CN106116698B - A kind of low-heat leads SiCN-Y2SiO5Environment barrier preparation method of composite coating - Google Patents
A kind of low-heat leads SiCN-Y2SiO5Environment barrier preparation method of composite coating Download PDFInfo
- Publication number
- CN106116698B CN106116698B CN201610453576.2A CN201610453576A CN106116698B CN 106116698 B CN106116698 B CN 106116698B CN 201610453576 A CN201610453576 A CN 201610453576A CN 106116698 B CN106116698 B CN 106116698B
- Authority
- CN
- China
- Prior art keywords
- sio
- sicn
- coating
- environment barrier
- low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
- C04B41/5062—Borides, Nitrides or Silicides
- C04B41/5066—Silicon nitride
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/87—Ceramics
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Products (AREA)
- Coating By Spraying Or Casting (AREA)
Abstract
The present invention relates to a kind of low-heat to lead SiCN-Y2SiO5Environment barrier preparation method of composite coating, by ceramic aggregate powder Y2SiO5Uniform suspension is obtained with being scattered in isopropanol solvent after SiCN mixing, hybrid adhesive is then added, it is ensured that SiCN-Y is prepared in conjunction with electrostatic spinning technique and Supersonic Plasma Spraying in binder sufficiently dissolution mixing in suspension2SiO5The compound external coating of environment barrier.Compared with prior art, the characteristic that there is the present invention preferable interfacial combined function and low-heat to lead, obtains the SiCN-Y of homogeneous multiple phases2SiO5Combinational environment barrier coating, does not need Post isothermal treatment.
Description
Technical field
The present invention relates to a kind of preparation methods of polymer precursor ceramic outer coating, lead more particularly, to a kind of low-heat
SiCN-Y2SiO5Environment barrier preparation method of composite coating.
Background technique
Ceramic Matrix Composites Reinforced by Carbon Fibers (C/SiC, CMCs) is a kind of novel high-performance composite material, 20
Since century 70, the new hot spot of structural material research field is become.C/SiC composite material is since it is with following two aspect
Advantage：One side continuous carbon fibre introduces the toughness for improving composite material, on the other hand remains SiC ceramic matrix strength
The advantages that high, high temperature resistant is a kind of high temperature structural material and functional material.It is obtained in military, civilian key areas
It is more and more widely used, such as high-temperature unit of aircraft engine, high speed brake material, rocket nozzle, space shuttle
Thermal protection system, nuclear reactor plasma facing material etc..But C/SiC composite material, under high temperature and high speed combustion gas environment, meeting is rapid
Oxidation occurs and generates SiO2Phase, the high temperature resistance that C/SiC composite material can be made to have had, however SiO2Mutually in high temperature item
It reacts under part with vapor, forms gaseous Si (OH)4Phase causes the failure of C/SiC composite material.This will be limited significantly
Its application, thus C/SiC composite material oxidation and vapor corrosion protection question become the heat of recent domestic research
One of point.High-temperature oxidation resistant protection is carried out to it simultaneously to have great importance to its high temperature application.
Environment barrier coating (Environmental barrier coatings, EBCs) is considered as solving SiC base to answer
The effective ways of condensation material high-temperature oxydation problem and vapor corrosion problem.Si coating due to C/SiC composite material physics,
Chemical compatibility is good and generally uses as transition zone, but single Si coating (3.4-4.5 × 10-6/ DEG C) it cannot be to C/
SiC(4.5-5.5×10-6/ DEG C) matrix offer is effectively protected, is finally quickly invalidated in the case where high temperature is aerobic and water vapor conditions.
Mullite coating (Mullite, CTE:5.5×10-6/ DEG C) because it is with preferable high-temperature stability, antioxygenic property, hypoxemia infiltration
Saturating rate, but since the mullite coating of thermal spraying is in high temperature preparation process, rapid cooling can occur crystalline transition and cause
Volume contraction causes the peeling of crackle generation and coating in coating；In addition, mullite coating is under high-temperature fuel gas Scouring Condition, meeting
Cause SiO2Volatilization, remaining porous Al2O3Coating, which is easy leafing, leads to coating failure.In order to solve problem above, compound
EBCs becomes current research hotspot.
Up to the present the preparation method of external coating is varied, is mainly the following：Air plasma spraying method
(APS), chemical vapor deposition (CVD), slurry cladding process (Slurry dip-coating), sol-gel method (Sol-gel),
Magnetron sputtering method, electron beam physical vapor deposit (EB-PVD) and polymer precursor ceramic coating method etc..Using independent atmosphere
Although plasma spraying technology preparation C/SiC composite material environment barrier coating can regulate and control to prepare it is laminar structured, in coating
There are certain porositys, but the structure in specific hole, are uniformly distributed and are difficult to control with the size in aperture, cannot achieve coating heat
The regulation of conductance and compactness；Simultaneously because the presence of thermal stress, leads to occur vertical crack in coating, it in this way will be to coating
Later period performance is unfavorable.It needs to carry out under 900-1200 DEG C of hot conditions using the coating of chemical vapor deposition preparation, and heavy
Product low efficiency, it is at high cost, it forms and is difficult to control in coating, tail gas is difficult to be recycled.The outer painting prepared using sol-gel method
The shortcomings that layer surface is easy to crack and coating layer thickness is insufficient and needs later period high-temperature heat treatment.And slurry cladding process is used to prepare
Coating is still deposited will repeatedly spin coating and the drawbacks of cannot once prepare completion, need Post isothermal treatment repeatedly.Same magnetron sputtering
Although method and electro beam physics vapour deposition method have prepared environment barrier coating, which needs
Early period target preparation, the high requirements on the equipment and be difficult to control, it is still necessary to further for prepared hot environment barrier performance
Raising.There are also polymer precursor china-clay method prepares coating method is used, such direct prepares coating of method will generate painting
Layer volume contraction is and at the same time the deposition efficiency of coating is low and compactness is poor.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of not only preparation efficiencies
Height, and interface cohesion is good, the low-heat of short preparation period leads SiCN-Y2SiO5Environment barrier preparation method of composite coating, in electrostatic
Under spining technology subsidiary conditions, the microballoon of heterogeneity and porous hollow can be obtained, it can be effective for supersonic speed etc.
Plasma spray prepares the coating of uniform, controllable porous structure.The spy that there is this coating preferable interfacial combined function and low-heat to lead
Property, it can effectively obtain the SiCN-Y of homogeneous multiple phases2SiO5Combinational environment barrier coating, does not need Post isothermal treatment.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of low-heat leads SiCN-Y2SiO5Environment barrier preparation method of composite coating, using following steps：
(1) using dehydrated alcohol as ball-milling medium, using planetary ball mill Y2SiO5Powder grinds after dry and obtains ceramic aggregate
Powder Y2SiO5, using the polysilazane after cumyl peroxide is crosslinked is added in tube furnace, it is pyrolyzed to obtain under argon atmosphere protection
To SiCN ceramic powders；
(2) by ceramic aggregate powder Y2SiO5Disperse respectively after 4~9: 1~6 uniform ground and mixeds with SiCN according to mass ratio
In isopropanol solvent, using magnetic agitation 5-20min, then 0.2-10wt% polyvinyl alcohol is added thereto as dispersing agent,
Continue magnetic agitation 5-20min, uniform suspension is then obtained using cell ultrasonic disintegrator ultrasonic vibration 10-40min；
(3) hybrid adhesive of epoxy resin and polyethersulfone resin composition is added into suspension, then control stirring turns
Speed is 200-600r/min, mechanical stirring 6-24h, while using 30-70 DEG C of constant temperature oil bath heating, it is ensured that binder is in suspension
In sufficiently dissolution mixing；
(4) slurry being mixed to get is put into the air for vacuumizing and being excluded in slurry in vacuum desiccator, is then transferred to note
In emitter, then syringe is packed into precise injection and is pumped, and connects syringe and nozzle；Respectively by nozzle and Sheng deionized water
The anode and cathode for receiving container connection power supply open simultaneously power supply and syringe pump and carry out EFI preparation, after will obtain
Porous microsphere presoma is stood, naturally dry after filtering；
(5) obtained porous microsphere presoma is put into sintered heat insulating 1-4h in 1000-1250 DEG C of high temperature box furnace, controlled
Heating rate and rate of temperature fall are 2-6 DEG C/min, and re-sieving obtains 30-125 μm of porous composite ceramics microballoon；
(6) by obtained porous composite ceramics microballoon in the C/SiC composite sample table for having Si/mullite coating
SiCN-Y is prepared using Supersonic Plasma Spraying in face2SiO5The compound external coating of environment barrier.
Ceramic aggregate powder Y in step (1)2SiO5Partial size be 0.5-1 μm, the partial sizes of SiCN ceramic powders is 20-
120nm, the temperature of tube furnace are controlled at 1000-1400 DEG C, are pyrolyzed 1-5h, heating rate and rate of temperature fall are 2-8 DEG C/min.
Ceramic aggregate powder Y in suspension described in step (2)2SiO5Mass ratio with isopropanol is 1~8: 2~10.
Concentration of the hybrid adhesive in suspension described in step (3) be 5-12wt%, this kind of hybrid adhesive by
Epoxy resin and the polyethersulfone resin composition that mass ratio is 1~4: 1~9.
Controlling injection rate in step (4) during electrospray is 1.5-4.0mL/min, supply voltage 5-20kV.
The present invention is in order to obtain the ceramic microsphere with porous and hollow structure lower thermal conductivity, and then later period preparation is uniform
Porous low-heat leads SiCN-Y2SiO5The compound external coating of environment barrier；And it is porous and hollow to have selected electrostatic spinning technique to prepare
Microballoon, process above condition are by many experiments, in conjunction with the principle summary point of electrostatic spinning technique preparation ceramic microspheres
The data result of analysis.If the beneficial effect of the application can not be obtained not under above-mentioned process conditions, the reason is as follows that：One side
Face, ceramic powder SiCN and Y2SiO5Only there is the above suitable proportion, guarantee that coating has excellent anti-oxidant and vapour resistant
The performance of corrosion, while two kinds of ceramic powder particles partial sizes are different, the sintering process regulation of micro-nano composite granule, to Porous hollow
The structure of ceramic powder is advantageous；On the other hand, only under the conditions of process above, ceramic powder can be uniformly suspended in solvent,
Binder can sufficiently modulate the viscosity and suspension effect of slurry, and above slurry spray technology parameter help to obtain the present invention
It is required that ceramic microsphere particle size range, to effectively prepare required composite coating.
When step (6) carries out Supersonic Plasma Spraying, control voltage is 350-500V, and electric current is 100-200 A, argon gas
Flow is 80-120L/min, and hydrogen flowing quantity 8-20L/min, powder feeder flow is 2-10g/min, and the mobile rate of spray gun is
400-1000mm/s, spray distance 8-15mm, substrate preheating temperature are 300-800 DEG C, and spraying number is 20-50 times, spraying
After naturally cool to room temperature, obtain SiCN-Y2SiO5The compound external coating of environment barrier.The present invention is in order to obtain porous low-heat
It leads and the preferable coating of interface cohesion, while the preparation method that coating deposition efficiency is high, has selected the above supersonic speed plasma spray
Painting technology；Process above parameter is all by many experiments, obtained from analysis and summary.If not under above-mentioned process conditions,
The melting of porous ceramics microballoon is bad, and the flow velocity of ceramic microsphere is improper, it is possible to prepare loose, be sintered bad and interface and tie
Close poor coating；Conversely, spraying flame melting temperature it is excessively high, ceramic microsphere flow velocity is too fast so that the micropore of porous microsphere and
Mesoporous to retain, coating is comparatively dense, while the excessively high coating interface that can also reduce of deposition process substrate temperature is combined and generated
Thermal stress leads to existing defects in coating.
Electrostatic spinning technique device is made of pedestal, jet port, high voltage power supply and reception container.In injector head and receive
Apply a high voltage electric field between container, voltage is usually from 1kV to 20kV.The material of spinning is needed to be dissolved in or hang first
Float in solvent appropriate, be suitably added suspending agent and binder stirs evenly, is added to the appearance with different size jet ports
In device.In jet port and the action direction of the electric field force and surface tension of liquid that apply between container is received on the contrary, will be half
The droplet surface of ball shape generates an outside power.When electric field gradually increases, the homophilic charge in solution is forced to be gathered in
Droplet surface, electric field caused by droplet surface charge make the drop of jet port gradually become taper (Taylor by hemispherical
Cone).When electric field is sufficiently large, jet stream is just sprayed from droplet surface.In general, the electric conductivity of solution is stronger, more easy to form
Injection.Injection stream is then accelerated and is elongated by electric field force, and viscosity and the injection rate difference of solution are formed by droplet size not
Together, so fall into receiving vessel occur inversion of phases granular size it is different, finally obtain various sizes of microsphere particle or
Various sizes of fiber.Then the microsphere particle that will solidify passes through filtering, naturally dry, the processes such as heat treatment
Obtain varying particle size, porous ceramic microsphere.Such microballoon has porous hollow, can by the regulation of late stage process
To obtain that the thermal conductivity of ceramic powders can be effectively reduced comprising micropore and mesoporous ceramic microsphere.It is special that such powder has
Porous structure, this has great importance for preparing low-heat and leading with the environment barrier coating of different composed structures.In electrostatic
Under spining technology subsidiary conditions, the microsphere powder of heterogeneity can be obtained, and then multiple groups are prepared using plasma spraying technology
Divide combinational environment barrier coating.The present invention synthesizes Y using technology made above2SiO5/ SiCN hollow microsphere, in conjunction with atmosphere etc. from
Son spraying, which is realized, to be obtained uniform, low-heat under controlled condition and leads, and has microstructural, oxidation resistant SiCN-Y2SiO5It is multiple
Cyclization border barrier coating.In addition, electrostatic spinning technique also have the characteristics that it is simple to operate, at low cost, easy to control.
Compared with prior art, the present invention has the following advantages that：
(1) SiCN-Y is prepared using electrostatic spinning technique auxiliary Supersonic Plasma Spraying method2SiO5Environment barrier is compound
External coating thickness is uniform, surface flawless and equally distributed micropore and meso-hole structure is presented.First of all for obtain low-heat lead and
The SiCN-Y that anti-oxidant and vapour resistant is had excellent performance2SiO5The compound external coating of environment barrier is easy system using electrostatic spinning technique
Standby porous and hollow ceramic microsphere, while microsphere powder ingredient can be regulated and controled, and the mobility of microballoon is preferably convenient for
Later period spraying uses；Can be by the sintering of control microballoon, and then control is the structure and performance of microballoon.In addition, supersonic speed etc.
Plasma spray can efficiently prepare ceramic coating, and the mechanical property of coating and interfacial combined function are all fine, and control
Spraying process processed, can be effectively retained the micropore and meso-hole structure of original porous microballoon, to be easier to obtain in homogeneous thickness
Low-heat lead ring border barrier external coating, the method are also suitably applied industrial production.
(2) SiCN-Y being prepared2SiO5The compound external coating crystallinity of environment barrier is good, strength of coating is high and interface
In conjunction with preferable, porous structure effectively reduces the thermal conductivity of coating while can prevent the formation of crackle, has preferable heat resistanceheat resistant
Shock stability and steam resistance oxidation characteristics energy.
(3) SiCN-Y being prepared2SiO5The compound external coating ingredient of environment barrier and microstructure easy-regulating, raw material are easy
, it is high-efficient, it is suitble to industrial production.
(4) the environment barrier composite coating being prepared has excellent anti-oxidant and vapour resistant corrosive nature, can be
1400 DEG C of vapor-oxygen (50%H2O-50%O2) under environment to C/SiC composite material effective protection 200h, oxidation weight loss
Less than 2%.
Detailed description of the invention
Fig. 1 is the SiCN-Y of preparation2SiO5The SEM photograph of ceramic microspheres；
Fig. 2 is SiCN-Y2SiO5The SEM photograph of the compound external coating section of environment barrier；
Fig. 3 is SiCN-Y2SiO5The relation curve of environment barrier compound external coating thermal conductivity and temperature.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Embodiment 1：
A kind of low-heat leads SiCN-Y2SiO5Environment barrier preparation method of composite coating, using following steps：
(1) it takes using solid sintering technology (Ziqi Sun, Meishuan Li, Yanchun Zhou.Thermal
properties of single-phase Y2SiO5[J].Journal of the European Ceramic
Society.29 (2009) 551-557.) synthesis Y2SiO5Powder, using dehydrated alcohol as ball-milling medium, using planetary ball mill
48h is ground for use (0.5-1 μm) after dry using agate mortar；Using by 20Wt% cumyl peroxide is added
(DCP) polysilazane (Northwestern Polytechnical University's preparation, PSN) after being crosslinked by 1200 DEG C of high temperature process furnances, protect by argon atmosphere
Shield is lower to be pyrolyzed 2h, controls heating rate and rate of temperature fall is 5 DEG C/min, SiCN ceramic powders (60nm) can be obtained；
(2) by the above ceramic aggregate powder Y2SiO5Disperse respectively behind (6: 4) uniformly ground and mixed with SiCN according to mass ratio
In isopropanol solvent, using magnetic agitation 15min, then 5.0Wt% polyvinyl alcohol (PVA) is added thereto and is used as dispersing agent,
Continue magnetic agitation 15min, uniform suspending liquid A is then obtained using cell ultrasonic disintegrator ultrasonic vibration 20min, control is outstanding
The mass ratio of ceramic aggregate and isopropanol is (3: 5) in supernatant liquid A；
(3) suspending liquid A is transferred in conical flask, while 10Wt% hybrid adhesive epoxy resin and polyether sulfone tree is added
Rouge, controlling its mass ratio is (1: 1), and then this conical flask is installed on iron stand, using mechanical stirring 12h, adjusts stirring and turns
Speed is 400r/min, while using 50 DEG C of constant temperature oil bath heating, it is ensured that binder sufficiently dissolution mixing in suspension；
(4) by above-mentioned configured slurry, it is put into the air for vacuumizing and being excluded in slurry in vacuum desiccator, is then transferred to
In 100mL syringe, then syringe is packed into precise injection and is pumped, and connects syringe and nozzle；Nozzle and Sheng are gone respectively
The anode and cathode for receiving container connection power supply of ionized water, open simultaneously power supply and syringe pump carries out EFI preparation, control note
Firing rate rate is 2.5mL/min, supply voltage 15kV.After prepared by EFI, the porous microsphere presoma of preparation is stood, mistake
Naturally dry after filter；
(5) the above porous microsphere presoma is put into sintered heat insulating 2h in 1200 DEG C of high temperature box furnaces, controls heating rate
It is 5 DEG C/min with rate of temperature fall, the porous composite ceramics microballoon of different pore size structure can be obtained, then sieving obtains 50-
75 μm of dusty spray.
(6) the porous dusty spray in step (5) is taken out, is tried in the C/SiC composite material with Si/mullite coating
It is porous that sample surface uses Supersonic Plasma Spraying to prepare, and low-heat is led and anti-oxidant SiCN-Y2SiO5The compound outer painting of environment barrier
Layer, control voltage are 400V, electric current 140A, argon flow 100L/min, hydrogen flowing quantity 10L/min, powder feeder flow
For 5g/min, the mobile rate of spray gun is 800mm/s, spray distance 9mm, and substrate preheating temperature is 600 DEG C, and spraying number is
30 times, room temperature is naturally cooled to after spraying, and C/SiC composite material SiCN-Y can be obtained2SiO5The compound outer painting of environment barrier
Layer.
SiCN-Y prepared by the embodiment of the present invention 1 as seen from Figure 12SiO5Porous and hollow knot is presented in ceramic microspheres
Structure, structure is uniform and size distribution ranges are narrow, and about 50-75 μm.Prepared SiCN-Y2SiO5The compound external coating of environment barrier
Thickness is uniform and there are equally distributed micropores and mesoporous, and coating layer thickness is about 150 μm, sees Fig. 2.Fig. 3 is SiCN-Y2SiO5
The relation curve of environment barrier compound external coating thermal conductivity and temperature, it can be seen from the figure that SiCN- prepared by embodiment 1
Y2SiO5The compound external coating of environment barrier has lower thermal conductivity, and compound external coating thermal conductivity is in 473-1173K temperature range
Interior, thermal conductivity variation in 1.4-2.2W/ (m K), when temperature is 873K, thermal conductivity is 1.4W/ (m K).
Embodiment 2：
A kind of low-heat leads SiCN-Y2SiO5Environment barrier preparation method of composite coating, using following steps：
(1) it takes using solid sintering technology (Ziqi Sun, Meishuan Li, Yanchun Zhou.Thermal
properties of single-phase Y2SiO5[J].Journal of the European Ceramic
Society.29 (2009) 551-557.) synthesis Y2SiO5Powder, using dehydrated alcohol as ball-milling medium, using planetary ball mill
48h is ground for use (0.5-1 μm) after dry using agate mortar；Using by 20Wt% cumyl peroxide is added
(DCP) polysilazane (Northwestern Polytechnical University's preparation, PSN) after being crosslinked by 1100 DEG C of high temperature process furnances, protect by argon atmosphere
Shield is lower to be pyrolyzed 3h, controls heating rate and rate of temperature fall is 4 DEG C/min, SiCN ceramic powders (80nm) can be obtained；
(2) by the above ceramic aggregate powder Y2SiO5Disperse respectively behind (5: 5) uniformly ground and mixed with SiCN according to mass ratio
In isopropanol solvent, using magnetic agitation 5min, then 0.5Wt% polyvinyl alcohol (PVA) is added thereto and is used as dispersing agent, after
Continuous magnetic agitation 5min, then obtains uniform suspending liquid A using cell ultrasonic disintegrator ultrasonic vibration 15min, and control suspends
The mass ratio of ceramic aggregate and isopropanol is (2: 5) in liquid A；
(3) suspending liquid A is transferred in conical flask, while 5Wt% hybrid adhesive epoxy resin and polyether sulfone tree is added
Rouge, controlling its mass ratio is (1: 2), and then this conical flask is installed on iron stand, for 24 hours using mechanical stirring, adjusts stirring and turns
Speed is 300r/min, while using 40 DEG C of constant temperature oil bath heating, it is ensured that binder sufficiently dissolution mixing in suspension；
(4) by above-mentioned configured slurry, it is put into the air for vacuumizing and being excluded in slurry in vacuum desiccator, is then transferred to
In 100mL syringe, then syringe is packed into precise injection and is pumped, and connects syringe and nozzle；Nozzle and Sheng are gone respectively
The anode and cathode for receiving container connection power supply of ionized water, open simultaneously power supply and syringe pump carries out EFI preparation, control note
Firing rate rate is 3mL/min, supply voltage 10kV.After prepared by EFI, the porous microsphere presoma of preparation is stood, filtering
Naturally dry afterwards；
(5) the above porous microsphere presoma is put into sintered heat insulating 3h in 1000 DEG C of high temperature box furnaces, controls heating rate
It is 5 DEG C/min with rate of temperature fall, the porous composite ceramics microballoon of different pore size structure can be obtained, then sieving obtains 30-
50 μm of dusty spray.
(6) the porous dusty spray in step (5) is taken out, is tried in the C/SiC composite material with Si/mullite coating
It is porous that sample surface uses Supersonic Plasma Spraying to prepare, and low-heat is led and anti-oxidant SiCN-Y2SiO5The compound outer painting of environment barrier
Layer, control voltage are 350V, electric current 120A, argon flow 90L/min, and hydrogen flowing quantity 12L/min, powder feeder flow is
6g/min, the mobile rate of spray gun are 600mm/s, and spray distance 8mm, substrate preheating temperature is 500 DEG C, and spraying number is 25
It is secondary, room temperature is naturally cooled to after spraying, and C/SiC composite material SiCN-Y can be obtained2SiO5The compound outer painting of environment barrier
Layer.
Embodiment 3：
A kind of low-heat leads SiCN-Y2SiO5Environment barrier preparation method of composite coating, using following steps：
(1) it takes using solid sintering technology (Ziqi Sun, Meishuan Li, Yanchun Zhou.Thermal
properties of single-phase Y2SiO5[J].Journal of the European Ceramic
Society.29 (2009) 551-557.) synthesis Y2SiO5Powder, using dehydrated alcohol as ball-milling medium, using planetary ball mill
48h is ground for use (0.5-1 μm) after dry using agate mortar；Using by 20Wt% cumyl peroxide is added
(DCP) polysilazane (Northwestern Polytechnical University's preparation, PSN) after being crosslinked by 1000 DEG C of high temperature process furnances, protect by argon atmosphere
Shield is lower to be pyrolyzed 4h, controls heating rate and rate of temperature fall is 2 DEG C/min, SiCN ceramic powders (120nm) can be obtained；
(2) by the above ceramic aggregate powder Y2SiO5Disperse respectively behind (7: 3) uniformly ground and mixed with SiCN according to mass ratio
In isopropanol solvent, using magnetic agitation 10min, then 0.8Wt% polyvinyl alcohol (PVA) is added thereto and is used as dispersing agent,
Continue magnetic agitation 10min, uniform suspending liquid A is then obtained using cell ultrasonic disintegrator ultrasonic vibration 25min, control is outstanding
The mass ratio of ceramic aggregate and isopropanol is (4: 7) in supernatant liquid A；
(3) suspending liquid A is transferred in conical flask, while 5Wt% hybrid adhesive epoxy resin and polyether sulfone tree is added
Rouge, controlling its mass ratio is (1: 4), and then this conical flask is installed on iron stand, using mechanical stirring 18h, adjusts stirring and turns
Speed is 380r/min, while using 45 DEG C of constant temperature oil bath heating, it is ensured that binder sufficiently dissolution mixing in suspension；
(4) by above-mentioned configured slurry, it is put into the air for vacuumizing and being excluded in slurry in vacuum desiccator, is then transferred to
In 100mL syringe, then syringe is packed into precise injection and is pumped, and connects syringe and nozzle；Nozzle and Sheng are gone respectively
The anode and cathode for receiving container connection power supply of ionized water, open simultaneously power supply and syringe pump carries out EFI preparation, control note
Firing rate rate is 2.0mL/min, supply voltage 20kV.After prepared by EFI, the porous microsphere presoma of preparation is stood, mistake
Naturally dry after filter；
(5) the above porous microsphere presoma is put into sintered heat insulating 2.5h in 1100 DEG C of high temperature box furnaces, control heating speed
Rate and rate of temperature fall are 5 DEG C/min, and the porous composite ceramics microballoon of different pore size structure can be obtained, and then sieving obtains
75-100 μm of dusty spray.
(6) the porous dusty spray in step (5) is taken out, is tried in the C/SiC composite material with Si/mullite coating
It is porous that sample surface uses Supersonic Plasma Spraying to prepare, and low-heat is led and anti-oxidant SiCN-Y2SiO5The compound outer painting of environment barrier
Layer, control voltage are 380V, electric current 130A, argon flow 100L/min, hydrogen flowing quantity 10L/min, powder feeder flow
For 8g/min, the mobile rate of spray gun is 700mm/s, and spray distance 10mm, substrate preheating temperature is 550 DEG C, sprays number
It is 35 times, room temperature is naturally cooled to after spraying, C/SiC composite material SiCN-Y can be obtained2SiO5Environment barrier is compound outer
Coating.
Embodiment 4
A kind of low-heat leads SiCN-Y2SiO5Environment barrier preparation method of composite coating, using following steps：
(1) using dehydrated alcohol as ball-milling medium, using planetary ball mill Y2SiO5Powder, grinding after dry and obtaining partial size is 0.5
μm ceramic aggregate powder Y2SiO5, using the polysilazane after cumyl peroxide is crosslinked is added in tube furnace, control heats up
Rate and rate of temperature fall are 2 DEG C/min, in 1000 DEG C of pyrolysis 5h under argon atmosphere protection, obtain the SiCN that partial size is 20nm
Ceramic powders；
(2) by ceramic aggregate powder Y2SiO5It is scattered in isopropyl respectively after 4: 1 uniform ground and mixeds according to mass ratio with SiCN
In alcoholic solvent, using magnetic agitation 5min, then 0.2wt% polyvinyl alcohol is added thereto as dispersing agent, continues magnetic agitation
Then 5min obtains uniform suspension using cell ultrasonic disintegrator ultrasonic vibration 10min, ceramic aggregate powder in suspension
Y2SiO5Mass ratio with isopropanol is 1: 2；
(3) epoxy resin is added into suspension and polyethersulfone resin is the hybrid adhesive of 1: 1 composition in mass ratio, mix
Closing concentration of the binder in suspension is 5wt%, and then controlling speed of agitator is 200r/min, and mechanical stirring 6h is adopted simultaneously
It is heated with 30 DEG C of constant temperature oil baths, it is ensured that binder sufficiently dissolution mixing in suspension；
(4) slurry being mixed to get is put into the air for vacuumizing and being excluded in slurry in vacuum desiccator, is then transferred to note
In emitter, then syringe is packed into precise injection and is pumped, and connects syringe and nozzle；Respectively by nozzle and Sheng deionized water
The anode and cathode for receiving container connection power supply, open simultaneously power supply and syringe pump carries out EFI preparation, control during electrospray
Injection rate processed be 1.5mL/min, supply voltage 5kV, after by obtained porous microsphere presoma stand, after filtering from
So dry；
(5) obtained porous microsphere presoma is put into sintered heat insulating 4h in 1000 DEG C of high temperature box furnaces, control heating speed
Rate and rate of temperature fall are 2 DEG C/min, and re-sieving obtains 30 μm of porous composite ceramics microballoon；
(6) by obtained porous composite ceramics microballoon in the C/SiC composite sample table for having Si/mullite coating
Face uses Supersonic Plasma Spraying, and control voltage is 350V, electric current 100A, argon flow 80L/min, hydrogen flowing quantity
For 8L/min, powder feeder flow is 2g/min, and the mobile rate of spray gun is 400mm/s, spray distance 8mm, substrate preheating temperature
Degree is 300 DEG C, and spraying number is 20 times, and room temperature is naturally cooled to after spraying, obtains SiCN-Y2SiO5Environment barrier is compound
External coating.
Embodiment 5
A kind of low-heat leads SiCN-Y2SiO5Environment barrier preparation method of composite coating, using following steps：
(1) using dehydrated alcohol as ball-milling medium, using planetary ball mill Y2SiO5Powder, grinding after dry and obtaining partial size is 1 μm
Ceramic aggregate powder Y2SiO5, using the polysilazane after cumyl peroxide is crosslinked is added in tube furnace, control heating is fast
Rate and rate of temperature fall are 8 DEG C/min, in 1400 DEG C of pyrolysis 1h under argon atmosphere protection, obtain the SiCN that partial size is 120nm and make pottery
Porcelain powder；
(2) by ceramic aggregate powder Y2SiO5It is scattered in isopropyl respectively after 9: 6 uniform ground and mixeds according to mass ratio with SiCN
In alcoholic solvent, using magnetic agitation 20min, then 10wt% polyvinyl alcohol is added thereto as dispersing agent, continues magnetic agitation
Then 20min obtains uniform suspension using cell ultrasonic disintegrator ultrasonic vibration 40min, ceramic aggregate powder in suspension
Y2SiO5Mass ratio with isopropanol is 8: 10；
(3) epoxy resin is added into suspension and polyethersulfone resin is the hybrid adhesive of 4: 9 compositions in mass ratio, mix
Closing concentration of the binder in suspension is 12wt%, and then controlling speed of agitator is 600r/min, mechanical stirring for 24 hours, simultaneously
It is heated using 70 DEG C of constant temperature oil baths, it is ensured that binder sufficiently dissolution mixing in suspension；
(4) slurry being mixed to get is put into the air for vacuumizing and being excluded in slurry in vacuum desiccator, is then transferred to note
In emitter, then syringe is packed into precise injection and is pumped, and connects syringe and nozzle；Respectively by nozzle and Sheng deionized water
The anode and cathode for receiving container connection power supply, open simultaneously power supply and syringe pump carries out EFI preparation, control during electrospray
Injection rate processed be 4mL/min, supply voltage 20kV, after by obtained porous microsphere presoma stand, after filtering from
So dry；
(5) obtained porous microsphere presoma is put into sintered heat insulating 1h in 1250 DEG C of high temperature box furnaces, control heating speed
Rate and rate of temperature fall are 6 DEG C/min, and re-sieving obtains 125 μm of porous composite ceramics microballoon；
(6) by obtained porous composite ceramics microballoon in the C/SiC composite sample table for having Si/mullite coating
Face uses Supersonic Plasma Spraying, and control voltage is 500V, electric current 200A, argon flow 120L/min, hydrogen flowing quantity
For 20L/min, powder feeder flow is 10g/min, and the mobile rate of spray gun is 1000 mm/s, spray distance 15mm, and matrix is pre-
Hot temperature is 800 DEG C, and spraying number is 50 times, and room temperature is naturally cooled to after spraying, obtains SiCN-Y2SiO5Environment barrier
Compound external coating.
Claims (8)
1. a kind of low-heat leads SiCN-Y2SiO5Environment barrier preparation method of composite coating, which is characterized in that use following steps：
(1) using dehydrated alcohol as ball-milling medium, using planetary ball mill Y2SiO5Powder grinds after dry and obtains ceramic aggregate powder
Y2SiO5, for the polysilazane after cumyl peroxide crosslinking is added in tube furnace, the lower pyrolysis of argon atmosphere protection obtains SiCN
Ceramic powders；
(2) by ceramic aggregate powder Y2SiO5Isopropanol is scattered in after 4~9: 1~6 uniform ground and mixeds according to mass ratio with SiCN
In solvent, using magnetic agitation 5-20min, then 0.2-10wt% polyvinyl alcohol is added thereto as dispersing agent, continues magnetic force
5-20min is stirred, uniform suspension is then obtained using cell ultrasonic disintegrator ultrasonic vibration 10-40min；
(3) hybrid adhesive of epoxy resin and polyethersulfone resin composition is added into suspension, then controlling speed of agitator is
200-600r/min, mechanical stirring 6-24h, while using 30-70 DEG C of constant temperature oil bath heating, it is ensured that binder fills in suspension
Divide dissolution mixing；
(4) slurry being mixed to get is put into the air for vacuumizing and being excluded in slurry in vacuum desiccator, is then transferred to syringe
In, then syringe is packed into precise injection and is pumped, and connects syringe and nozzle；Respectively by the reception of nozzle and Sheng deionized water
Container connects the anode and cathode of power supply, opens simultaneously power supply and syringe pump and carries out EFI preparation, after it is porous by what is obtained
Microballoon presoma is stood, naturally dry after filtering；
(5) obtained porous microsphere presoma is put into sintered heat insulating 1-4h in 1000-1250 DEG C of high temperature box furnace, control heating
Rate and rate of temperature fall are 2-6 DEG C/min, and re-sieving obtains 30-125 μm of porous composite ceramics microballoon；
(6) obtained porous composite ceramics microballoon is adopted on the C/SiC composite sample surface with Si/mullite coating
SiCN-Y is prepared with Supersonic Plasma Spraying2SiO5The compound external coating of environment barrier.
2. a kind of low-heat according to claim 1 leads SiCN-Y2SiO5Environment barrier preparation method of composite coating, feature
It is, ceramic aggregate powder Y in step (1)2SiO5Partial size be 0.5-1 μm, the partial sizes of SiCN ceramic powders is 20-120nm.
3. a kind of low-heat according to claim 1 leads SiCN-Y2SiO5Environment barrier preparation method of composite coating, feature
It is, the temperature of tube furnace is controlled at 1000-1400 DEG C in step (1), is pyrolyzed 1-5h, heating rate and rate of temperature fall are 2-
8℃/min。
4. a kind of low-heat according to claim 1 leads SiCN-Y2SiO5Environment barrier preparation method of composite coating, feature
It is, ceramic aggregate powder Y in suspension described in step (2)2SiO5Mass ratio with isopropanol is 1~8: 2~10.
5. a kind of low-heat according to claim 1 leads SiCN-Y2SiO5Environment barrier preparation method of composite coating, feature
It is, concentration of the hybrid adhesive in suspension described in step (3) is 5-12wt%.
6. a kind of low-heat according to claim 1 leads SiCN-Y2SiO5Environment barrier preparation method of composite coating, feature
It is, the epoxy resin and polyethersulfone resin that hybrid adhesive described in step (3) is 1~4: 1~9 by mass ratio form.
7. a kind of low-heat according to claim 1 leads SiCN-Y2SiO5Environment barrier preparation method of composite coating, feature
It is, controlling injection rate during EFI in step (4) is 1.5-4.0mL/min, supply voltage 5-20kV.
8. a kind of low-heat according to claim 1 leads SiCN-Y2SiO5Environment barrier preparation method of composite coating, feature
It is, when step (6) carries out Supersonic Plasma Spraying, control voltage is 350-500V, electric current 100-200A, argon flow
For 80-120L/min, hydrogen flowing quantity 8-20L/min, powder feeder flow is 2-10g/min, and the mobile rate of spray gun is 400-
1000mm/s, spray distance 8-15mm, the C/SiC composite sample preheating temperature with Si/mullite coating are 300-
800 DEG C, spraying number is 20-50 times, naturally cools to room temperature after spraying, obtains SiCN-Y2SiO5Environment barrier is compound outer
Coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610453576.2A CN106116698B (en) | 2016-06-21 | 2016-06-21 | A kind of low-heat leads SiCN-Y2SiO5Environment barrier preparation method of composite coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610453576.2A CN106116698B (en) | 2016-06-21 | 2016-06-21 | A kind of low-heat leads SiCN-Y2SiO5Environment barrier preparation method of composite coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106116698A CN106116698A (en) | 2016-11-16 |
| CN106116698B true CN106116698B (en) | 2018-11-16 |
Family
ID=57470177
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610453576.2A Active CN106116698B (en) | 2016-06-21 | 2016-06-21 | A kind of low-heat leads SiCN-Y2SiO5Environment barrier preparation method of composite coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106116698B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109161837A (en) * | 2018-11-12 | 2019-01-08 | 舟山腾宇航天新材料有限公司 | A kind of preparation method of high life YSZ thermal barrier coating |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103101946A (en) * | 2013-02-22 | 2013-05-15 | 厦门大学 | Preparation method of alumina nano-microsphere |
| CN105384467A (en) * | 2015-12-14 | 2016-03-09 | 中国航空工业集团公司北京航空制造工程研究所 | Environmental barrier coating used for ceramic base composite material matrix, and making method thereof |
| CN105483597A (en) * | 2016-02-16 | 2016-04-13 | 哈尔滨工程大学 | Preparation method of thermal barrier coating of lanthanum zirconate fiber doped lanthanum zirconate |
| CN105603351A (en) * | 2016-02-19 | 2016-05-25 | 河南普莱姆涂层科技有限公司 | Method for preparing rare earth modified NiAl thermal barrier coating adhesion layer through plasma spraying |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150147524A1 (en) * | 2013-11-26 | 2015-05-28 | Christopher A. Petorak | Modified thermal barrier composite coatings |
-
2016
- 2016-06-21 CN CN201610453576.2A patent/CN106116698B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103101946A (en) * | 2013-02-22 | 2013-05-15 | 厦门大学 | Preparation method of alumina nano-microsphere |
| CN105384467A (en) * | 2015-12-14 | 2016-03-09 | 中国航空工业集团公司北京航空制造工程研究所 | Environmental barrier coating used for ceramic base composite material matrix, and making method thereof |
| CN105483597A (en) * | 2016-02-16 | 2016-04-13 | 哈尔滨工程大学 | Preparation method of thermal barrier coating of lanthanum zirconate fiber doped lanthanum zirconate |
| CN105603351A (en) * | 2016-02-19 | 2016-05-25 | 河南普莱姆涂层科技有限公司 | Method for preparing rare earth modified NiAl thermal barrier coating adhesion layer through plasma spraying |
Non-Patent Citations (2)
| Title |
|---|
| Molten silicate reactions with plasma sprayed ytterbium silicate coatings;Hengbei Zhao等;《Surface & Coatings Technology》;20160114;第288卷;第151–162页 * |
| 等离子喷涂法制备炭/炭复合材料硅酸钇涂层研究;黄敏等;《新型炭材料》;20100630;第25卷(第3期);第187-191页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106116698A (en) | 2016-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108558422B (en) | Preparation method of three-dimensional carbon fiber toughened ultrahigh-temperature ceramic matrix composite with high breaking power | |
| CN105755418B (en) | A kind of ceramic fibre/whisker strengthens composite thermal barrier coating and preparation method thereof | |
| CN103469207B (en) | High-temperature oxidation resistant and corrosion resistant glass ceramic composite coating and preparation technology thereof | |
| CN109837496A (en) | A kind of preparation method of ytterbium silicate plasma spraying powder | |
| CN106048596A (en) | Method for preparing Ti2AlC phase ceramic coating through cold spraying in-situ formation | |
| CN112851330B (en) | Method for preparing whisker toughening composite coating by liquid phase method spraying process | |
| CN107827461A (en) | A kind of resistance to ablation fiber reinforced Si-B-C-N zircon ceramic based composites, its preparation method and application | |
| CN105924234A (en) | Carbon/carbon (C/C) composite material surface low-porosity complex-phase ceramic coating and preparation method thereof | |
| CN114000090B (en) | Preparation method of oxide/oxide composite material surface environment barrier coating | |
| CN107673762A (en) | C/C composite material surface oxidation-resistants ZrSi2‑Y2O3/ SiC composite coatings and preparation method | |
| CN112374917A (en) | High-temperature ceramic coating and preparation method thereof | |
| CN105198501A (en) | Preparation method of carbon/carbon composite material surface metal tungsten gradient coating | |
| CN108424174B (en) | Multi-element complex phase nano boride, corresponding ultrahigh temperature oxidation resistant coating and preparation method | |
| CN110282976A (en) | A kind of preparation method of three-dimensional structure hafnium carbide-titanium silicon-carbon complex phase ceramic | |
| CN108059354A (en) | It is a kind of to prepare unleaded alkali metal-free low-temperature co-fired ceramics using traditional glass melting technology（LTCC）The method of powder | |
| CN108892524A (en) | A kind of C/SiC composite material and preparation method thereof | |
| CN106116698B (en) | A kind of low-heat leads SiCN-Y2SiO5Environment barrier preparation method of composite coating | |
| CN109704816A (en) | A kind of high temperature self-healing duplex heat treatment and its preparation method and application formed on basis material | |
| CN114133251A (en) | Impregnation slurry and preparation method thereof | |
| CN101514474B (en) | Method for preparing Y2SiO5/MoSi2 composite coat by sonoelectrodeposition | |
| CN112299862B (en) | Thermal protection coating on surface of porous thermal insulation material and preparation method thereof | |
| WO2023186094A1 (en) | Thermal barrier coating and preparation method therefor | |
| CN106083209B (en) | A kind of preparation method of micro-structured configuration interlayer interface Mullite/ yttrium silicate composite coatings | |
| CN111153712A (en) | Porous ceramic interpenetrating network neutron shielding composite material and preparation method thereof | |
| CN109678560A (en) | A kind of high temperature anti-ablation coating and its preparation method and application formed on basis material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |