CN108503390A - Surface of carbon/carbon composite inlays SiC-ZrB2-ZrSi2The preparation method of compound anti-oxidation coating - Google Patents

Surface of carbon/carbon composite inlays SiC-ZrB2-ZrSi2The preparation method of compound anti-oxidation coating Download PDF

Info

Publication number
CN108503390A
CN108503390A CN201810419500.7A CN201810419500A CN108503390A CN 108503390 A CN108503390 A CN 108503390A CN 201810419500 A CN201810419500 A CN 201810419500A CN 108503390 A CN108503390 A CN 108503390A
Authority
CN
China
Prior art keywords
zrsi
zrb
carbon
sic
powder
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.)
Granted
Application number
CN201810419500.7A
Other languages
Chinese (zh)
Other versions
CN108503390B (en
Inventor
付前刚
周磊
童明德
续润洲
张佩
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Northwestern Polytechnical University
Original Assignee
Northwestern Polytechnical University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Northwestern Polytechnical University filed Critical Northwestern Polytechnical University
Priority to CN201810419500.7A priority Critical patent/CN108503390B/en
Publication of CN108503390A publication Critical patent/CN108503390A/en
Application granted granted Critical
Publication of CN108503390B publication Critical patent/CN108503390B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • C04B41/80—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
    • 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
    • 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
    • C04B41/5071—Silicides

Abstract

The present invention relates to a kind of surface of carbon/carbon composite to inlay SiC ZrB2‑ZrSi2The preparation method of compound anti-oxidation coating is prepared for a kind of superhigh temperature ceramics coating that multiphase is inlayed, the ZrB in the multiple phase coating system coating of this arteface using water heat electrophoresis deposition method combination solid state diffusion method2、ZrSi2Content is more, is evenly distributed.Solid state diffusion method generates SiC buffer layers by the infiltration of Si with C/C composite material base precursor reactants, improves the binding force of coating and matrix, on the other hand embeds the Si powder in powder and reacts generation SiC with C powder, SiC is to ZrB2‑ZrSi2The filling of porous layer and the agglomeration of high temperature improve the compactness of coating entirety.The SiC ZrB of the present invention2‑ZrSi2Compound anti-oxidation coating is well combined with matrix, has excellent anti-thermal shock and antioxygenic property.The coating sample increases weight after 50 thermal cycles from room temperature to 1500 DEG C as 15.2gm‑2.After aoxidizing 580h at 1500 DEG C, the weight loss of unit area is only 15.6gm‑2。

Description

Surface of carbon/carbon composite inlays SiC-ZrB2-ZrSi2The system of compound anti-oxidation coating Preparation Method
Technical field
The invention belongs to antioxidant coating preparing technical field, it is related to a kind of surface of carbon/carbon composite and inlays SiC- ZrB2-ZrSi2A kind of preparation method of compound anti-oxidation coating, and in particular to water heat electrophoresis deposition method combination solid state diffusion method preparation tool There is the SiC-ZrB of mosaic texture2-ZrSi2The method of compound anti-oxidation coating.
Background technology
A kind of composite material of the carbon/carbon compound material as matrix phase and the full carbonaceous that reinforced phase is identity element, due to It is only made of single carbon, not only with the excellent ablation resistance of carbon and graphite material, low-density, coefficient of thermal expansion Low advantage, and also excellent mechanical property, such as high intensity, high-modulus, good fracture toughness and wear-resisting property, these Performance can still be kept at a high temperature of 2000 DEG C or more, what is more important under 1500 DEG C or more hot environments its intensity with temperature The performance that the increase of degree goes up not down becomes a kind of especially new and high technology material with development prospect, has been widely used in Empty day field.But C/C composite materials will be aoxidized under the aerobic environment more than 450 DEG C, limit it in oxidizing atmosphere Under extensive use.
Antioxidant coating is considered as solving the problems, such as the effective ways of carbon/carbon compound material oxidant protection under high temperature.To prevent C/C composite materials aoxidize at high temperature, and domestic and international researcher has carried out a large amount of theoretical and experimental study, develop a variety of anti- Oxide covering system.
In recent years, ceramic coating becomes research hotspot, while being also that research at present is most deep, development antioxygen the most ripe Change coating system, wherein superhigh temperature ceramics are considered as ideal C/C composite materials antioxidant coating material.Especially ZrB2, since it is with high-melting-point, low-density, good thermal stability and corrosion resistance, to obtain extensive research.But It is ZrB2When temperature is higher than 1673K, a large amount of volatile B of generation can be aoxidized2O3And then it leaves porous, discontinuous without anti- The ZrO of oxidability2Layer, shows poor antioxygenic property [P.Hu, G.L.Wang, Z.Wang, Oxidation mechanism and resistance of ZrB2-SiCcomposites,Corros.Sci.51(2009)2724- 2732.].Currently, for ZrB2The oxidizable problem under superhigh temperature, an effective method is exactly to introduce SiC.In oxidation In the process, fine and close ZrO is formed2The magma cell of particle dispersion distribution, to improve the antioxygenic property of coating [O.N.Grigoriev,B.A.Galanov,V.A.Lavrenko,A.D.Panasyuk,S.M.Ivanov,A.V.Koroteev, K.G.Nickel,Oxidation of ZrB2-SiC-ZrSi2ceramics in oxygen,J.Eur.Ceram.Soc.30 (2010)2397-2405.].However, due to ZrB2The hard-to-sinter of ceramics, prepared coating are often not fine and close enough.In addition, passing ZrB in coating prepared by the investment of system2Content is less and particle is easy to reunite [X.Y.Yao, H.J.Li, Y.L.Zhang,H.Wu,X.F.Qiang,A SiC-Si-ZrB2multiphase oxidation protective ceramic Coating for SiC-coated carbon/carbon composites, Ceram.Int.38 (2012) 2095- 2100.]。ZrB2The non-uniform dispersion of particle is so that coating is susceptible to stress concentration to generate in preparation or oxidation process Crackle [H.B.Ouyang, C.Y.Li, J.F.Huang, L.Y.Cao, J.Fei, J.Lu, Z.W.Xu, Self-healing ZrB2- SiO2oxidation resistance coating for SiC coated carbon/carbon composites, Corros.Sci.110(2016)265-272.].In addition, since coating is not fine and close enough and ZrB2Content is less, ZrB2In short-term It is interior can by exhaustive oxidation [P.Wang, S.B.Zhou, X.H.Zhang, K.X.Gui, Y.X.Li, J.D.An, W.B.Han, Thermal cycling and oxidation resistance of B modified ZrB2-SiC coatings on SiC coated graphite,Surf.Coat.Technol.280(2015)330-337.].Therefore, ZrB is improved2In coating In content and its dispersibility and coating compactness, be improve ZrB2The key of-SiC coating antioxygenic properties.
Invention content
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes that a kind of surface of carbon/carbon composite inlays SiC- ZrB2-ZrSi2The preparation method of compound anti-oxidation coating prepares porous ZrB with simple water heat electrophoresis deposition method first2- ZrSi2Layer, then using selection solid state diffusion method to porous ZrB2-ZrSi2Layer is densified, and SiC-ZrB is obtained2-ZrSi2It is compound Coating.
Technical solution
A kind of surface of carbon/carbon composite inlays SiC-ZrB2-ZrSi2The preparation method of compound anti-oxidation coating, feature It is that steps are as follows：
Step 1：C/C composite materials are pre-oxidized in Muffle furnace；
Step 2：Based on mass fraction, according to the ZrB of 60wt%-80wt%2The ZrSi of powder and 20wt%-40wt%2Powder Body is scattered in isopropanol and is configured to suspension, is stirred evenly after suspension is ultrasonically treated, obtains suspending liquid A；The ZrB2And ZrSi2Powder carries out dry ball milling；Isopropyl alcohol concentration is 5-30g/L in the suspension；
Step 3：Elemental iodine is added into suspending liquid A and obtains mixture, then heating stirring obtains suspension B；The addition A concentration of 1-5g/L of the elemental iodine in suspension B；
Step 4：Suspension B is poured into water heating kettle, then the C/C composite materials after pre-oxidation are clipped in water heating kettle On cathode folder, anode is graphite, is put into baking oven after then sealing water heating kettle, by negative and positive the two poles of the earth of water heating kettle and DC constant voltage Power supply connects and carries out water heat electrophoresis deposition；In the deposition process：It is 80-150 DEG C to control oven temperature, supply voltage 100- 180V, electrophoresis time 5-30min；
Step 5：Then it is drying to obtain in an oven with ZrB2-ZrSi2The C/C composite materials of coating；
Step 6：There is ZrB by what step 5 obtained2-ZrSi2The C/C composite materials of coating are embedded in mixed powder, close Graphite crucible is sealed, then puts it into high temperature graphitization stove and is heat-treated under protection of argon gas, later furnace cooling；It is described Heat treating regime is：Temperature 1873-2373K, processing time 2-6h, heating rate 5-10K/min；The quality of the mixed powder Score is：Si powder, the C powder of 15wt%-25wt% and the Al of 5wt%-15wt% of 60wt%-80wt%2O3Powder；
After high-temperature heat treatment, is taken out out of graphite crucible and obtain surface of carbon/carbon composite and inlay SiC-ZrB2- ZrSi2Compound anti-oxidation coating.
The ZrB of the step 22And ZrSi2The grain size of powder is 1-5 μm.
ZrB in the step 22And ZrSi2The dry ball milling time of powder is 24-48h.
The temperature that C/C composite materials pre-oxidize in the step 1 is 600-900 DEG C, preoxidation time 3-10min.
It is ultrasonically treated in the step 2 and is specially：Suspension is put into supersonic generator and shakes 30-90min；Stirring Processing is specially：Using magnetic agitation 6-24h.
Heating stirring is in the step 3：Magnetic agitation 2-8h at a temperature of 60-150 DEG C.
The drying temperature of the step 5 is 50-100 DEG C, drying time 2-4h.
The mixed grinding time of mixed powder is 60min in the step 6.
Purity >=99.8% of the isopropanol.
Purity >=99.7% of the iodine.
Advantageous effect
A kind of surface of carbon/carbon composite proposed by the present invention inlays SiC-ZrB2-ZrSi2The system of compound anti-oxidation coating Preparation Method uses water heat electrophoresis deposition method by ZrB first2、ZrSi2Ceramic powder uniform deposition to C/C composite material surfaces, C/C composite material surfaces form ZrB2-ZrSi2Porous layer, to ensure ZrB in coating2Content and dispersibility, ZrSi2Plus Enter, is conducive to improve ZrB2Agglutinating property.The solid state diffusion method then used is on the one hand by the infiltration of Si and C/C matrices of composite materials Reaction generates SiC buffer layers, improves the binding force of coating and matrix, and the Si powder on the other hand embedded in powder reacts life with C powder At SiC, SiC is to ZrB2-ZrSi2The filling of porous layer and the agglomeration of high temperature improve the compactness of coating entirety.
The present invention is prepared for a kind of superhigh temperature ceramics coating that multiphase is inlayed using water heat electrophoresis deposition method combination solid state diffusion method, The ZrB in the multiple phase coating system coating of this arteface2、ZrSi2Content is more, is evenly distributed.Solid state diffusion method passes through the molten of Si It oozes and generates SiC buffer layers with C/C composite material base precursor reactants, improve the binding force of coating and matrix, on the other hand embed powder Si powder in material is reacted with C powder generates SiC, and SiC is to ZrB2-ZrSi2The filling of porous layer and the agglomeration of high temperature improve The compactness of coating entirety.In addition, jljl does not mutually form multi phase interface in the coating, and occur pinning phase in composite coating, Can mutually be induced the crackle in coating using these multi phase interfaces and pinning makes its steering, alleviates the thermal stress of crack tip, The thermal stress of crack tip is set to be released and redistribute, crackle encounters these pinnings in expansion process and meets generation partially Turn or terminate, and then reduce flaw size, inhibits its propagation.To improve the toughness of ceramic coating.Prepared by the present invention SiC-ZrB2-ZrSi2Compound anti-oxidation coating has a kind of novel mosaic texture, is well combined with matrix, has excellent resist Thermal shock and antioxygenic property.The coating sample increases weight after 50 thermal cycles from room temperature to 1500 DEG C as 15.2gm-2.After aoxidizing 580h at 1500 DEG C, the weight loss of unit area is only 15.6gm-2。
Description of the drawings
Fig. 1 is that the XRD spectrum wherein (a) of prepared coating is ZrB2-ZrSi2Coating (b) is SiC-ZrB2-ZrSi2It applies Layer.
Fig. 2 is that the SEM photograph wherein (a) of prepared coating is ZrB2-ZrSi2Coating surface SEM photograph (b) is ZrB2- ZrSi2Coating section SEM photograph (c) is SiC-ZrB2-ZrSi2Coating surface SEM photograph (d) is SiC-ZrB2-ZrSi2Coating Section SEM photograph.
Specific implementation mode
In conjunction with embodiment, attached drawing, the invention will be further described：
Embodiment 1：
(1) commercially available ZrB is selected2And ZrSi2Powder passes through dry ball milling for 24 hours respectively, and average grain diameter control is at 5 μm or so, iodine Simple substance, purity >=99.7% and isopropanol, purity >=99.8% are raw material；
(2) C/C composite materials are pre-oxidized into 3min in 900 DEG C of Muffle furnace；
(3) appropriate ZrB is taken2Powder, ZrSi2Powder, both control mass ratio are：ZrSi2Powder：30wt%, ZrB2Powder Body：70wt% is scattered in the conical flask for filling 170mL isopropanols, is configured to the suspension of a concentration of 30g/L, then will suspend Liquid, which is put into supersonic generator, shakes 60min, and magnet rotor is put into after taking-up, is placed on magnetic stirring apparatus and stirs 12h, obtains outstanding Supernatant liquid A；
(4) elemental iodine is added into suspending liquid A, obtains mixture, a concentration of 3g/L of iodine in mixture, after sealing conical flask It is placed on magnetic stirring apparatus and stirs and heat, mixing time 4h, 80 DEG C of heating temperature obtains suspension B；
(5) suspension B is poured into water heating kettle, then the C/C composite samples after pre-oxidation is clipped in water heating kettle Cathode folder on, anode is graphite, is put into baking oven after then sealing water heating kettle.Negative and positive the two poles of the earth of water heating kettle and direct current are permanent Voltage source connects and carries out water heat electrophoresis deposition.In deposition process, control oven temperature is 100 DEG C, supply voltage 100V, electrophoresis Time 10min closes installation's power source after water heat electrophoresis deposition and naturally cools to room temperature；
(6) above-mentioned apparatus is opened, sample is taken out, then dry 4h obtains C/C composite materials ZrB at 60 DEG C2-ZrSi2Coating Sample；
(7) it is in mass ratio：Si powder：75wt%, C powder：15wt%, Al2O3Powder：The ratio of 10wt% weighs suitable city Sell Si powder, C powder and Al2O3Powder is fully ground 60min to being uniformly mixed, is subsequently placed in graphite crucible in mortar；
(8) ZrB will be carried obtained by step (6)2-ZrSi2The C/C composite materials of coating are embedded in mixed described in step (7) It closes in powder, sealed graphite crucible, then puts it into high temperature graphitization stove and handle 2h in 2373K under protection of argon gas, rise Warm rate 10K/min, later furnace cooling；
(9) after high-temperature heat treatment, sample and powder are taken out out of graphite crucible, is brushed away with brush and is adhered to painting The powder of layer surface is up to SiC-ZrB2-ZrSi2Compound anti-oxidation coating.
Embodiment 2：
(1) commercially available ZrB is selected2And ZrSi2Powder passes through dry ball milling 36h respectively, and average grain diameter control is at 3 μm or so, iodine Simple substance, purity >=99.7% and isopropanol, purity >=99.8% are raw material；
(2) C/C composite materials are pre-oxidized into 10min in 600 DEG C of Muffle furnace；
(3) appropriate ZrB is taken2Powder, ZrSi2Powder, both control mass ratio are：ZrSi2Powder：20wt%, ZrB2Powder Body：80wt% is scattered in the conical flask for filling 150mL isopropanols, is configured to the suspension of a concentration of 20g/L, then will suspend Liquid, which is put into supersonic generator, shakes 30min, and magnet rotor is put into after taking-up, is placed on magnetic stirring apparatus and stirs 8h, obtains outstanding Supernatant liquid A；
(4) elemental iodine is added into suspending liquid A, obtains mixture, a concentration of 4g/L of iodine in mixture, after sealing conical flask It is placed on magnetic stirring apparatus and stirs and heat, mixing time 3h, 80 DEG C of heating temperature obtains suspension B；
(5) suspension B is poured into water heating kettle, then the C/C composite samples after pre-oxidation is clipped in water heating kettle Cathode folder on, anode is graphite, is put into baking oven after then sealing water heating kettle.Negative and positive the two poles of the earth of water heating kettle and direct current are permanent Voltage source connects and carries out water heat electrophoresis deposition.In deposition process, control oven temperature is 80 DEG C, supply voltage 120V, electrophoresis Time 8min closes installation's power source after water heat electrophoresis deposition and naturally cools to room temperature；
(6) above-mentioned apparatus is opened, sample is taken out, then dry 3h obtains C/C composite materials ZrB at 80 DEG C2-ZrSi2Coating Sample；
(7) it is in mass ratio：Si powder：80wt%, C powder：15wt, Al2O3Powder：The ratio of 5wt% weighs suitable commercially available Si Powder, C powder and Al2O3Powder is fully ground 60min to being uniformly mixed, is subsequently placed in graphite crucible in mortar；
(8) ZrB will be carried obtained by step (6)2-ZrSi2The C/C composite materials of coating are embedded in mixed described in step (7) It closes in powder, sealed graphite crucible, then puts it into high temperature graphitization stove and handle 4h in 2173K under protection of argon gas, rise Warm rate 5K/min, later furnace cooling；
(9) after high-temperature heat treatment, sample and powder are taken out out of graphite crucible, is brushed away with brush and is adhered to painting The powder of layer surface is up to SiC-ZrB2-ZrSi2Compound anti-oxidation coating.
Embodiment 3：
(1) commercially available ZrB is selected2And ZrSi2Powder passes through dry ball milling 48h respectively, and average grain diameter control is at 1 μm, elemental iodine, Purity >=99.7% and isopropanol, purity >=99.8% are raw material；
(2) C/C composite materials are pre-oxidized into 5min in 800 DEG C of Muffle furnace；
(3) appropriate ZrB is taken2Powder, ZrSi2Powder, both control mass ratio are：ZrSi2Powder：40wt%, ZrB2Powder Body：60wt% is scattered in the conical flask for filling 160mL isopropanols, is configured to the suspension of a concentration of 10g/L, then will suspend Liquid, which is put into supersonic generator, shakes 30min, and magnet rotor is put into after taking-up, is placed on magnetic stirring apparatus and stirs 10h, obtains outstanding Supernatant liquid A；
(4) elemental iodine is added into suspending liquid A, obtains mixture, a concentration of 5g/L of iodine in mixture, after sealing conical flask It is placed on magnetic stirring apparatus and stirs and heat, mixing time 2h, 100 DEG C of heating temperature obtains suspension B；
(5) suspension B is poured into water heating kettle, then the C/C composite samples after pre-oxidation is clipped in water heating kettle Cathode folder on, anode is graphite, is put into baking oven after then sealing water heating kettle.Negative and positive the two poles of the earth of water heating kettle and direct current are permanent Voltage source connects and carries out water heat electrophoresis deposition.In deposition process, control oven temperature is 100 DEG C, supply voltage 110V, electrophoresis Time 15min closes installation's power source after water heat electrophoresis deposition and naturally cools to room temperature；
(6) above-mentioned apparatus is opened, sample is taken out, then dry 2h obtains C/C composite materials ZrB at 100 DEG C2-ZrSi2It applies Layer sample；
(7) it is in mass ratio：Si powder：70wt%, C powder：15wt%, Al2O3Powder：The ratio of 15wt% weighs suitable city Sell Si powder, C powder and Al2O3Powder is fully ground 60min to being uniformly mixed, is subsequently placed in graphite crucible in mortar；
(8) ZrB will be carried obtained by step (6)2-ZrSi2The C/C composite materials of coating are embedded in mixed described in step (7) It closes in powder, sealed graphite crucible, then puts it into high temperature graphitization stove and handle 3h in 2273K under protection of argon gas, rise Warm rate 8K/min, later furnace cooling；
(9) after high-temperature heat treatment, sample and powder are taken out out of graphite crucible, is brushed away with brush and is adhered to painting The powder of layer surface is up to SiC-ZrB2-ZrSi2Compound anti-oxidation coating.

Claims (10)

1. a kind of surface of carbon/carbon composite inlays SiC-ZrB2-ZrSi2The preparation method of compound anti-oxidation coating, feature exist In steps are as follows：
Step 1：C/C composite materials are pre-oxidized in Muffle furnace；
Step 2：Based on mass fraction, according to the ZrB of 60wt%-80wt%2The ZrSi of powder and 20wt%-40wt%2Powder, It is scattered in isopropanol and is configured to suspension, stirred evenly after suspension is ultrasonically treated, obtain suspending liquid A；The ZrB2And ZrSi2Powder carries out dry ball milling；Isopropyl alcohol concentration is 5-30g/L in the suspension；
Step 3：Elemental iodine is added into suspending liquid A and obtains mixture, then heating stirring obtains suspension B；The iodine list of the addition A concentration of 1-5g/L of the matter in suspension B；
Step 4：Suspension B is poured into water heating kettle, the C/C composite materials after pre-oxidation are then clipped in the cathode in water heating kettle On folder, anode is graphite, is put into baking oven after then sealing water heating kettle, by negative and positive the two poles of the earth of water heating kettle and DC constant voltage power supply It connects and carries out water heat electrophoresis deposition；In the deposition process：It is 80-150 DEG C to control oven temperature, supply voltage 100- 180V, electrophoresis time 5-30min；
Step 5：Then it is drying to obtain in an oven with ZrB2-ZrSi2The C/C composite materials of coating；
Step 6：There is ZrB by what step 5 obtained2-ZrSi2The C/C composite materials of coating are embedded in mixed powder, seal stone Then black crucible puts it into high temperature graphitization stove and is heat-treated under protection of argon gas, later furnace cooling；At the heat Reason system is：Temperature 1873-2373K, processing time 2-6h, heating rate 5-10K/min；The mass fraction of the mixed powder For：Si powder, the C powder of 15wt%-25wt% and the Al of 5wt%-15wt% of 60wt%-80wt%2O3Powder；
After high-temperature heat treatment, is taken out out of graphite crucible and obtain surface of carbon/carbon composite and inlay SiC-ZrB2-ZrSi2It is multiple Close antioxidant coating.
2. surface of carbon/carbon composite inlays SiC-ZrB according to claim 12-ZrSi2The preparation of compound anti-oxidation coating Method, it is characterised in that：The ZrB of the step 22And ZrSi2The grain size of powder is 1-5 μm.
3. surface of carbon/carbon composite inlays SiC-ZrB according to claim 12-ZrSi2The preparation of compound anti-oxidation coating Method, it is characterised in that：ZrB in the step 22And ZrSi2The dry ball milling time of powder is 24-48h.
4. surface of carbon/carbon composite inlays SiC-ZrB according to claim 12-ZrSi2The preparation of compound anti-oxidation coating Method, it is characterised in that：The temperature that C/C composite materials pre-oxidize in the step 1 is 600-900 DEG C, preoxidation time 3- 10min。
5. surface of carbon/carbon composite inlays SiC-ZrB according to claim 12-ZrSi2The preparation of compound anti-oxidation coating Method, it is characterised in that：It is ultrasonically treated in the step 2 and is specially：Suspension is put into supersonic generator and shakes 30- 90min；Stir process is specially：Using magnetic agitation 6-24h.
6. surface of carbon/carbon composite inlays SiC-ZrB according to claim 12-ZrSi2The preparation of compound anti-oxidation coating Method, it is characterised in that：Heating stirring is in the step 3：Magnetic agitation 2-8h at a temperature of 60-150 DEG C.
7. surface of carbon/carbon composite inlays SiC-ZrB according to claim 12-ZrSi2The preparation of compound anti-oxidation coating Method, it is characterised in that：The drying temperature of the step 5 is 50-100 DEG C, drying time 2-4h.
8. surface of carbon/carbon composite inlays SiC-ZrB according to claim 12-ZrSi2The preparation of compound anti-oxidation coating Method, it is characterised in that：The mixed grinding time of mixed powder is 60min in the step 6.
9. surface of carbon/carbon composite inlays SiC-ZrB according to claim 12-ZrSi2The preparation of compound anti-oxidation coating Method, it is characterised in that：Purity >=99.8% of the isopropanol.
10. surface of carbon/carbon composite inlays SiC-ZrB according to claim 12-ZrSi2The system of compound anti-oxidation coating Preparation Method, it is characterised in that：Purity >=99.7% of the iodine.
CN201810419500.7A 2018-05-04 2018-05-04 Surface mosaic SiC-ZrB of carbon/carbon composite material2-ZrSi2Preparation method of composite oxidation-resistant coating Active CN108503390B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810419500.7A CN108503390B (en) 2018-05-04 2018-05-04 Surface mosaic SiC-ZrB of carbon/carbon composite material2-ZrSi2Preparation method of composite oxidation-resistant coating

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810419500.7A CN108503390B (en) 2018-05-04 2018-05-04 Surface mosaic SiC-ZrB of carbon/carbon composite material2-ZrSi2Preparation method of composite oxidation-resistant coating

Publications (2)

Publication Number Publication Date
CN108503390A true CN108503390A (en) 2018-09-07
CN108503390B CN108503390B (en) 2021-02-02

Family

ID=63399936

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810419500.7A Active CN108503390B (en) 2018-05-04 2018-05-04 Surface mosaic SiC-ZrB of carbon/carbon composite material2-ZrSi2Preparation method of composite oxidation-resistant coating

Country Status (1)

Country Link
CN (1) CN108503390B (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110372417A (en) * 2019-08-23 2019-10-25 航天特种材料及工艺技术研究所 A kind of antioxidant coating and preparation method thereof
CN110818426A (en) * 2019-12-18 2020-02-21 中国矿业大学 HfB on surface of carbon material2-TaSi2Preparation method of-SiC oxidation resistant coating
CN111848220A (en) * 2020-07-30 2020-10-30 中国人民解放军火箭军工程大学 MB2Ultrahigh-temperature-based ceramic coating and preparation method thereof
CN112174698A (en) * 2020-10-16 2021-01-05 南京宁贺表面技术有限公司 Carbon material surface antioxidant protective coating and preparation method thereof
CN112409005A (en) * 2020-11-23 2021-02-26 航天特种材料及工艺技术研究所 Preparation method of net-size C/SiC ceramic matrix composite
CN113563119A (en) * 2021-08-11 2021-10-29 西安工程大学 Preparation method of C/C composite material surface oxidation-resistant coating
CN116120080A (en) * 2023-02-21 2023-05-16 无锡博智复合材料有限公司 ZrB (ZrB) 2 ZrC-SiC modified carbon/carbon composite material and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102746028A (en) * 2012-05-26 2012-10-24 苏州宏久航空防热材料科技有限公司 Oxide-particle-embedded silicon carbide coating and preparation method thereof
CN103011829A (en) * 2012-12-28 2013-04-03 郑州大学 Method for sintering zirconium diboride ceramic material
CN104150960A (en) * 2014-08-06 2014-11-19 陕西科技大学 Preparation method for ZrB2-SiO2 composite high-temperature oxidation resistant coating
CN106966764A (en) * 2016-06-12 2017-07-21 北京航空航天大学 Thermostructural composite high-temperature oxidation resistant composite coating and preparation method thereof
CN107673762A (en) * 2017-10-30 2018-02-09 西北工业大学 C/C composite material surface oxidation-resistants ZrSi2‑Y2O3/ SiC composite coatings and preparation method

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102746028A (en) * 2012-05-26 2012-10-24 苏州宏久航空防热材料科技有限公司 Oxide-particle-embedded silicon carbide coating and preparation method thereof
CN103011829A (en) * 2012-12-28 2013-04-03 郑州大学 Method for sintering zirconium diboride ceramic material
CN104150960A (en) * 2014-08-06 2014-11-19 陕西科技大学 Preparation method for ZrB2-SiO2 composite high-temperature oxidation resistant coating
CN106966764A (en) * 2016-06-12 2017-07-21 北京航空航天大学 Thermostructural composite high-temperature oxidation resistant composite coating and preparation method thereof
CN107673762A (en) * 2017-10-30 2018-02-09 西北工业大学 C/C composite material surface oxidation-resistants ZrSi2‑Y2O3/ SiC composite coatings and preparation method

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MINGFU WANG等: "Effect of SiC platelet and ZrSi2 additive on sintering and mechanical properties of ZrB2-based ceramics by hot-pressing", 《MATERIALS AND DESIGN》 *
曹丽云等: "《碳/碳复合材料AlPO4抗氧化陶瓷涂层研究》", 31 December 2017, 西北工业大学出版社 *
李贺军等: "《先进复合材料学》", 31 December 2016, 西北工业大学出版社 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110372417A (en) * 2019-08-23 2019-10-25 航天特种材料及工艺技术研究所 A kind of antioxidant coating and preparation method thereof
CN110818426A (en) * 2019-12-18 2020-02-21 中国矿业大学 HfB on surface of carbon material2-TaSi2Preparation method of-SiC oxidation resistant coating
CN111848220A (en) * 2020-07-30 2020-10-30 中国人民解放军火箭军工程大学 MB2Ultrahigh-temperature-based ceramic coating and preparation method thereof
CN112174698A (en) * 2020-10-16 2021-01-05 南京宁贺表面技术有限公司 Carbon material surface antioxidant protective coating and preparation method thereof
CN112409005A (en) * 2020-11-23 2021-02-26 航天特种材料及工艺技术研究所 Preparation method of net-size C/SiC ceramic matrix composite
CN113563119A (en) * 2021-08-11 2021-10-29 西安工程大学 Preparation method of C/C composite material surface oxidation-resistant coating
CN116120080A (en) * 2023-02-21 2023-05-16 无锡博智复合材料有限公司 ZrB (ZrB) 2 ZrC-SiC modified carbon/carbon composite material and preparation method and application thereof
CN116120080B (en) * 2023-02-21 2023-11-21 无锡博智复合材料有限公司 ZrB (ZrB) 2 ZrC-SiC modified carbon/carbon composite material and preparation method and application thereof

Also Published As

Publication number Publication date
CN108503390B (en) 2021-02-02

Similar Documents

Publication Publication Date Title
CN108503390A (en) Surface of carbon/carbon composite inlays SiC-ZrB2-ZrSi2The preparation method of compound anti-oxidation coating
Huang et al. A MoSi2/SiC oxidation protective coating for carbon/carbon composites
CN107032816A (en) A kind of silicon carbide nanometer line enhancing C/C SiC ZrB2The preparation method of ceramic matric composite
CN107814591A (en) A kind of carbon material surface boride is modified the preparation method of silicon substrate antioxidant coating
CN109678511A (en) A kind of densification HfC (Si)-HfB2The preparation method of complex phase ceramic
CN114591102B (en) C/C composite material SiB 6 Glass oxidation resistant coating and method for producing the same
CN106495745B (en) A kind of preparation method of the crystal whisker toughened yttrium silicate of β-yttrium silicate/YAS coating
CN101407433B (en) Preparation of carbon/carbon composite material molybdenum disilicide outer coating
CN103409732A (en) Composite processing method for realizing metallization of surfaces of diamonds
Zhu et al. SiC/SiC-ZrSi2 coating with micro-pore to protect C/C composites against oxidation for long-life service at high temperatures
CN110357635A (en) A method of improving carbon-based or ceramic matric composite surface oxidation-resistant coating bond strength
CN103387422A (en) Method for preparing silicon carbide/molybdenum disiticide composite coating on surface of carbon material
CN105712746B (en) A kind of method that C/C composite material surfaces prepare the superior Si Mo Cr coatings of thermal shock resistance
CN108424162A (en) A kind of preparation method of superhigh temperature ceramics constituency modifying carbon/carbon composite material
CN112853260B (en) Preparation method of powder embedding infiltration coating
CN105753514B (en) A kind of preparation method of the anti-oxidant SiC composite protection layer of carbon element of graphite material surface
CN101844936A (en) Method for preparing C/C composite material nanometer silicon carbide-mullite-molybdenum disilicide composite external coating
CN105350294B (en) A kind of chopped carbon fiber of applying silicon carbide layer and preparation method thereof
CN109704798A (en) The method that vacuum impregnation association reaction melt infiltration RMI prepares C/SiC-Diamond composite material
CN106673708A (en) Method for preparing silicon carbide nanowire porous layer on surface of carbon/carbon composite material
CN103435354A (en) Method for preparing SiC nanowire-toughened C<f>/SiC composite
CN102603344B (en) Preparing process of silicon carbide whisker toughened zirconium diboride ceramic
CN106631161B (en) A method of composite coating resistant to high temperature oxidation is prepared on carbon-based material surface
CN105669231B (en) A kind of fibre reinforced MoSi2The preparation method of SiC ceramic based composites
CN101838157B (en) Method for preparing carbon/carbon composite material nanometer silicon carbide-mullite composite external coating

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant