CN110396002A - A kind of preparation method of the high-temperature oxidation resistant non-oxidized substance of resistance to ablation base dense coating - Google Patents
A kind of preparation method of the high-temperature oxidation resistant non-oxidized substance of resistance to ablation base dense coating Download PDFInfo
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- 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
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- 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
- C04B41/507—Borides
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- 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
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Abstract
The present invention relates to a kind of preparation methods of the high-temperature oxidation resistant non-oxidized substance of resistance to ablation base dense coating, belong to composite material and coat preparing technology field.It selects the other powder of submicron order as raw material in the method for the invention, obtains the high ZrB of good sphericity, consistency height, good fluidity, apparent density in conjunction with mist projection granulating and plasma spheroidization technology2‑SiC‑La2O3Powder used for plasma spraying, then the high coating of consistency is prepared by plasma spraying technology, which can bear the ablation examination of 300s under 2000 DEG C of surface temperatures, can satisfy the application demand under the aerobic ablation environment of high temperature.
Description
Technical field
Present invention relates particularly to a kind of preparation method of the high-temperature oxidation resistant non-oxidized substance of resistance to ablation base dense coating, belong to multiple
Condensation material and coat preparing technology field.
Background technique
Carbon fiber reinforced carbon matrix composite material (C/C) specific strength is high, specific modulus is high, corrosion-resistant, high temperature resistant, low-density,
And there is good mechanical behavior under high temperature and hot property, it is the ideal thermal structure material of aerospace field.But in face of flight
Device military service process high temperature, high pressure, high speed, oxygen flow working environment, the carbonaceous material easily quilt in carbon-based composite material
It aoxidizes (400 DEG C or more of aerobic environment starts to be oxidized), the performance of material is difficult to keep for a long time.For carbon base body composite wood
Anti-oxidant ablative cork coatings are prepared on its surface often to reach effective protection effect in the high-temperature oxydation ablation problem of material.
ZrB2- SiC coating is a relatively broad anti-oxidant ablative cork coatings material system of Recent study, it passes through
The compound protection temperature range for having widened material of two kinds of materials.The B that boride ceramics generates2O3Fusing point is lower (450 DEG C), In
1200 DEG C or more volatilizations are serious, and coating structure is caused to destroy.SiC is slower in 800~1200 DEG C of temperature range internal oxidition rates, raw
At SiO2It is larger to measure less and viscosity, good packing can not be played the role of.ZrB2- SiC coating is in 800~1200 DEG C of temperature
Slowly oxidation generates ZrO in section2And B2O3, B at this time2O3Viscosity is suitable for that can serve as packing phase.As temperature is increased to
1200~1600 DEG C, the SiO that SiC oxidation generates2Play the role of packing.In addition, ZrO2With SiO2ZrSiO is formed at high temperature4
Grain, which may also function as, rolls nail effect, slows down SiO2Volatilization, extend the guard time of coating.There is scholar to have studied ZrB2- SiC is applied
Influence of two kinds of material relative scales to coating performance in layer, the results showed that, the ZrB with 20~30vol.%SiC2- SiC is applied
Layer has best antioxygenic property.In addition, the uniformity that SiC is distributed on unit area is higher, the SiO of generation is aoxidized2In
ZrO2Also more uniform, such SiO of middle distribution2It more effectively fills hole, make defect up to hinder the entrance of oxygen so that improving
The antioxygenic property of material.But under the aerobic ablation environment of 1800 DEG C or more higher temperature, ZrB2In-SiC coating
SiO under active oxidation and high temperature can occur for silicon carbide2Volatilization, cause coating is final during high-temperature service only to retain
Loose zirconium oxide (the ZrO of un-sintered densification2) skeleton, to lose protection effect.Therefore, it is necessary to zirconium diboride-silicon carbide
System carries out modification appropriate, to overcome disadvantage mentioned above, to meet the military service demand under the aerobic ablation environment of higher temperature.
Plasma flame flow temperature caused by plasma spraying technology is high, heat is concentrated, and is very suitable to prepare anti-oxidant resistance to
Ablative coating.It but due to two kinds of zirconium diboride, silicon carbide material melting point height, and is all covalent compound, the low difficulty of self-diffusion coefficient
Sintering, therefore be difficult to obtain fine and close coating, even if using the higher plasma spraying mode of temperature, prepared coating is still deposited
In many holes and crackle, lead to coating anti-ablation reduced performance.In addition, powder used for plasma spraying is mainly using micro- at present
Meter level material powder mixes powder by ball milling and adds atomizing granulating technology that reunion powder is made, and then generallys use sintering process to reunion
Powder is sintered to improve the mechanical strength of powder and compactness.Due to two kinds of zirconium diboride, silicon carbide powder fusing points
High hard-to-sinter, sintering processes can not effectively improve the compactness and mechanical strength of powder.The powder obtained by above-mentioned process
Body, general structure is loose, rough surface and intensity are lower, in coating preparation process, powder be easily broken in conveying and
It is difficult to melt.Simultaneously as raw material powder particles are larger, deposited using anti-oxidant ablative coating prepared by air plasma spraying system
The problems such as gap is more, loosely organized, and distribution consistency degree is lower on a microscopic scale for particle, is unfavorable for coating Burning corrosion resistance
The holding of energy.
Summary of the invention
In consideration of it, the present invention provides a kind of preparation method of the high-temperature oxidation resistant non-oxidized substance of resistance to ablation base dense coating, one
Aspect improves ZrB by addition lanthana2On the other hand the ablation resistance and compactness of-SiC coating pass through optimization spraying
Partial size, sphericity and the consistency of powder meet the requirement of plasma spraying, so that it is high and meet high temperature and have to obtain consistency
The coating of demand under oxygen ablation environment.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of preparation method of the high-temperature oxidation resistant non-oxidized substance of resistance to ablation base dense coating, the method includes following steps
It is rapid:
Zirconium diboride powder, silicon carbide powder and lanthanum oxide powder and poly- second of the step 1. by partial size for 200nm~500nm
Enol (PVA) and water are uniformly mixed, and obtain suspension；
In suspension, the mass percent of polyvinyl alcohol is 0.1%~0.3%, the sum of the mass percent of three kinds of powders
It is 39%~60%, the volume ratio of zirconium diboride powder and silicon carbide powder is 7:3, body of the lanthanum oxide powder in three kinds of powders
Product percentage is 5%~20%；
Further, the sum of the mass percent of three kinds of powders in suspension preferably 39%~42%；Lanthanum oxide powder
Percentage by volume preferably 10%~15% in three kinds of powders；
Further, using ball milling method progress raw material powder mixing, ball milling 4h~6h at 200r/min~500r/min,
Ratio of grinding media to material is 4~5:1, is uniformly mixed each ingredient, obtains suspension；
Suspension is transported in spray drying granulation tower and carries out mist projection granulating by step 2., and the powder after granulation is done
Dry processing simultaneously passes through test sieve, obtains the ZrB that partial size is 20 μm~90 μm2-SiC-La2O3Reunion powder；
Spray drying granulation technological parameter: 280 DEG C~330 DEG C of inlet temperature, 110 DEG C~140 DEG C of outlet temperature, spray head turns
Fast 25Hz~40Hz, wriggling revolution speed 35rpm~45rpm；
Further, the powder after granulation is dry at 100 DEG C~150 DEG C；
Step 3. is by ZrB2-SiC-La2O3Reunion powder is sent into plasma spheroidization equipment and carries out spheroidising, by nodularization
Powder afterwards crosses test sieve, obtains the ZrB that partial size is 10 μm~70 μm2-SiC-La2O3Nodularization powder；
Plasma spheroidization technological parameter: main gas (argon gas) flow 65SCFH~70SCFH, auxiliary gas (H2) flow 5SCFH~
8SCFH, carrier gas (argon gas) flow 2SCFH~5SCFH, powder feeding rate 4.5RPM~5.5RPM, chamber pressure 14psia~
16psia, power are 35kW~40kW；
Step 4. uses air plasma spraying technique by ZrB2-SiC-La2O3Nodularization powder is sprayed in substrate, in base
ZrB is formed on bottom2-SiC-La2O3Coating；
Air plasma spraying technological parameter: spray distance is 80mm~110mm, electric current 700A~900A, main gas (argon
Gas) flow be 70SCFH~90SCFH, auxiliary gas (helium) flow be 30SCFH~50SCFH, carrier gas (argon gas) flow be 8SCFH
~12SCFH, powder feeding rate are 2RPM~4RPM.
Further, coating with a thickness of 0.1mm~0.3mm.
The utility model has the advantages that
(1) it is the powder of sub-micron (200nm~500nm) as raw material powder that the present invention, which selects partial size, and the reduction of partial size has
Conducive to melting between powder during nodularization more sufficiently, so that each component distributing is more uniform, it is anti-oxidant resistance to be conducive to coating
The raising of ablation property；
(2) present invention selects lanthana as additive, and lanthana fusing point is at 2300 DEG C or so, compared with zirconium diboride, carbonization
Two kinds of powder fusing points of silicon will be low, close with zirconium diboride, silicon carbide eutectic temperature, can be used as low melting point and mutually fills in powder
The hole and crackle in portion, to improve the compactness of coating；The silica that lanthana fusing point is generated between Oxidation of SiC again
Between the zirconium oxide of zirconium boride oxidation generation, loss caused by the volatilization of element silicon in ablation process, while oxygen can be made up
The densification of zirconium oxide can be promoted at high temperature by changing lanthanum, and the ablation layer generated is made to keep causing under the higher temperature longer time
It is close, to improve the anti-oxidant ablation resistance of coating；
(3) densification is carried out to the powder after mist projection granulating using plasma spheroidization technology in the present invention, makes nodularization
Powder good sphericity, consistency height, good fluidity, apparent density afterwards is high, improves the consistency and cohesive force of powder itself,
Meet the requirement of plasma spraying；
(4) the coating consistency using the method for the invention preparation is high, and improves the anti-oxidant resistance to ablation of coating
Performance, the coating can bear the ablation examination of 300s under 2000 DEG C of surface temperatures, breach 1800 DEG C of technical bottleneck.
Detailed description of the invention
Fig. 1 is ZrB prepared by embodiment 42-SiC-La2O3Surface Scanning Electron microscope (SEM) figure of nodularization powder and
Surface scan elemental analysis figure.
Fig. 2 is ZrB prepared by embodiment 42-SiC-La2O3The microcosmic particle diameter distribution scanning electron microscope of nodularization powder
Figure.
Fig. 3 is ZrB prepared by embodiment 42-SiC-La2O3The cross sectional scanning electron microscope figure and Surface scan of nodularization powder
Elemental analysis figure.
Fig. 4 is ZrB prepared by embodiment 42-SiC-La2O3The surface of coating and cross sectional scanning electron microscope figure.
Fig. 5 is ZrB prepared by embodiment 42-SiC-La2O3Coating examines (surface temperature 2000 through oxy-acetylene flame stream ablation
DEG C, examine time 300s) after surface macro morphology figure and ablation center microscopic appearance figure.
Fig. 6 is ZrB prepared by embodiment 42-SiC-La2O3Coating examines (surface temperature 2000 through oxy-acetylene flame stream ablation
DEG C, examine time 300s) before and after X-ray diffraction (XRD) map and ZrB2、m-ZrO2、c-ZrO2And La2Zr2O7XRD diagram
The comparison diagram of spectrum.
For coating prepared by comparative example 1, through oxy-acetylene flame stream ablation examination, (2000 DEG C of surface temperature, examine the time to Fig. 7
The microscopic appearance figure of surface macro morphology figure and ablation center after 300s).
Specific embodiment
The present invention is further elaborated with reference to the accompanying drawings and detailed description, wherein the method is as without especially
Explanation is conventional method, and the raw material can be gotten from open business unless otherwise instructed.
In following embodiment:
SEM characterization: it is observed using Japanese new and high technology Co., Ltd. S-4800 type cold field emission scanning electron microscope real
Apply ZrB prepared in example2-SiC-La2O3Nodularization morphology microstructure and prepared coating morphology；
X-ray diffraction analysis: X ' the Pert PRO MPD type polycrystal X ray of PANalytical company, Holland production is utilized
Diffraction analysis instrument is to ZrB prepared in embodiment2-SiC-La2O3Coating is analyzed；Test condition: the K of CuαRay, Ni
Filter plate, tube voltage 40kV, tube current 40mA, DS=0.957 ° of slit sizes, PSD=2.12,4 °/min of scanning speed；
Spray drying granulation tower: the LGZ-8 drying machine with centrifugal spray of Wuxi east liter Spray Grain-make Drier tool factory；
Induction plasma nodularization equipment: the 40kW grade induction of Canadian TEKNA Plasma Systems Inc company production
Plasma powder spheroidising system, device model are PL-35 type.
Air plasma spraying equipment: the U.S. produces Praxair GTS-5500 type air plasma spraying equipment, spray gun choosing
With SG-100, powder feeder uses 1264 type powder feeders.
PVA (polyvinyl alcohol): purity >=98%, by graceful scientific and technological (Beijing) the Co., Ltd production of Fox.
ZrB2: partial size 500nm, purity >=98%, by graceful scientific and technological (Beijing) the Co., Ltd production of Fox.
SiC: partial size 500nm, purity >=98%, by graceful scientific and technological (Beijing) the Co., Ltd production of Fox.
La2O3: partial size 500nm, purity >=99.9% are produced by Beijing Chemical Co., Ltd., Hua Weirui section.
Ablation examination, oxy-acetylene lance driving device model are carried out to prepared coating using oxygen-acetylene flame sprayed coating system
For FP-73, nozzle diameter 2mm, oxygen pressure 0.7MPa, oxygen flow 25L/min, acetylene pressure 0.05MPa, acetylene
Flow 50L/min, compressed air pressure 0.3MPa examine distance 25mm, examine 2000 DEG C of temperature, examine time 300s.
Embodiment 1
(1) 191.5g zirconium diboride, 43g silicon carbide, 15.5g lanthana, 0.75g PVA and 375g deionized water are added
Enter into ball grinder, ratio of grinding media to material 4:1, the ball milling 4h at 200r/min, is uniformly mixed each ingredient, obtains suspension；
(2) suspension is transferred in spray drying granulation tower and carries out mist projection granulating, the powder after granulation is first placed in 100
Dry 15h in DEG C baking oven obtains the ZrB that partial size is 20 μm~90 μm using test sieve2-SiC-La2O3Reunion powder；
Wherein, spray drying granulation technological parameter: 280 DEG C of inlet temperature, 110 DEG C of outlet temperature, rotating speed of shower nozzle 25Hz, compacted
Dynamic revolution speed 35rpm；
(3) by ZrB2-SiC-La2O3Reunion powder is sent into induction plasma nodularization equipment and carries out spheroidising, by nodularization
Powder afterwards passes through test sieve, obtains the ZrB that partial size is 10 μm~70 μm2-SiC-La2O3Nodularization powder；
Wherein, induction plasma spheroidizing process parameter: main gas (argon gas) flow 70SCFH, auxiliary gas (H2Gas) flow 8SCFH,
Carrier gas (argon gas) flow 5SCFH, powder feeding rate 4.5RPM, chamber pressure 16psia, the power of plasma spheroidization is 40kW；
(4) use air plasma spraying technique by ZrB2-SiC-La2O3Nodularization powder is sprayed on C/C composite substrate
On, the ZrB that thickness is about 0.15mm is formed on the substrate2-SiC-La2O3Coating；
Wherein, air plasma spraying technological parameter: spray distance 80mm, electric current 900A, main gas (argon gas) flow
90SCFH, auxiliary gas (helium) flow 50SCFH, carrier gas (argon gas) flow 12SCFH, powder feeding rate 2RPM.
According to SEM characterization result it is found that prepared ZrB2-SiC-La2O3The nodularization powder ball smooth in surface compact
Shape, particle diameter distribution are 10 μm~60 μm, and section is fine and close, and porosity is lower.Prepared ZrB2-SiC-La2O3Nodularization powder flow
Dynamic property is 21.62s/50g, apparent density 3.17g/cm3。
Prepared ZrB2-SiC-La2O3Coating flawless and comparatively dense, which can be resistant to surface temperature 2000
DEG C, the ablation examination of 300s, the mass ablative rate of the coating is 2.31 × 10-3g/s。
Embodiment 2
(1) by 179.25g zirconium diboride, 40.25g silicon carbide, 30.5g lanthana, 1g PVA and 375g deionized water
It is added in ball grinder, ratio of grinding media to material 4:1, the ball milling 5h at 300r/min, is uniformly mixed each ingredient, obtains suspension；
(2) suspension is transferred in spray drying granulation tower and carries out mist projection granulating, the powder after granulation is first placed in 120
Dry 15h in DEG C baking oven obtains the ZrB that partial size is 20 μm~90 μm using test sieve2-SiC-La2O3Reunion powder；
Wherein, spray drying granulation technological parameter: 290 DEG C of inlet temperature, 120 DEG C of outlet temperature, rotating speed of shower nozzle 30Hz, compacted
Dynamic revolution speed 35rpm；
(3) by ZrB2-SiC-La2O3Reunion powder is sent into induction plasma nodularization equipment and carries out spheroidising, by nodularization
Powder afterwards passes through test sieve, obtains the ZrB that partial size is 10 μm~70 μm2-SiC-La2O3Nodularization powder；
Wherein, induction plasma spheroidizing process parameter: main gas (argon gas) flow 68SCFH, auxiliary gas (H2Gas) flow 7SCFH,
Carrier gas (argon gas) flow 4SCFH, powder feeding rate 4.8RPM, chamber pressure 15.5psia, the power of plasma spheroidization is 38kW；
(4) use air plasma spraying technique by ZrB2-SiC-La2O3Nodularization powder is sprayed on C/C composite substrate
On, the ZrB that thickness is about 0.15mm is formed on the substrate2-SiC-La2O3Coating；
Wherein, air plasma spraying technological parameter: spray distance 90mm, electric current 850A, main gas (argon gas) flow
80SCFH, auxiliary gas (helium) flow 40SCFH, carrier gas (argon gas) flow 10SCFH, powder feeding rate 3RPM.
According to SEM characterization result it is found that prepared ZrB2-SiC-La2O3The nodularization powder ball smooth in surface compact
Shape, particle diameter distribution are 10 μm~60 μm, and section is fine and close, and porosity is lower.Prepared ZrB2-SiC-La2O3Nodularization powder flow
Dynamic property is 23.95s/50g, apparent density 2.96g/cm3。
Prepared ZrB2-SiC-La2O3Coating flawless and comparatively dense, which can be resistant to surface temperature 2000
DEG C, the ablation examination of 300s, the mass ablative rate of the coating is 0.75 × 10-3g/s。
Embodiment 3
(1) 167.5g zirconium diboride, 37.5g silicon carbide, 45g lanthana, 1.25g PVA and 375g deionized water are added
Enter into ball grinder, ratio of grinding media to material 5:1, the ball milling 5h at 400r/min, is uniformly mixed each ingredient, obtains suspension；
(2) suspension is transferred in spray drying granulation tower and carries out mist projection granulating, the powder after granulation is first placed in 140
Dry 18h in DEG C baking oven obtains the ZrB that partial size is 20 μm~90 μm using test sieve2-SiC-La2O3Reunion powder；
Wherein, spray drying granulation technological parameter: 320 DEG C of inlet temperature, 130 DEG C of outlet temperature, rotating speed of shower nozzle 35Hz, compacted
Dynamic revolution speed 40rpm；
(3) by ZrB2-SiC-La2O3Reunion powder is sent into induction plasma nodularization equipment and carries out spheroidising, by nodularization
Powder afterwards passes through test sieve, obtains the ZrB that partial size is 10 μm~70 μm2-SiC-La2O3Nodularization powder；
Wherein, induction plasma spheroidizing process parameter: main gas (argon gas) flow 66SCFH, auxiliary gas (H2Gas) flow 6SCFH,
Carrier gas (argon gas) flow 3SCFH, powder feeding rate 5.0RPM, chamber pressure 15psia, the power of plasma spheroidization is 36kW；
(4) use air plasma spraying technique by ZrB2-SiC-La2O3Nodularization powder is sprayed on C/C composite substrate
On, the ZrB that thickness is about 0.15mm is formed on the substrate2-SiC-La2O3Coating；
Wherein, air plasma spraying technological parameter: spray distance 100mm, electric current 750A, main gas (argon gas) flow
75SCFH, auxiliary gas (helium) flow 35SCFH, carrier gas (argon gas) flow 10SCFH, powder feeding rate 3.5RPM.
According to SEM characterization result it is found that prepared ZrB2-SiC-La2O3The nodularization powder ball smooth in surface compact
Shape, particle diameter distribution are 10 μm~60 μm, and section is fine and close, and porosity is lower.Prepared ZrB2-SiC-La2O3Nodularization powder flow
Dynamic property is 22s/50g, apparent density 3.28g/cm3。
Prepared ZrB2-SiC-La2O3For coating to flawless and comparatively dense, which can be resistant to surface temperature
2000 DEG C, the ablation examination of 300s, the mass ablative rate of the coating is 0.95 × 10-3g/s。
Embodiment 4
(1) by 155.75g zirconium diboride, 35g silicon carbide, 59.25g lanthana, 1.5g PVA and 375g deionized water
It is added in ball grinder, ratio of grinding media to material 5:1, the ball milling 6h at 500r/min, is uniformly mixed each ingredient, obtains suspension；
(2) suspension is transferred in spray drying granulation tower and carries out mist projection granulating, the powder after granulation is first placed in 150
Dry 10h in DEG C baking oven obtains the ZrB that partial size is 20 μm~90 μm using test sieve2-SiC-La2O3Reunion powder；
Wherein, spray drying granulation technological parameter: 330 DEG C of inlet temperature, 140 DEG C of outlet temperature, rotating speed of shower nozzle 40Hz, compacted
Dynamic revolution speed 45rpm；
(3) by ZrB2-SiC-La2O3Reunion powder is sent into induction plasma nodularization equipment and carries out spheroidising, by nodularization
Powder afterwards passes through test sieve, obtains the ZrB that partial size is 10 μm~70 μm2-SiC-La2O3Nodularization powder；
Wherein, induction plasma spheroidizing process parameter: main gas (argon gas) flow 65SCFH, auxiliary gas (H2Gas) flow 5SCFH,
Carrier gas (argon gas) flow 2SCFH, powder feeding rate 5.5RPM, chamber pressure 14psia, the power of plasma spheroidization is 35kW；
(4) use air plasma spraying technique by ZrB2-SiC-La2O3Nodularization powder is sprayed on C/C composite substrate
On, the coating that thickness is about 0.15mm is formed on the substrate；
Wherein, air plasma spraying technological parameter: spray distance 110mm, electric current 700A, main gas (argon gas) flow are
70SCFH, auxiliary gas (helium) flow 30SCFH, carrier gas (argon gas) flow 8SCFH, powder feeding rate 4RPM.
As can be seen from FIG. 1, prepared ZrB2-SiC-La2O3The nodularization powder spherical shape smooth in surface compact, each element
It is evenly distributed.As can be seen from FIG. 2, the ZrB of preparation2-SiC-La2O3Nodularization diameter of particle is distributed as 10 μm~60 μm or so.It is made
Standby ZrB2-SiC-La2O3Nodularization powder fluidity is 24.7s/50g, apparent density 3.18g/cm3.As can be seen from FIG. 3, institute
The ZrB of preparation2-SiC-La2O3The section of nodularization powder is fine and close, and porosity is lower, and each element is uniformly distributed.
As can be seen from FIG. 4, prepared ZrB2-SiC-La2O3Coating almost flawless, there are a small amount of gaps, more cause
It is close.According to Fig. 5 and Fig. 6 it is found that at 2000 DEG C ZrB after ablation 300s2-SiC-La2O3Coating is complete, occurs cenotype after ablation
La2Zr2O7, the fine and close state of levelling is presented in ablation center.Prepared ZrB2-SiC-La2O3The mass ablative rate of coating is 2.31
×10-3g/s。
Comparative example 1
(1) 204g zirconium diboride, 46g silicon carbide, 0.75g PVA and 375g deionized water are added in ball grinder,
Ratio of grinding media to material is 4:1, the ball milling 4h at 200r/min, is uniformly mixed each ingredient, obtains suspension；
(2) suspension is transferred in spray drying granulation tower and carries out mist projection granulating, the powder after granulation is first placed in 100
Dry 15h in DEG C baking oven obtains the ZrB that partial size is 20 μm~90 μm using test sieve2- SiC reunion powder；
Wherein, spray drying granulation technological parameter: 280 DEG C of inlet temperature, 110 DEG C of outlet temperature, rotating speed of shower nozzle 25Hz, compacted
Dynamic revolution speed 35rpm；
(3) by ZrB2- SiC reunion powder is sent into induction plasma nodularization equipment and carries out spheroidising, after nodularization
Powder passes through test sieve, obtains the ZrB that partial size is 10 μm~70 μm2- SiC nodularization powder；
Wherein, induction plasma spheroidizing process parameter: main gas (argon gas) flow 70SCFH, auxiliary gas (H2Gas) flow 8SCFH,
Carrier gas (argon gas) flow 5SCFH, powder feeding rate 4.5RPM, chamber pressure 16psia, the power of plasma spheroidization is 40kW；
(4) use air plasma spraying technique by ZrB2- SiC nodularization powder is sprayed in C/C composite substrate, In
The ZrB that thickness is about 0.15mm is formed in substrate2- SiC coating；
Wherein, air plasma spraying technological parameter: spray distance 80mm, electric current 900A, main gas (argon gas) flow
90SCFH, auxiliary gas (helium) flow 50SCFH, carrier gas (argon gas) flow 12SCFH, powder feeding rate 2RPM.
To prepared ZrB2- SiC coating carry out the ablation of oxy-acetylene flame stream examination, Fig. 7 show examination after coating it is macro
See the microscopic appearance of pattern and center.It can be found that being not added with La2O3ZrB2- SiC coating is at 2000 DEG C, the ablation of 300s
After examination, partial coating falls off, and exposes C/C matrix, and coating has failed, and the microscopic appearance of coating shows as that there are the non-of hole
Fine and close pattern.
In conclusion the above is merely preferred embodiments of the present invention, being not intended to limit the scope of the present invention.
All within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in of the invention
Within protection scope.
Claims (10)
1. a kind of preparation method of the high-temperature oxidation resistant non-oxidized substance of resistance to ablation base dense coating, it is characterised in that: the method packet
Include following steps:
Zirconium diboride powder, silicon carbide powder and the lanthanum oxide powder and polyvinyl alcohol that partial size is 200nm~500nm by step 1.
And water is uniformly mixed, and obtains suspension；Wherein, the volume ratio of zirconium diboride powder and silicon carbide powder is 7:3, lanthana powder
Percentage by volume of the body in three kinds of powders is 5%~20%；
Suspension is transported in spray drying granulation tower and carries out mist projection granulating by step 2., and place is dried in the powder after granulation
Test sieve is managed and passed through, the ZrB that partial size is 20 μm~90 μm is obtained2-SiC-La2O3Reunion powder；
Step 3. is by ZrB2-SiC-La2O3Reunion powder is sent into plasma spheroidization equipment and carries out spheroidising, after nodularization
Powder crosses test sieve, obtains the ZrB that partial size is 10 μm~70 μm2-SiC-La2O3Nodularization powder；
Step 4. uses air plasma spraying technique by ZrB2-SiC-La2O3Nodularization powder is sprayed in substrate, in substrate
Form ZrB2-SiC-La2O3Coating.
2. the preparation method of the high-temperature oxidation resistant non-oxidized substance of resistance to ablation base dense coating according to claim 1, feature
Be: in suspension, the mass percent of polyvinyl alcohol is 0.1%~0.3%, zirconium diboride powder, silicon carbide powder and oxygen
Changing the sum of mass percent of lanthanum powder is 39%~60%.
3. the preparation method of the high-temperature oxidation resistant non-oxidized substance of resistance to ablation base dense coating according to claim 2, feature
Be: the sum of the mass percent of zirconium diboride powder, silicon carbide powder and lanthanum oxide powder in suspension be 39%~
42%.
4. the preparation method of the high-temperature oxidation resistant non-oxidized substance of resistance to ablation base dense coating according to claim 1, feature
Be: the volume of lanthanum oxide powder account for the sum of zirconium diboride powder, silicon carbide powder and lanthanum oxide powder volume 10%~
15%.
5. the preparation method of the high-temperature oxidation resistant non-oxidized substance of resistance to ablation base dense coating according to claim 1, feature
Be: in step 1, ball milling 4h~6h at 200r/min~500r/min, ratio of grinding media to material is 4~5:1, is uniformly mixed, is hanged
Turbid.
6. the preparation method of the high-temperature oxidation resistant non-oxidized substance of resistance to ablation base dense coating according to claim 1, feature
It is: in step 2, spray drying granulation technological parameter: 280 DEG C~330 DEG C of inlet temperature, 110 DEG C~140 DEG C of outlet temperature,
Rotating speed of shower nozzle 25Hz~40Hz, wriggling revolution speed 35rpm~45rpm.
7. the preparation method of the high-temperature oxidation resistant non-oxidized substance of resistance to ablation base dense coating according to claim 1, feature
Be: in step 2, the powder after granulation is dry at 100 DEG C~150 DEG C.
8. the preparation method of the high-temperature oxidation resistant non-oxidized substance of resistance to ablation base dense coating according to claim 1, feature
It is: in step 3, plasma spheroidization technological parameter: main gas (argon gas) flow 65SCFH~70SCFH, auxiliary gas (hydrogen) flow
5SCFH~8SCFH, carrier gas (argon gas) flow 2SCFH~5SCFH, powder feeding rate 4.5RPM~5.5RPM, chamber pressure 14psia
~16psia, power are 35kW~40kW.
9. the preparation method of the high-temperature oxidation resistant non-oxidized substance of resistance to ablation base dense coating according to claim 1, feature
Be: in step 4, air plasma spraying technological parameter: spray distance is 80mm~110mm, electric current 700A~900A, main gas
(argon gas) flow is 70SCFH~90SCFH, and auxiliary gas (helium) flow is 30SCFH~50SCFH, and carrier gas (argon gas) flow is
8SCFH~12SCFH, powder feeding rate are 2RPM~4RPM.
10. the preparation method of the high-temperature oxidation resistant non-oxidized substance of resistance to ablation base dense coating according to claim 1, feature
It is: ZrB2-SiC-La2O3Coating with a thickness of 0.1mm~0.3mm.
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| CN113956050A (en) * | 2021-10-11 | 2022-01-21 | 南京航空航天大学 | Ablation-resistant ZrB on surface of C-C composite material2-SiC-La2O3-SiC coating and method for producing the same |
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