CN105463403B - A kind of preparation method of ceramic matric composite boron nitride interface coating - Google Patents
A kind of preparation method of ceramic matric composite boron nitride interface coating Download PDFInfo
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- CN105463403B CN105463403B CN201510825266.4A CN201510825266A CN105463403B CN 105463403 B CN105463403 B CN 105463403B CN 201510825266 A CN201510825266 A CN 201510825266A CN 105463403 B CN105463403 B CN 105463403B
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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
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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
- C23C16/44—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
- C23C16/448—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 characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C16/4481—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 characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials by evaporation using carrier gas in contact with the source material
Abstract
The present invention relates to a kind of preparation of the preparation method, more particularly to fiber surface and substrate surface boron nitride coating of ceramic matric composite boron nitride interface coating, belong to ceramic matric composite toughening technology field.The present invention is from the single constituent element NH containing B, N simultaneously3BH3It is used as the precursor at BN interfaces, this precursor nontoxic pollution-free, nonflammable, non-explosive B:N=1：1, it is easy to form the BN of stoichiometric proportion, it is ensured that the BN of preparation has preferable stoichiometric proportion, it is to avoid B, N disproportionate problem in double elements precursor, and there is no corrosive gas in preparation process；The present invention can be prepared by 400 DEG C~900 DEG C low temperature chemical vapor deposition methods in reaction temperature, preferably 700~900 DEG C yields to improve BN, and the sedimentation products BN contents of acquisition are more than 97%.Low temperature depositing can improve the strength retention ratio of fiber as far as possible, and strength retention ratio is more than 90% after deposition, and strength retention ratio is more than 70% after high-temperature heat treatment.
Description
Technical field
The present invention relates to a kind of preparation method of ceramic matric composite boron nitride interface coating, more particularly to fiber surface
With the preparation of substrate surface boron nitride coating, belong to ceramic matric composite Toughness Design technical field.
Background technology
Ceramic matric composite (ceramic matrix composites) by continuous ceramic fiber, ceramic matrix and by
The boundary layer composition for spontaneously forming or manually preparing.Ceramic matric composite possess low-density, high intensity, high temperature resistant, it is corrosion-resistant,
The excellent properties such as anti-oxidant, good toughness, there is important application in terms of China's Aero-Space.Such as the burning of fanjet
Room, fixed blade, missile-borne radome, thermal protection system of aerospace craft etc..
The toughness of ceramic matric composite is the emphasis that researchers study, and the key of toughness reinforcing is that have a good fibre
Dimension-basal body interface.The interface of Continuous Fiber Reinforced Ceramic Matrix Composites plays transmission load, can make crack deflection, de- combination,
So as to increase the effect of toughness, so to there is an appropriate weak binding interface between fibrous matrix.It is general this in order to reach
Effect has two methods：One is to use porous matrix, such as oxide composite, and two be to prepare fiber coat.It is many with using
Hole matrix phase ratio, it is that very promising oxide composite increases to prepare fiber coat as the weak binding interface of fibrous matrix
Tough method.In this case, when the crack propagation in matrix is to when coating cated fiber, crackle can be in matrix/painting
Bed boundary, coat inside are deflected in coating/fiber interface, and fiber is finally broken in the place away from the plane of disruption, final fine
Dimension is extracted, and the friction of fiber consumes a part of load in withdrawal process, adds toughness.
The interlayer materials for meeting low modulus and low shear strength requirement simultaneously are generally pyrolytic carbon (PyC) and nitridation at present
Boron (BN), boron nitride (BN) has the layered crystal structure similar to pyrolytic carbon, compared with pyrolytic carbon, also with preferable antioxygen
Change performance, the liquid B formed after oxidation2O3Crackle can be made up, be preferable interface phase candidate material, in recent years as interface
The importance mutually studied.Traditional preparation method has many defects, wherein, polymer conversion cracking process polymer pyrolysis rate is not
Height, and volume contraction is larger, or even make coating cracking or in coat inside formation bubble, it is therefore desirable to by multiple coating and
Cracking, causes the adhesion of fiber；Boric acid-urea method coating quality is low, while also easily causing fiber adhesion；Carbothermic method
Some total material of fiber surface is participated in reacting as reactant, and fibre strength can be damaged necessarily to some extent.And
Chemical Vapor Deposition Equipment is simple, easy to maintenance, and flexibility is strong, can be by reaction chamber size and reacting gas residence time
Adjust to control coating layer thickness, can be from Nano grade to micron level.And coating is fine and close, uniform, can preferably control
The density of coating, purity and grain size.
Yu Cheng (Cheng Y, et al.BN coatings prepared by low pressure chemical
vapor deposition using boron trichloride–ammonia–hydrogen–argon mixture
Gases. document) et al. use BCl3-NH3-H2- Ar systems are prepared for BN coatings in graphite base with low pressure chemical vapor deposition, prepare optimal
Temperature, pressure be respectively 1000 DEG C, 1000Pa, what is obtained after deposition is the t-BN coatings of turbine-like, through 1300 DEG C high warm
H-BN has been obtained after processing.In addition, BF3-NH3-H2- Ar systems are also used more, and BBr3-NH3-H2- Ar systems are then less.
Haitang Wu(Haitang Wu,et al.Deposition of BN interphase coatings from B-
trichloroborazine and its effects on the mechanical properties of SiC/SiC
Composites. document) with Cl3B3N3H3For single precursor, BN coatings are deposited on silicon carbide fibre, deposition is have studied
The influence of temperature, reaction time, dilution hydrogen flowing quantity to coating morphology and crystal formation, and have studied the SiC/SiC as interface
Mechanical property, find bending resistance have been improved.While single group member precursor such as B (N (CH3)2)3, H3B-N(C2H5)3Deng also obtaining
Checking.
But traditional BX3-NH3System has the generation of corrosive gas, the NH of generation during the course of the reaction4X blocks pipe
Road, preparation temperature is higher, and damage is had to fibrous mechanical property.And single precursor such as B (N (CH3)2)3, H3B-N(C2H5)3Deng
Containing a large amount of Methyl groups, NH need to be passed through3Eliminate, and carbon residue is more in the coating ultimately produced, Cl3B3N3H3Then contain halogen family
Corrosive gas presence is had in element, product.
The content of the invention
The technology of the present invention solves problem：Overcome the deficiencies in the prior art, propose a kind of ceramic matric composite nitridation
The preparation method of boron interface coating, this method uses single NH3BH3It is used as precursor, it is to avoid etchant gas goes out in product
It is existing, the influence of no residual carbon, it is ensured that the generation of the boron nitride of stoichiometric proportion, while also reducing the preparation at boron nitride interface
Temperature.
The present invention technical solution be：
A kind of preparation method of ceramic matric composite boron nitride interface coating, step is：
(1) deposition substrate is subjected to purification pretreatment；
(2) pretreated substrate will be purified to be placed in the reative cell of chemical vapor deposition stove to set inclination angle, NH3BH3First
Drive body and reaction outdoor is connected to setting means, closed air-channel system is formed with reative cell；Be passed through setting species, flow and when
Between carrier gas fully clean displacement air-channel system in air；When reaction chamber temperature is anti-with the heating of 5~20 DEG C/min heating rates
Room is answered to 400 DEG C~900 DEG C (preferably 700~900 DEG C), after temperature stabilization, reaction it is outdoor with 90~200 DEG C (preferably 100~
180 DEG C) distillation NH3BH3Precursor, flow carrier gas of the flores by setting species is delivered to reative cell, now flores
Start, in substrate surface deposition reaction, to generate boron nitride；It is 5Kpa-100Kpa, deposition that chamber pressure is kept in deposition process
After the completion of process, stop the conveying of flores, keep carrier gas circulation, until reative cell program is cooled to room temperature, close carrier gas,
The substrate with deposit is taken out, the thickness of deposit is 50nm-3 μm；
(3) substrate with deposit that step (2) is obtained is subjected to high-temperature process, treatment temperature：1000~1600 DEG C,
Handle atmosphere:Ar、N2、H2Or Ar/H2Mixed gas, processing time：1~5h.
Substrate is substrate such as graphite flake, silicon chip or sapphire sheet in the step (1), can also be ceramic fibre such as quartz
Fiber, alumina fibre, aluminosilicate fiber, silicon carbide fibre, carbon fiber or silicon nitride fiber, can also be that above-mentioned fiber is compiled
The ceramic fiber prefabrication being made into；
When substrate is substrate in the step (1), its purification pretreatment mode is：By substrate successively in acetone, ethanol, different
Ultrasound 15-20min is distinguished in propyl alcohol, deionized water, then takes out and is dried up with hair-dryer；
Substrate is the ceramics such as quartz fibre, alumina fibre, aluminosilicate fiber or silicon nitride fiber in the step (1)
When fiber or its fiber preform, its purification pretreatment mode is：Ceramic fibre or ceramic fiber prefabrication are put into acetone
It is cleaned by ultrasonic 30~120min, Muffle furnace is then put into air atmosphere, be warming up to 400~600 DEG C, 2~4h is incubated, with stove
Cool down to room temperature；
When ceramic fibre is silicon carbide fibre or carbon fiber or its fiber preform in the step (1), it purifies pre- place
Reason mode is：Ceramic fibre or ceramic fiber prefabrication are put into 30~120min of ultrasonic cleaning in acetone, then in an oven
In 100~120 DEG C, 100~120min drying；
Setting inclination angle refers to the plane or ceramic fiber prefabrication that substrate, ceramic fibre beam constituted in the step (2)
Plane and the angle of carrier gas conveying direction, in cvd furnace, suitable inclination angle scope can integrate deposition temperature in guarantee reative cell
Degree is uniform accurately, depositional area is big and deposition efficiency is high, and angle preferred scope is 5 ° -15 °.
Distillation mode 1 is in the step (2)：The NH of quality will be set3BH3Precursor with set length it is evenly laid out
One end of pipeline away from reative cell, with heating tape from one end farthest apart from reative cell gradually at the uniform velocity to close to the one of reative cell
End heating NH3BH3Precursor, makes NH3BH3Precursor gradually distils, and gradually passes through carrier gas and be delivered to reative cell；
Distillation mode 2 is in the step (2)：With self-feeding sublimator in the outdoor distillation of reaction, concrete mode is：By
Auto-feeder is to set speed at the uniform velocity by NH3BH3Precursor is delivered to one end of coupled sublimator, subsequently enters
In container, meanwhile, closed container is heated by induction coil, makes NH3BH3Precursor distils；Sublimator has two gas in post plane
Body connector, is connected by pipeline with auto-feeder and carrier gas respectively, and upper vessel portion has a gas connection ports, carrier gas during distillation
Thus continuously it is passed into entrained precursor in reative cell；
Described distillation mode 2 uses the device of self-feeding sublimator to include motor, worm screw, storage tank, sublimator
And heating coil；Heating coil, which is used to give to have on the left of sublimator heating, sublimator, a company on the right side of carrier gas inlet, sublimator
Adapter, the top of sublimator, which has, is provided with valve on outlet pipe, outlet pipe, outlet pipe carries out outlet gas by barometer
The test of body pressure；Precursor is placed in storage tank, and motor is fixedly connected with one end of worm screw, and worm screw passes through storage tank and distillation
Entered after connecting tube on the right side of device inside sublimator, the worm screw protrusion most 2mm of sublimator medial surface, the band when electric motor operation
Dynamic worm screw rotates, and worm screw, which rotates, drives the precursor in storage tank to enter in sublimator, and sublimator is added by heating coil
Heat, so that precursor distils, the product of distillation is delivered to reative cell by carrier gas from outlet pipe；
Carrier gas is Ar, N in the step (2)2、H2Or Ar/H2Mixed gas, the deposition of deposit in the step (2)
Thickness can be obtained by extending reaction time or increase frequency of depositing；
Step (2) Program cooling refers in 300 DEG C of 0.2~10 DEG C/min coolings maintained above, less than 300 DEG C with
1~10 DEG C/min programs cool or Temperature fall.
The solid-state catabolite that there is nominal mass in sublimation process can not distil, and left behind.So in distillation side
In formula 2, change after precursor is sent into closed container by traditional auto-feeder and directly conveyed precursor by being passed through carrier gas
Method into reative cell, and be changed to auto-feeder and send into precursor after closed container, liter is directly heated in sublimator
China, flores is delivered in reative cell by carrier gas.This method not only ensure that the lasting supply of gaseous products, also solve
Solid is sent directly into reative cell by traditional auto-feeder, and solid powder, which all participates in reaction, causes the coating surface coarse not
Foot；
With the raising (special more than 200 DEG C) of sublimation temperature, bulky grain powder is more in flores, causes after deposition
Fiber surface coating is more coarse.But the yield of flores can be improved with the raising of temperature, so as to improve deposition speed
Rate.So, can be according to difference the need for, consider the smooth factor of efficiency and coating and select suitable sublimation temperature.
In order to obtain the performance of needs under different application environments, it may be necessary to different composition, structure and thickness
BN, can meet different needs by adjusting the factors such as depositing temperature, system pressure, carrier gas flux, reaction time.
Beneficial effect
(1) present invention is from the single constituent element NH containing B, N simultaneously3BH3As the precursor at BN interfaces, this precursor is nontoxic
It is pollution-free, nonflammable, non-explosive B:N=1：1, it is easy to form the BN of stoichiometric proportion, it is ensured that the BN of preparation has preferable
Stoichiometric proportion, it is to avoid B, N disproportionate problem in double elements precursor, and there is no corrosivity gas in preparation process
Body；
(2) present invention can be prepared by 400 DEG C~900 DEG C low temperature chemical vapor deposition methods in reaction temperature, preferably 700~
900 DEG C of yields to improve BN, the sedimentation products BN contents of acquisition are more than 97%.Low temperature depositing can improve fiber as far as possible
Strength retention ratio is more than 90% after strength retention ratio, deposition, and strength retention ratio is more than 70% after high-temperature heat treatment；
(3) 90-200 DEG C of sublimation temperature is selected in distillation mode 1 of the present invention, both can guarantee that precursor can effectively distil simultaneously
And the flores of larger particles will not be produced, make depositing coating fine and close, surface is smooth homogeneous；
(4) distillation mode 2 of the invention not only ensure that the lasting supply of precursor gaseous products, also solve tradition certainly
Solid is sent directly into reative cell by dynamic feed appliance, and solid powder, which all participates in reaction, causes the coarse deficiency of coating surface；
(5) substrate is deposited with carrier gas conveying direction and with certain inclination angle in the present invention, and inclination angle scope is 5 ° -15 °, should
Angle can ensure that depositing temperature is uniform accurately, depositional area is big and deposition efficiency is high in reative cell comprehensive；
(6) interface coating uniform compact prepared by method of the invention, the designability at interface preferably, can be according to coating
The factors such as depositing temperature, system pressure, carrier gas flux reaction time are adjusted the need for thickness, component, the coating of acquisition
Thickness thickness in the μ m of 50nm~3 is controllable, and composition can be unformed boron nitride (a-BN), Turbostratic boron nitride (t-
BN), the good hexagonal boron nitride of crystallinity (h-BN) and their mix products；
(7) coating prepared by method of the invention can be in the substrates such as silicon chip, graphite flake, sapphire sheet, quartz fibre, oxidation
The oxides such as aluminum fiber, aluminosilicate fiber, silicon carbide fibre, carbon fiber, silicon nitride fiber, non-oxidized substance fiber and its fiber
Extensive use is obtained on precast body；
(8) method technique of the invention is simple, favorable repeatability.
Brief description of the drawings
Fig. 1 is by self-feeding sublimator structural representation used in distillation mode 2 of the present invention；
Fig. 2 is the chemical gas-phase deposition system structural representation used in the embodiment of the present invention 1；
Fig. 3 deposit and NH when depositing temperature is respectively 500 DEG C, 700 DEG C, 900 DEG C for the present invention3BH3Fu of precursor
In leaf infrared transmission spectra；
Fig. 4 is alumina fibre boron nitride coating cross section microscopic appearance figure in the embodiment of the present invention 1；
Fig. 5 is silicon nitride fiber boron nitride coating cross section microscopic appearance figure in the embodiment of the present invention 2；
Fig. 6 is alumina fibre boron nitride coating cross section microscopic appearance figure in the embodiment of the present invention 3；
Fig. 7 is Si/SiO in the embodiment of the present invention 42Piece surface topography；
Fig. 8 is Si/SiO in the embodiment of the present invention 42Boron nitride coating Fourier infrared transmission spectra on piece；
Fig. 9 is alumina fibre boron nitride coating cross section microscopic appearance figure in the embodiment of the present invention 5；
Figure 10 is the structural representation of the cvd furnace used in embodiments of the invention 5.
Embodiment
In conjunction with embodiment, the invention will be further described：
Embodiment 1
A kind of preparation method of the surfaces nitrided boron interface coating of alumina fibre, step is：
(1) it is 14cm by length, the beam of alumina fibre 10 of 500/beam carries out purification pretreatment, and preprocessing process is：
It is first placed into acetone and is cleaned by ultrasonic 50min, is then placed in Muffle furnace and is heated in air atmosphere, heating-up temperature 500
DEG C, room temperature is down in heat time 2h, furnace cooling, to remove alumina fibre surface coating；
(2) alumina fibre obtained by step (1) is fixed on the stuffed quartz support that cross section is right angled triangle
On, the long 15cm in inclined-plane of support, inclination angle is 5 °, and then stuffed quartz branch is placed in the hot-wall cvd cvd furnace of horizontal positioned
Deposited tube reative cell in, the overall length of quartz ampoule (quartz deposition pipe) is 1.2m, and its center 36cm is sunk in resistance tubular type
In product stove, its left end protrusion cvd furnace high order end 40cm, its right-hand member protrusion cvd furnace low order end 44cm are anti-apart from quartz deposition pipe
Answer the 3.0g NH that horizontal positioned length is 15cm at the low order end 5cm of room3BH3Precursor, is first passed through 280sccm/cm2Ar is cleaned
Pipeline 15min, is heated to 900 DEG C, after temperature stabilization with 10 DEG C/min heating rates again afterwards, with heating tape from NH3BH3Pioneer
The low order end (such as Fig. 2) of body passes through 180sccm/cm with 100 DEG C of constant-speed heating precursors from right to left, now flores2Ar
Gas is transported in the reative cell of deposited tube as carrier gas, and flores carries out reactive deposition on alumina fibre surface, and reaction is heavy
The product time be deposited tube reative cell in 2 hours, deposition process pressure be 100Kpa, deposition process after the completion of, stop distillation
The conveying of product, keeps carrier gas circulation, until reative cell is cooled to room temperature with 5 DEG C/min rate of temperature fall, closes carrier gas, takes out
Alumina fibre with deposit, the thickness of deposit is 870nm.Wherein, specific chemical gaseous phase used in embodiment 1
Depositing system signal is as shown in Figure 2；
(3) alumina fibre with deposit that step (2) is obtained is subjected to high-temperature process, treatment temperature：1000 DEG C,
Handle atmosphere:Ar gases, processing time：2h.
The cross section microscopic appearance figure of product floating coat obtained above is as shown in figure 4, as shown in Figure 4, coating is consistent
It is close, it is well combined with fiber；
Carry out tensile strength test to band coating alumina fibre obtained above, testing standard with reference to national military standard on
Carbon mono-filaments tensile property testing standard GJB 1871-1994《Individual carbon fibers Erichsen test method》.
The single fiber tensile strength that the pretreated alumina fibre of purification is carried out in above-mentioned steps (1) is 2.75GPa；
The single fiber tensile strength of the alumina fibre precast body of the coating obtained in above-mentioned steps (2) is
2.5GPa, its strength retention ratio is 91%；
The single fiber tensile strength of the alumina fibre precast body of coating is after being heat-treated in above-mentioned steps (3)
2.28GPa, its strength retention ratio is 83%.
Embodiment 2
A kind of preparation method of silicon nitride fiber boron nitride interface coating, step is：
(1) it is 14cm by length, the beam of silicon nitride fiber 10 of 500/beam carries out purification pretreatment, and preprocessing process is：
It is first placed into acetone and is cleaned by ultrasonic 50min, is then placed in Muffle furnace and is heated in air atmosphere, heating-up temperature 500
DEG C, room temperature is down in heat time 2h, furnace cooling, to remove silicon nitride fiber surface coating；
(2) silicon nitride fiber obtained by step (1) is fixed on the stuffed quartz support that cross section is right angled triangle
On, the long 15cm in inclined-plane of support, inclination angle is 5 °, and then stuffed quartz branch is placed in the hot-wall cvd cvd furnace of horizontal positioned
Deposited tube reative cell in, the overall length of deposited tube is 1.2m, and its center 36cm is in cvd furnace, and its left end protrusion is heavy
Product stove high order end 40cm, its right-hand member protrusion cvd furnace low order end 44cm, the horizontal positioned length at the low order end 5cm of cvd furnace
For 15cm 0.5g NH3BH3Precursor, is first passed through 280sccm/cm2Ar detergent line 15min, afterwards again with 10 DEG C/min liters
Warm speed is heated to 500 DEG C, after temperature stabilization, with heating tape from NH3BH3The low order end (such as Fig. 2) of precursor is with 180 DEG C from the right side
To left constant-speed heating precursor, now flores passes through 100sccm/cm2Ar gas is transported to the reaction of deposited tube as carrier gas
In room, flores carries out reactive deposition on silicon nitride fiber surface, during the reactive deposition time is 1.5 hours, deposition process
The pressure of deposited tube reative cell is 100Kpa, after the completion of deposition process, stops the conveying of flores, keeps carrier gas circulation, directly
Room temperature is cooled to 5 DEG C/min rate of temperature fall to reative cell, carrier gas is closed, takes out the silicon nitride fiber with deposit, sink
The thickness of product thing is 300nm；
(3) silicon nitride fiber with deposit that step (2) is obtained is subjected to high-temperature process, treatment temperature：1200 DEG C,
Handle atmosphere:N2Gas, processing time：2h.
The cross section microscopic appearance figure of product floating coat obtained above is as shown in figure 5, as shown in Figure 5, coating is consistent
It is close, it is well combined with fiber；
Carry out tensile strength test to band coating silicon nitride fiber obtained above, testing standard with reference to national military standard on
Carbon mono-filaments tensile property testing standard GJB 1871-1994《Individual carbon fibers Erichsen test method》.
The single fiber tensile strength that the pretreated silicon nitride fiber of purification is carried out in above-mentioned steps (1) is 1.85GPa；
The single fiber tensile strength of the silicon nitride fiber precast body of the coating obtained in above-mentioned steps (2) is
1.72GPa, its strength retention ratio is 93%；
The single fiber tensile strength of the silicon nitride fiber precast body of coating is after being heat-treated in above-mentioned steps (3)
1.57GPa, its strength retention ratio is 85%.
Embodiment 3
A kind of preparation method of the surfaces nitrided boron interface coating of alumina fibre, step is：
(1) it is 10cm by length, the beam of alumina fibre 10 of 500/beam carries out purification pretreatment, and preprocessing process is：
It is first placed into acetone and is cleaned by ultrasonic 50min, is then placed in Muffle furnace and is heated in air atmosphere, heating-up temperature 500
DEG C, room temperature is down in heat time 2h, furnace cooling, to remove alumina fibre surface coating；
(2) alumina fibre obtained by step (1) is fixed on the stuffed quartz support that cross section is right angled triangle
On, the long 11cm in inclined-plane of support, inclination angle is 8 °, and then stuffed quartz branch is placed in the hot-wall cvd cvd furnace of horizontal positioned
Deposited tube reative cell in, the overall length of deposited tube is 1.2m, and its center 36cm is in cvd furnace, its left end protrusion deposition
Stove high order end 40cm, its right-hand member protrusion cvd furnace low order end 44cm, the horizontal positioned at the low order end 5cm of deposited tube reative cell
Length is 15cm 3.0g NH3BH3Precursor, is first passed through 280sccm/cm2Ar detergent line 15min, afterwards again with 10 DEG C/
Min heating rates are heated to 900 DEG C, after temperature stabilization, with heating tape from NH3BH3The low order end (such as Fig. 2) of precursor is with 100 DEG C
Constant-speed heating precursor from right to left, now flores pass through 180sccm/cm2Ar gas is transported to deposited tube as carrier gas
In reative cell, flores carries out reactive deposition on alumina fibre surface, and the reactive deposition time is 2 hours, deposition process
The pressure of middle deposited tube reative cell is 100Kpa, after the completion of deposition process, stops the conveying of flores, keeps carrier gas circulation,
Until reative cell is cooled to room temperature with 5 DEG C/min rate of temperature fall, carrier gas is closed, the alumina fibre with deposit is taken out,
The thickness of deposit is 970nm；
(3) alumina fibre with deposit that step (2) is obtained is subjected to high-temperature process, treatment temperature：1000 DEG C,
Handle atmosphere:Ar gases, processing time：2h.
The cross section microscopic appearance figure of product floating coat obtained above is as shown in fig. 6, it will be appreciated from fig. 6 that coating is consistent
It is close, it is well combined with fiber；
Carry out tensile strength test to band coating alumina fibre obtained above, testing standard with reference to national military standard on
Carbon mono-filaments tensile property testing standard GJB 1871-1994《Individual carbon fibers Erichsen test method》.
The single fiber tensile strength that the pretreated alumina fibre of purification is carried out in above-mentioned steps (1) is 2.76GPa；
The single fiber tensile strength of the alumina fibre precast body of the coating obtained in above-mentioned steps (2) is
2.48GPa, its strength retention ratio is 90%；
The single fiber tensile strength of the alumina fibre precast body of coating is after being heat-treated in above-mentioned steps (3)
2.32GPa, its strength retention ratio is 84%.
Embodiment 4
A kind of Si/SiO2The preparation method of the surfaces nitrided boron coating of piece, step is：
(1) by 1.5cm × 2cm Si/SiO2Piece carries out purification pretreatment, and preprocessing process is：It is sequentially placed into acetone, second
It is each in alcohol, isopropanol and deionized water to be cleaned by ultrasonic 15min, then take out and dried up with hair-dryer；
(2) by the Si/SiO obtained by step (1)2Piece is fixed on the stuffed quartz support that cross section is right angled triangle
On, the long 3cm in inclined-plane of support, inclination angle is 5 °, and then stuffed quartz branch is placed in the hot-wall cvd cvd furnace of horizontal positioned
In deposited tube reative cell, the overall length of deposited tube is 1.2m, and its center 36cm is in cvd furnace, its left end protrusion cvd furnace
High order end 40cm, its right-hand member protrusion cvd furnace low order end 44cm, horizontal positioned is long at the low order end 5cm of deposited tube reative cell
Spend the 0.5gNH for 15cm3BH3Precursor, is first passed through 280sccm/cm2Ar detergent line 15min, afterwards again with 10 DEG C/min liters
Warm speed is heated to 900 DEG C, after temperature stabilization, with heating tape from NH3BH3The low order end (such as Fig. 2) of precursor is with 180 DEG C from the right side
To left constant-speed heating precursor, now flores passes through 180sccm/cm2Ar gas is transported to the reaction of deposited tube as carrier gas
In room, flores is in Si/SiO2Piece surface carries out reactive deposition, and the reactive deposition time is deposition in 1 hour, deposition process
The pressure of tube reaction room is 100Kpa, after the completion of deposition process, stops the conveying of flores, keeps carrier gas circulation, until anti-
Answer room to be cooled to room temperature with 5 DEG C/min rate of temperature fall, close carrier gas, take out the Si/SiO with deposit2Piece；
(3) Si/SiO with deposit for obtaining step (2)2Piece carries out high-temperature process, treatment temperature：1000 DEG C,
Handle atmosphere:Ar gases, processing time：2h.
The surface topography and FTIR collection of illustrative plates of product floating coat obtained above as shown in Figure 7 and Figure 8, can by Fig. 7 and Fig. 8
Know, Si/SiO2Piece Surface Creation BN coatings, coating uniform compact.
Embodiment 5
A kind of preparation method of the surfaces nitrided boron interface coating of alumina fibre, step is：
(1) it is 14cm by length, the beam of alumina fibre 10 of 500/beam carries out purification pretreatment, and preprocessing process is：
It is first placed into acetone and is cleaned by ultrasonic 50min, is then placed in Muffle furnace and is heated in air atmosphere, heating-up temperature 500
DEG C, room temperature is down in heat time 2h, furnace cooling, to remove alumina fibre surface coating；
(2) alumina fibre obtained by step (1) is fixed on the stuffed quartz support that cross section is right angled triangle
On, the long 15cm in inclined-plane of support, inclination angle is 5 °, and then stuffed quartz branch is placed in the hot-wall cvd cvd furnace of horizontal positioned
Deposited tube reative cell in, the overall length of quartz ampoule (quartz deposition pipe) is 1.2m, and its center 36cm is sunk in resistance tubular type
In product stove, its left end protrusion cvd furnace high order end 40cm, its right-hand member protrusion cvd furnace low order end 44cm；
First it is passed through 280sccm/cm2Ar detergent line 15min, are heated to 700 DEG C with 10 DEG C/min heating rates again afterwards,
After temperature stabilization, by auto-feeder to set speed at the uniform velocity by NH3BH3Precursor is delivered in coupled sublimator,
As shown in figure 1, simultaneously, sublimator is heated by induction coil, 180 DEG C of heating-up temperature makes NH3BH3Precursor distils；180sccm/
cm2Ar gas enters sublimator as carrier gas by interface on the left of sublimator, and conveying flores is entered in reative cell by top exit,
As shown in Figure 10, flores carries out reactive deposition on alumina fibre surface, and the reactive deposition time is 2 hours, is deposited
After the completion of the pressure of deposited tube reative cell is 100Kpa, deposition process in journey, stop the conveying of flores, keep carrier gas stream
It is logical, until reative cell is cooled to room temperature with 5 DEG C/min rate of temperature fall, carrier gas is closed, the aluminum oxide with deposit is taken out fine
Dimension, the thickness of deposit is 420nm；
(3) alumina fibre with deposit that step (2) is obtained is subjected to high-temperature process, treatment temperature：1000 DEG C,
Handle atmosphere:Ar gases, processing time：2h.
Coatings cross-section microscopic appearance figure obtained above is as shown in figure 9, as shown in Figure 9, coating uniform compact, with fiber
It is well combined；
Carry out tensile strength test to band coating alumina fibre obtained above, testing standard with reference to national military standard on
Carbon mono-filaments tensile property testing standard GJB 1871-1994《Individual carbon fibers Erichsen test method》.
The single fiber tensile strength that the pretreated alumina fibre of purification is carried out in above-mentioned steps (1) is 2.71GPa；
The single fiber tensile strength of the alumina fibre precast body of the coating obtained in above-mentioned steps (2) is
2.49GPa, its strength retention ratio is 92%；
The single fiber tensile strength of the alumina fibre precast body of coating is after being heat-treated in above-mentioned steps (3)
2.22GPa, its strength retention ratio is 82%.
To NH3BH3The deposit that precursor and embodiment 1,2,5 are obtained carries out Fourier's infrared transmission test, obtains Fu
In leaf infrared transmission spectra as shown in figure 3, it can be seen from Fig. 3 boron ammonia alkane complex compound generate sedimentation products N-H, B-H
Vibration peak disappear, only positioned at 1369cm-1B-N stretching vibration and 795cm-1B-N flexural vibrations, illustrate deposition
Product boron nitride.And the yield with the rise boron nitride of temperature is higher.
The content not being described in detail in description of the invention belongs to the known technology of professional and technical personnel in the field.
Claims (8)
1. a kind of preparation method of boron nitride interface coating, it is characterised in that step is：
(1) deposition substrate is subjected to purification pretreatment；
(2) pretreated substrate will be purified to be placed in the reative cell of chemical vapor deposition stove to set inclination angle, NH3BH3Precursor
Reaction outdoor is connected to setting means, closed air-channel system is formed with reative cell；It is passed through setting species, flow and time
The air that carrier gas is fully cleaned in displacement air-channel system；When reaction chamber temperature is with 5~20 DEG C/min heating rate heating responses room
It is outdoor with 90~200 DEG C of distillation NH in reaction after temperature stabilization to 400 DEG C~900 DEG C3BH3Precursor, flores is by carrying
Gas is delivered to reative cell, and now flores starts in substrate surface deposition reaction, generates boron nitride；Kept in deposition process anti-
Chamber pressure is answered for 5Kpa-100Kpa, after the completion of deposition process, stops the conveying of flores, carrier gas circulation is kept, until reacting
Room program is cooled to room temperature, closes carrier gas, takes out the substrate with deposit, the thickness of deposit is 50nm-3 μm；
(3) substrate with deposit that step (2) is obtained is subjected to high-temperature process, obtains the base with boron nitride interface coating
Bottom；
Distillation mode is in the step (2)：Distilled with self-feeding sublimator in reaction outdoor, concrete mode is：By
Auto-feeder is to set speed at the uniform velocity by NH3BH3Precursor is delivered to one end of coupled sublimator, subsequently enters
In container, meanwhile, closed container is heated by induction coil, makes NH3BH3Precursor distils；Sublimator has two gas in post plane
Body connector, is connected by pipeline with auto-feeder and carrier gas respectively, and upper vessel portion has a gas connection ports, carrier gas during distillation
Thus continuously it is passed into entrained precursor in reative cell；Auto-feeder used in described distillation mode includes electricity
Motivation, worm screw, storage tank, sublimator and heating coil；Heating coil, which is used to give on the left of sublimator heating, sublimator, has carrier gas to enter
Mouthful, there is a connecting tube on the right side of sublimator, the top of sublimator, which has, is provided with valve, escape pipe on outlet pipe, outlet pipe
Road carries out the test of outlet gas pressure by barometer；Precursor is placed in storage tank, and one end of motor and worm screw is fixed
Connection, worm screw is entered inside sublimator after passing through the connecting tube on the right side of storage tank and sublimator, worm screw protrusion sublimator medial surface
Most 2mm, drive worm screw to rotate when electric motor operation, and worm screw, which rotates, drives the precursor in storage tank to enter in sublimator,
Sublimator is heated by heating coil, so that precursor distils, the product of distillation is defeated from outlet pipe by carrier gas
Deliver to reative cell.
2. a kind of preparation method of boron nitride interface coating according to claim 1, it is characterised in that：The heating of reative cell
Temperature is 700~900 DEG C.
3. a kind of preparation method of boron nitride interface coating according to claim 1, it is characterised in that：The distillation of precursor
Temperature is 100~180 DEG C.
4. a kind of preparation method of boron nitride interface coating according to claim 1, it is characterised in that：The step (1)
Middle substrate is substrate such as graphite flake, silicon chip or sapphire sheet, and its purification pretreatment mode is：By substrate successively acetone, ethanol,
Ultrasound 15-20min is distinguished in isopropanol, deionized water, then takes out and is dried up with hair-dryer.
5. a kind of preparation method of boron nitride interface coating according to claim 1, it is characterised in that：The step (1)
When middle substrate is quartz fibre, alumina fibre, aluminosilicate fiber or silicon nitride fiber or its fiber preform, it purifies pre-
Processing mode is：Ceramic fibre or ceramic fiber prefabrication are put into 30~120min of ultrasonic cleaning in acetone, then in air
Muffle furnace is put into atmosphere, 400~600 DEG C are warming up to, 2~4h is incubated, room temperature is down in furnace cooling.
6. a kind of preparation method of boron nitride interface coating according to claim 1, it is characterised in that：The step (1)
When middle ceramic fibre is silicon carbide fibre or carbon fiber or its fiber preform, its purification pretreatment mode is：By ceramic fibre
Or ceramic fiber prefabrication is put into acetone 30~120min of ultrasonic cleaning, then in an oven in 100~120 DEG C, 100~
120min is dried.
7. a kind of preparation method of boron nitride interface coating according to claim 1, it is characterised in that：The step (2)
Middle setting inclination angle refers to the plane or ceramic fiber prefabrication plane that substrate, ceramic fibre beam constituted and carrier gas conveying direction
Angle, angle preferred scope is 5 ° -15 °.
8. a kind of preparation method of boron nitride interface coating according to claim 1, it is characterised in that：Described step
(3) when high temperature is handled, treatment temperature：1000~1600 DEG C, handle atmosphere:Ar、N2、H2Or Ar/H2Mixed gas, processing
Time：1~5h.
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