | A kind of suction wave mode SiC nanowire enhancing SiBCN composite ceramic coat and preparation method |
| CN111441104B (en) * | 2020-03-10 | 2022-10-28 | 哈尔滨工业大学 | Method for preparing CSiNB quaternary fibers from carbon fibers |
| CN112851359B (en) * | 2021-01-22 | 2022-05-10 | 哈尔滨工业大学 | Suction type SiBCN nano-fiber and preparation method thereof |
| CN113173791B (en) * | 2021-03-26 | 2022-07-12 | 中国科学院上海硅酸盐研究所 | SiBCN interface coating for SiC fiber reinforced composite material, and preparation method and application thereof |
| CN115368155B (en) * | 2022-07-22 | 2023-07-25 | 湖南晶碳新材料有限公司 | Preparation method and application of composite material crucible for Czochralski silicon single crystal |
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