[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

CN106630978B - The alumina fibre rigidity thermal insulation tile multilayer materials of surface toughening, coating composition, preparation method and applications - Google Patents

The alumina fibre rigidity thermal insulation tile multilayer materials of surface toughening, coating composition, preparation method and applications Download PDF

Info

Publication number
CN106630978B
CN106630978B CN201610825929.7A CN201610825929A CN106630978B CN 106630978 B CN106630978 B CN 106630978B CN 201610825929 A CN201610825929 A CN 201610825929A CN 106630978 B CN106630978 B CN 106630978B
Authority
CN
China
Prior art keywords
coating
thermal insulation
insulation tile
powder
high emissivity
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
Application number
CN201610825929.7A
Other languages
Chinese (zh)
Other versions
CN106630978A (en
Inventor
鲁胜
裴雨辰
张凡
郭慧
吴宪
刘斌
赵英民
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.)
Aerospace Research Institute of Materials and Processing Technology
Original Assignee
Aerospace Research Institute of Materials and Processing Technology
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 Aerospace Research Institute of Materials and Processing Technology filed Critical Aerospace Research Institute of Materials and Processing Technology
Priority to CN201610825929.7A priority Critical patent/CN106630978B/en
Priority to CN201810298020.XA priority patent/CN108455978B/en
Priority to CN201810295856.4A priority patent/CN108383391B/en
Priority to CN201810292275.5A priority patent/CN108467260B/en
Publication of CN106630978A publication Critical patent/CN106630978A/en
Application granted granted Critical
Publication of CN106630978B publication Critical patent/CN106630978B/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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/14—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silica
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B28—WORKING CEMENT, CLAY, OR STONE
    • B28B—SHAPING CLAY OR OTHER CERAMIC COMPOSITIONS; SHAPING SLAG; SHAPING MIXTURES CONTAINING CEMENTITIOUS MATERIAL, e.g. PLASTER
    • B28B1/00—Producing shaped prefabricated articles from the material
    • B28B1/26—Producing shaped prefabricated articles from the material by slip-casting, i.e. by casting a suspension or dispersion of the material in a liquid-absorbent or porous mould, the liquid being allowed to soak into or pass through the walls of the mould; Moulds therefor ; specially for manufacturing articles starting from a ceramic slip; Moulds therefor
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/0605—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances by sublimating
    • 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
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • 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
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
    • C04B2235/602—Making the green bodies or pre-forms by moulding
    • C04B2235/6023—Gel casting

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to the alumina fibre rigidity thermal insulation tile multilayer materials of surface toughening, coating composition, preparation method and applications.The composite includes Woelm Alumina fibrous matrix, surface toughening aluminum oxide dense ceramic layers, high emissivity oxide thermal barrier coating and low chemical catalysis coefficient glass coating.The coating composition includes surface toughening aluminum oxide ceramic of compact layer composition, high emissivity oxide thermal barrier coating compositions and low chemical catalysis coefficient glass coating composition.The preparation method of the composite includes being sequentially prepared described matrix, the dense ceramic layers, the thermal barrier coating and the glass coating.Present invention also offers application of the composite in the thermally protective materials of aircraft outer surface.The present invention is using novel technology, using the matrix and coating composition of uniqueness, be made have can in 1600 DEG C of environment long-time it is reusable, with superior durothermic composite.

Description

Alumina fibre rigidity thermal insulation tile multilayer materials, the coatings combine of surface toughening Thing, preparation method and applications
Technical field
The present invention relates to alumina fibre rigidity thermal insulation tile multilayer materials of surface toughening and preparation method thereof, belong to Functional composite material technical field.
Background technology
Oxide ceramic fibre rigidity thermal insulation tile multilayer materials use as the thermally protective materials of aircraft outer surface, With heatproof height, light weight, it is reusable many advantages, such as.Therefore, it is heat-insulated to employ rigidity for U.S. space shuttle large area Watt multilayer materials are as thermally protective materials.Typical rigid thermal insulation tile multilayer materials matrix includes LI-900 and LI- 2200(US3952083)、FRCI(US4148962)、HTP(R.P.Banas,et,al.,Thermophysical and Mechanical Properties of the HTP Family of Rigid Ceramic Insulation Materials,AIAA-85-1055)、AETB(Daniel B.Leiser et.,al.,Options for Improving Rigidized Ceramic Heatshilds,Ceramic Engineering and Science Proceedings,6, No.7-8, pp.757-768,1985) and BRI (US6716782B2).Above-mentioned five kinds of rigid thermal insulation tile multilayer materials are all It is using quartz fibre as key component.However, using quartz fibre as the rigid thermal insulation tile multilayer materials material of key component Reusable temperature extremes is 1500 DEG C, during higher than this temperature value, quartz fibre can quick crystallization, so as to cause thermal insulation tile to be received Compression deformation, and then fail.Therefore the rigid thermal insulation tile multilayer materials using quartz fibre as key component are used as flight Heat-barrier material reliability when being used higher than 1500 DEG C in device outer surface is very low.
GE companies of the U.S. are that the protection of space shuttle outer surface heat develops mullite rigidity thermal insulation tile multilayer materials (Reusable External Insulation, REI-Mullite, NASA TMX-2719, the 17-60 pages), its temperature tolerance is excellent In the complete rigid thermal insulation tile multilayer materials of quartz of LI-900.
The development work of rigid ceramic thermal insulation tile fibrous matrix is carried out since the eighties in last century in China.Shandong work Industry ceramic research designing institute discloses a kind of preparation method of heat insulation tile of shuttle in CN 101691138A.This space flight flies Machine thermal insulation tile by the quartz fibre of 50% to 95% mass fraction, the alumina fibre of 5% to 50% mass fraction and 0 to The boron nitride powder agglutinant composition of 5% mass fraction.Contain a large amount of alkali metal in thermal insulation tile coating formula disclosed in the patent With alkaline-earth metal ions, coating viscosity can be caused to significantly reduce under high temperature, limit the temperature in use of thermal insulation tile, thus it is such It is only capable of used below at 1200 DEG C.
A kind of composition of light rigidity ceramic insulation watt and preparation method thereof is disclosed in CN102199042A.This kind of rigidity Ceramic insulation watt is made up of 50% to 100% quartz fibre and 0% to 50% mullite fiber, adds ceramic fibre quality 0.01 to 15% boron nitride powder agglutinant, while the silicon carbide powder of ceramic fibre quality 0 to 20% is added as high temperature Anti-rad.CN 104529369A and CN201510632711.5 disclose it is a kind of by quartz fibre, alumina fibre and/or The preparation method of the rigid thermal insulation tile multilayer materials of Zirconium oxide fibre composition.
The flying speed of high-speed aircraft of new generation reaches several Mach even more than ten Mach, aircraft windward side large area position Put temperature and be likely to be breached 1500 DEG C to 1650 DEG C, it is therefore necessary to develop the higher rigid thermal insulation tile multilayer materials material of temperature tolerance Material, to meet the thermal protection demand of high-speed aircraft of new generation.
Alumina fibre has fabulous temperature tolerance, and reusable temperature is up to 1600 DEG C for a long time.U.S. Zircar is public Department produces a kind of alumina fibre plate, and the product for civilian use can be used as to be used for high temperature inner lining of furnace, chemical reactor thermal protection etc. and used. Zircar companies are holded in close confidence to the production technology of the fiberboard, and no open source literature is disclosed to it.Zircar companies are simultaneously A kind of ceramic forerunner suitable for its alumina plate surface densification is also sold, its specific formula can also be looked into without open source literature. Aircraft outer surface heat-barrier material is used as however, having no using the Zircar alumina fibres plate of surface recombination high emissivity coating Report.Therefore, the surface toughening alumina fibre rigidity thermal insulation tile multi-layer composite materials of 1600 DEG C of independent research long-time heatproof Material, and it is applied to the heat-insulated field of aerospace field superhigh temperature, there is important strategic importance.
Freezing gel injection molding is widely used in preparing porous ceramics class material.Chinese Academy of Sciences's Shanghai silicate research It is proposed by alumina sol carry out ceramics freezing casting prepare alumina porous ceramic (CN200610119248.5, CN200610119233.9, CN200710037605.8).Xi'an University of Technology utilizes Freeze Drying Technique, prepares and is applied to admittedly The porous ceramic film material (CN200810150654.7) of oxide body fuel cell；Tsing-Hua University Wang Chang'an etc. proposes a kind of " cold Jelly-gel forming " prepares the technique (CN200710099624.3) of porous ceramic film material.The ceramic raw material that above-mentioned all patents use It is powder, pore-foaming agent is water or tert-butyl alcohol etc..This forming method is in actual ceramic preparation process, the formed ice of freezing The defects of crystalline substance is changed into large-size after evaporation of the solvent, causes blank strength low, has a strong impact on the performance of material.Such The porous ceramic film material porosity prepared using ceramic powder precursor as raw material, with freezing gel molding process is generally not more than 50%, the thermal conductivity of product is higher；And the hole in porous ceramics is oriented alignment, the anisotropy of material is caused.
High temperature resistant rigidity thermal insulation tile multilayer materials are as aircraft outer surface large area heat-barrier material in use, needing In the compound high emissivity coating in thermal insulation tile windward side.High emissivity coating can be by caused big portion absolutely during aircraft flight Aerodynamic Heating re-radiation is divided to go back to low temperature background space.On the other hand, the thermal insulation tile surface being densified by coating can sock in During aircraft surface plasma thermal current by watt hole enter thermal insulation tile body interior, mass-and heat-transfer occurs. Finally, high emissivity coating also acts as the effect of waterproof.
Because alumina fibre thermal insulation tile is porous material, porosity is more than 80%, and thickness direction compressive strength is only 1.5MPa, when directly spraying high emissivity coating using plasma sputtering to the material surface, it is sprayed-on the thermal insulation tile table of layer The easy efflorescence fracture in face.Therefore densification toughness reinforcing must be carried out to the thermal insulation tile surface that will spray high emissivity coating.
US4093771 disclose a kind of high reaction activity reaction curing glass powder (Reaction Cured Glass, ) and the preparation method using RCG as the glass coating of raw material RCG.This glass glaze is adapted as Lightweight ceramic ceramic tiles Luo Kexi The face coat of moral heat-barrier material (Lockheed Insulation, LI, US 3952083) uses.Typical RCG coating formulas Curing glass powder and 2.5% molybdenum disilicide high emissivity material composition, sintering temperature are reacted by the high activity of 97.5% mass fraction Spend for 1150 DEG C, sintering time is 1.5 hours.However, RCG glass coating shock resistances are poor, long-time temperature in use does not surpass Cross 1260 DEG C.
US 5079082 discloses a kind of fibrous insulating material (the Toughened Uni-piece of monolithic of Strengthening and Toughening Fibrous Insulation, TUFI) preparation method.The patent adds four silicon borides on the basis of RCG glass coatings Powder is as coating sintering aid.By the particle diameter for reducing particle in coating paste so that coated substance is more during spray-on coating slurry Penetrate into more in fibrous matrix, so as to form the fibre reinforced composites of gradient.Typically TUFI coating formulas are 77.5%RCG glass dust, 2.5% 4 silicon boride sintering aid and 20% molybdenum disilicide high emissivity material.Sintering temperature is 1220 DEG C, sintering time is 1.5 hours.TUFI coatings increase substantially than RCG glass coating shock resistances, once as space flight The major programme of the aircraft thermal insulation tile face coat such as aircraft thermal insulation tile and X-37, X-43, X-51 widely uses.TUFI coatings Long-term use of temperature is no more than 2600 ℉ (1427 DEG C).The rigid thermal insulation tile multilayer of TUFI coatings and the various trades mark of U.S.'s exploitation Matrices of composite material (LI, FRCI, AETB, BRI) can be well matched with compound.
US 7767305B1 disclose a kind of efficiently tantalum base coating composite material (High Efficiency Tantalum- Based Composite, HETC) preparation method.TaSi2, MoSi2 and RCG glass dust compares in HETC coating formulas Example can be wanted according to the linear expansion coefficient, emissivity index request and temperature tolerance index of rigid thermal insulation tile multilayer materials matrix Seek optimization design.HETC coatings are applicable not only to above-mentioned oxide ceramic fibre rigidity thermal insulation tile multilayer materials, are also suitable In carbon fiber class light rigidity thermal insulation tile multilayer materials.TaSi2 in HETC coatings plays reduction coating surface chemistry and urged Change the effect of coefficient.
GE companies of the U.S. match somebody with somebody while REI-Mullite mullite fiber rigidity thermal insulation tile multilayer materials are developed Set develops the high emissivity thermal barrier coating suitable for the thermal insulation tile system, and its main component is nickel oxide, chromium oxide, cobalt oxide Etc. the refractory ceramics such as high emissivity material and titanium dioxide, barium zirconate, strontium titanates filler (NASA CR-4227, Thermal Protection System of the Space Shuttle, Appendix III-16).
At home, CN103467074A and CN201510632090.0 individually discloses a kind of high-temperaure coating and its preparation Method and its improved method, prepared high emissivity coating hemisphere compose emissivity more than or equal to 0.85 entirely, its hot expansion property Good matching can be realized with the rigid thermal insulation tile multilayer materials described in CN201510632711.5.
The content of the invention
The purpose of the present invention is to overcome the reusable light rigidity thermal insulation tile multilayer materials of existing quartz fibre base The shortcomings that temperature tolerance deficiency, it is higher, reusable, light finally to provide a kind of temperature tolerance using different technical schemes Matter, surface toughening alumina fibre rigidity thermal insulation tile multilayer materials and preparation method thereof, for such as a new generation at a high speed The large area thermal protection system design of aircraft outer surface provides material solution and supported.
Therefore, the present invention realizes the purpose of the present invention by following technical solution：
1st, a kind of surface toughening aluminum oxide ceramic of compact layer composition, it is characterised in that the surface toughening aluminum oxide causes Close ceramic layer combination thing includes two kinds of colloidal sol continuous phases and at least one refractory ceramics powder disperse phase, and described two colloidal sols connect Continuous mutually to include the first colloidal sol continuous phase and the second colloidal sol continuous phase, the first colloidal sol continuous phase is alkaline sol continuous phase, institute It is alumina sol and/or zirconia sol to state the second colloidal sol continuous phase；At least one refractory ceramics powder disperse phase choosing The group that free fused silica powder, alumina powder, boron nitride powder, aluminum nitride powder, zirconia powder and titanium dioxide form；Preferably, At least one refractory ceramics powder disperse phase is aluminum nitride powder and/or fused silica powder.
2nd, the surface toughening aluminum oxide ceramic of compact layer composition according to technical scheme 1, it is characterised in that the table Face toughening aluminum oxide ceramic of compact layer composition is by described two colloidal sol continuous phases and at least one refractory ceramics powder Disperse phase composition.
3rd, the surface toughening aluminum oxide ceramic of compact layer composition according to technical scheme 1 or 2, it is characterised in that：
The dosage of the first colloidal sol continuous phase is 25 mass % of 1 mass parts the first colloidal sol continuous phase；
The second colloidal sol continuous phase is 40 mass % of 0.7 to 0.8 mass parts the second colloidal sol continuous phase；And/or
At least one refractory ceramics disperse phase is that the particle diameter of 0.2 to 0.3 mass parts is 1 micron to 2 microns resistance to Refractory ceramics disperse phase.
4th, the surface toughening aluminum oxide ceramic of compact layer composition according to technical scheme 3, it is characterised in that the table Face toughening aluminum oxide ceramic of compact layer composition is following composition：
The alkaline silica sol that (1) 1 part of mass fraction is 25%, the aluminum oxide that 0.7 to 0.8 part of mass fraction is 40% are molten Glue, the aluminum nitride powder that 0.2 to 0.3 part of particle diameter is 1 to 2 micron；
The alkaline silica sol that (2) 1 parts of mass fractions are 25%, the oxidation that 0.7 to 0.8 part of mass fraction is 30% to 35% Zirconium colloidal sol, the aluminum nitride powder that 0.2 to 0.3 part of particle diameter is 1 to 2 micron；
The alkaline silica sol that (3) 1 parts of mass fractions are 25%, the oxidation that 0.7 to 0.8 part of mass fraction is 30% to 35% Zirconium colloidal sol, the fused silica powder that 0.2 to 0.3 part of particle diameter is 1 to 2 micron.
5th, a kind of high emissivity coating composition, it is characterised in that comprising selected from by yttria-stabilized zirconia powder, quartz In the group that glass dust, barium zirconate powder, nickel oxide powder, alumina powder, Zirconium powder, borosilicate glass powder form at least It is a kind of；It is further preferred that the high emissivity coating composition includes：
(1) yttria-stabilized zirconia powder；
(2) nickel oxide powder；With
(3) fused silica powder.
6th, the high emissivity coating composition according to technical scheme 1, it is characterised in that the high emissivity coating group Compound is made up of following component：
(1) yttria-stabilized zirconia powder；
(2) nickel oxide powder；With
(3) fused silica powder.
7th, the high emissivity coating composition according to technical scheme 5 or 6, it is characterised in that：
The granularity of yttria-stabilized zirconia powder is 1 micron to 3 microns；
The granularity of nickel oxide powder is 1 micron to 3 microns；And/or
The granularity of fused silica powder is 1 micron to 3 microns.
8th, the high emissivity coating composition according to any one of technical scheme 5 to 7, it is characterised in that：
The parts by weight of yttria-stabilized zirconia powder in the high emissivity coating composition are 1 part；
The parts by weight of nickel oxide powder in the high emissivity coating composition are 1.8 to 2.2 parts；And/or
The parts by weight of fused silica powder in the high emissivity coating composition are 2.8 to 3.2 parts.
9th, a kind of low chemical catalysis coefficient glass coating composition, it is characterised in that the low chemical catalysis coefficient glass Coating composition includes continuous phase, high emissivity phase and the low chemical catalysis coefficient disperse phase of high temperature.
10th, the low chemical catalysis coefficient glass coating composition according to technical scheme 9, it is characterised in that described low Chemical catalysis coefficient glass coating composition is by continuous phase, high emissivity phase and the low chemical catalysis coefficient disperse phase composition of high temperature.
11st, the low chemical catalysis coefficient glass coating composition according to technical scheme 9 or 10, it is characterised in that：
The continuous phase sinters continuous phase for reaction curing glass；
The high emissivity is mutually molybdenum disilicide high emissivity phase；And/or
The low chemical catalysis coefficient disperse phase of the high temperature is in the group being made up of tantalum silicide, silication mercury and tungsten silicide It is at least one.
12nd, the low chemical catalysis coefficient glass coating composition according to technical scheme 11, it is characterised in that：
The continuous phase is that reaction curing glass sintering continuous phase is 1 parts by weight；
The high emissivity is mutually that molybdenum disilicide high emissivity is mutually 0.4 to 0.6 parts by weight；And/or
The low chemical catalysis coefficient disperse phase of the high temperature is 0.4 to 0.6 parts by weight.
13rd, the low chemical catalysis coefficient glass coating composition according to any one of technical scheme 9 to 12, its feature It is, the low chemical catalysis coefficient disperse phase of the high temperature comprises at least tungsten silicide and/or silication mercury.
14th, a kind of rigid thermal insulation tile multilayer materials, it is characterised in that the rigid thermal insulation tile multilayer materials by In to including successively outside：
(1) Woelm Alumina fibrous matrix；
(2) surface toughening aluminum oxide dense ceramic layers；
(3) high emissivity oxide thermal barrier coating；With
(4) low chemical catalysis coefficient glass coating.
15th, the rigid thermal insulation tile multilayer materials according to technical scheme 14, it is characterised in that：
Described matrix is made by alumina fibre and acidic silicasol；
The surface toughening aluminum oxide dense ceramic layers are as the surface toughening oxidation any one of technical scheme 1 to 4 Aluminium ceramic of compact layer composition coats；
The high emissivity oxide thermal barrier coating is as the surface toughening aluminum oxide any one of technical scheme 5 to 8 Ceramic of compact layer composition coats；And/or
The low chemical catalysis coefficient glass coating is as the low chemical catalysis coefficient any one of technical scheme 9 to 13 Coating composition for glass coats.
16th, the rigid thermal insulation tile multilayer materials according to technical scheme 15, it is characterised in that the aluminum oxide is fine The mass ratio of acidic silicasol described in peacekeeping is 1:195 to 205, the concentration of the acidic silicasol is 8 mass % to 10 matter Measure %.
17th, the rigid thermal insulation tile multilayer materials according to any one of technical scheme 14 to 16, it is characterised in that：
The thickness of the surface toughening aluminum oxide dense ceramic layers is 3mm to 5mm；
The thickness of the high emissivity oxide thermal barrier coating is 100 microns to 200 microns；And/or
The thickness of the low chemical catalysis coefficient glass coating is 100 microns to 200 microns.
18th, the method for rigid thermal insulation tile multilayer materials any one of a kind of manufacturing technology scheme 14 to 17, its It is characterised by, methods described comprises the following steps：
(1) alumina fibre and the acidic silicasol are mixed and stirred for uniformly, filtering, by filter cake in wet mold Wet base is made in tool, wet base is freezed in freezing in mould, is made and freezes base, base will be frozen and dried, sintering, the porous oxidation is made Aluminum fiber matrix；
(2) the manufacture surface toughening aluminum oxide ceramic of compact layer composition is coated in the Woelm Alumina fiber base On the surface of body, dry and solidify, so as to form the surface toughening aluminum oxide dense ceramic layers；
(3) by using plasma sputtering method by the high emissivity oxide thermal barrier coating in the surface toughening On aluminum oxide dense ceramic layers, so as to form the high emissivity oxide thermal barrier coating；With
(4) by low chemical catalysis coefficient glass coating composition on the high emissivity oxide thermal barrier coating simultaneously Sintering, so as to form low chemical catalysis coefficient glass coating.
19th, the method according to technical scheme 18, it is characterised in that in the step (1)：
Using oar blade type shearing stirrer dispersed alumina fiber, mixing speed is 2000 to 3000 revs/min, during stirring Between be 10 to 30 minutes；
The filtering uses 50 mesh filter screen filtrations；
The freezing is freezed using liquid nitrogen, and liquid nitrogen did not had the freezing die surface 15cm to 20cm during freezing, cold It is 1 hour to 2 hours to freeze the time；
The jelly base is in 120 DEG C of dryings；And/or
The sintering temperature of the sintering is 1250 DEG C to 1500 DEG C, and the soaking time of sintering is 1 hour to 4 hours.
20th, the method according to technical scheme 18 or 19, it is characterised in that in the step (2)：
The drying is carried out in room temperature, described to be solidificated in 200 DEG C to 400 DEG C progress.
21st, the method according to any one of technical scheme 18 to 20, it is characterised in that in the step (3), institute The technological parameter for stating plasma sputtering method is as follows：Sputtering carrier gas uses oxygen/propane flame, and propane flow is 1150 to 1250 L/h, oxygen flow is 2200 to 2300 ls/h, and the heat flow density of jet-stream wind is 1.15 to 1.20MW/m2。
22nd, the method any one of root technical scheme 18 to 21, it is characterised in that described in the step (4) Low chemical catalysis coefficient glass coating is coated using spraying method, and nebulizer gas pressure is 0.2 to 0.5MPa；And/or sintering institute The temperature for stating low chemical catalysis coefficient glass coating is 1200 to 1250 DEG C, and the soaking time of sintering is 0.5 to 1.5 hour.
23rd, the rigid thermal insulation tile multilayer materials or technical scheme 18 according to any one of technical scheme 14 to 17 To rigid thermal insulation tile multilayer materials made from the method any one of 22 aircraft outer surface thermally protective materials, Superhigh temperature chemical reactor thermally protective materials, nuclear reactor superhigh temperature thermally protective materials, superhigh temperature furnace insulation liner or metal Application in fondant filter.
The present invention passes through repetition test, it is determined that is suitable for by alumina fibre rigidity thermal insulation tile multilayer produced by the present invention Coating is formed on composite causes rigid thermal insulation tile multilayer materials to have the required surface toughening oxygen of estimated performance Change aluminium ceramic of compact layer composition, surface toughening aluminum oxide ceramic of compact layer composition and low chemical catalysis coefficient glass coating group Compound.The inventive method prepares fibrous matrix using freezing gel molding process, selects described suitable surface toughening to aoxidize Aluminium ceramic of compact layer composition, surface toughening aluminum oxide ceramic of compact layer composition and low chemical catalysis coefficient glass coatings combine Thing sequentially forms surface toughening aluminum oxide dense ceramic layers, surface toughening aluminum oxide dense ceramic layers and low chemical catalysis coefficient glass Glass coating.Thus obtained rigid thermal insulation tile multilayer materials are that a kind of alumina fibre rigidity thermal insulation tile of surface toughening is more Layer composite, including alumina fibre thermal insulation tile matrix A, surface toughening compact aluminum oxide ceramic layer B, high emissivity coating C With low chemical catalysis coefficient dense glass coating D.Wherein, the technological process bag of the rigid thermal insulation tile multilayer materials is prepared Include：
1. prepare fibrous matrix A using freezing gel molding process.In the past freezing gel injection molding method mainly prepare with Ceramic powder is the porous ceramics of raw material, and as the civilian occasion such as melted metal filter, the present invention is innovatively by the technique Shaping applied to alumina fibre thermal insulation tile fibrous matrix.
2. to matrix A outer surface coating, the especially salic colloidal sol of surface toughening compact aluminum oxide ceramic layer and nitrogen Change the densification composition of aluminium powder body, the high temperature sintering after reagent solidification, so as to prepare surface toughening compact aluminum oxide ceramic Layer B；
3. prepare one layer of high emissivity coating C again in ceramic layer B outside using plasma sputtering spraying method；
4. because the present inventor has found through many experiments, high emissivity oxide thermal barrier coating causes in surface toughening aluminum oxide The surface of close ceramic layer can not obtain smooth coating, therefore prepare resistance to height in the outer layer of high emissivity oxide thermal barrier coating again The low catalysic coefficient dense glass coating D of temperature.
The present invention innovative point at least that：
(1) the alumina fibre rigidity thermal insulation tile multilayer materials of the surface toughening prepared by the present invention can be at 1600 DEG C Reusable for a long time in environment, temperature tolerance is better than existing rigid thermal insulation tile multilayer materials, such as with quartz fibre Deng the rigid thermal insulation tile multilayer materials material for key component；
(2) present invention is innovatively prepared with high performance alumina fibre rigidity using freezing gel injection molding method Thermal insulation tile multilayer materials matrix；
(3) the present inventor have developed a kind of alumina fibre rigidity thermal insulation tile multilayer materials surface toughness reinforcing densification Method；
(4) the present inventor have developed a kind of alumina fibre rigidity thermal insulation tile multilayer materials surface high emissivity and apply Layer formula and technique；
(5) the present inventor have developed high emissivity coating formula and innovatively use plasma sputtering spraying side Method prepares high emissivity coating.
The alumina fibre rigidity thermal insulation tile multilayer materials of surface toughening of the present invention can be used as such as aircraft appearance Thermally protective materials, superhigh temperature chemical reactor thermally protective materials, nuclear reactor superhigh temperature thermally protective materials, the superhigh temperature kiln in face The multiple uses such as insulating inner lining, melted metal filter use.
Brief description of the drawings
Fig. 1 is alumina fibre rigidity thermal insulation tile multilayer materials structural representation of the present invention.Wherein 1 is that aluminum oxide is fine Tie up thermal insulation tile agent structure；2 be surface toughening compact aluminum oxide ceramic layer；3 be to be prepared using plasma sputtering spraying coating process Rough high emissivity coating；4 be the low chemical catalysis coefficient smooth glass coating prepared using spraying-sintering process；5 are The reserved respiratory region of design, after alumina fibre rigidity thermal insulation tile multilayer materials are heated in use, in matrix Air spatial context can be dissipated to by the passage.
Fig. 2 is alumina fibre rigidity thermal insulation tile multilayer materials preparation technology flow chart of the present invention, is divided into matrix system Prepared by standby, surface densification, high emissivity coating and low catalysic coefficient coating prepares four steps.
Fig. 3 is the stereoscan photograph of alumina fibre rigidity thermal insulation tile multilayer materials matrix of the present invention.
Embodiment
As described above, the present invention provides a kind of surface toughening aluminum oxide ceramic of compact layer composition, institute in first aspect State surface toughening aluminum oxide ceramic of compact layer composition and include two kinds of colloidal sol continuous phases and at least one refractory ceramics powder more Dephasing, described two colloidal sol continuous phases include the first colloidal sol continuous phase and the second colloidal sol continuous phase, the first colloidal sol continuous phase For alkaline sol continuous phase, the second colloidal sol continuous phase is alumina sol and/or zirconia sol；At least one is resistance to Refractory ceramics powder disperse phase is selected from by fused silica powder, alumina powder, boron nitride powder, aluminum nitride powder, zirconia powder and titanium The group of white powder composition, preferably aluminum nitride powder and/or fused silica powder.
In some preferred embodiments, the surface toughening aluminum oxide ceramic of compact layer composition is by described two molten Glue continuous phase and at least one refractory ceramics powder disperse phase composition.
In some preferred embodiments, the dosage of the first colloidal sol continuous phase is 25 mass % of 1 mass parts The first colloidal sol continuous phase.
Also it is preferred that the second colloidal sol continuous phase connects for 40 mass % of 0.7 to 0.8 mass parts the second colloidal sol Continuous phase.
Also it is preferred that the particle diameter that at least one refractory ceramics disperse phase is 0.2 to 0.3 mass parts is 1 micro- The refractory ceramics disperse phase of rice to 2 microns.
In some further preferred embodiments, the surface toughening aluminum oxide ceramic of compact layer composition can wrap Containing 1 part of mass fraction for 25% alkaline silica sol, the alumina sol that 0.7 to 0.8 part of mass fraction is 40%, 0.2 to 0.3 The aluminum nitride powder that part particle diameter is 1 to 2 micron.In other preferred embodiment, the surface toughening aluminum oxide is fine and close Ceramic layer combination thing can include the alkaline silica sol that 1 part of mass fraction is 25%, 0.7 to 0.8 part of mass fraction be 30% to 35% zirconia sol, the aluminum nitride powder that 0.2 to 0.3 part of particle diameter is 1 to 2 micron.In other preferred embodiment In, the surface toughening aluminum oxide ceramic of compact layer composition can include the alkaline silica sol that 1 part of mass fraction is 25%, The zirconia sol that 0.7 to 0.8 part of mass fraction is 30% to 35%, the quartz glass that 0.2 to 0.3 part of particle diameter is 1 to 2 micron Powder.
Second aspect of the present invention provides a kind of high emissivity coating composition, and the high emissivity coating composition includes Selected from by yttria-stabilized zirconia powder, fused silica powder, barium zirconate powder, nickel oxide powder, alumina powder, zirconia powder At least one of group that body, borosilicate glass powder form.It is further preferred that the high emissivity coating composition includes：(1) oxygen Change yttrium stable zirconium oxide powder；(2) nickel oxide powder；(3) fused silica powder.
In some preferred embodiments, the high emissivity coating composition is made up of following component：(1) aoxidize Yttrium stable zirconium oxide powder；(2) nickel oxide powder；(3) fused silica powder.
In some preferred embodiments, the granularity of the yttria-stabilized zirconia powder is 1 micron to 3 microns (example Such as 1,2 or 3 micron).The granularity of the nickel oxide powder is 1 micron to 3 microns (such as 1,2 or 3 micron).In addition, the quartz The granularity of glass dust is 1 micron to 3 microns (such as 1,2 or 3 micron).
In some preferred embodiments, the yttria-stabilized zirconia powder in the high emissivity coating composition Parts by weight think 1 part, the parts by weight of the nickel oxide powder in the high emissivity coating composition are 1.8 to 2.2 parts, the height The parts by weight of fused silica powder in emissivity coating composition are 2.8 to 3.2 parts.
The present invention provides a kind of low chemical catalysis coefficient glass coating composition, the low chemical catalysis in the third aspect Coefficient glass coating composition includes continuous phase, high emissivity phase and the low chemical catalysis coefficient disperse phase of high temperature.
It is further preferred that the low chemical catalysis coefficient glass coating composition is by continuous phase, high emissivity phase and high temperature Low chemical catalysis coefficient disperse phase composition.
In some preferred embodiments, the continuous phase can be that reaction curing glass sinters continuous phase.It is excellent in addition Choosing, the high emissivity can be mutually molybdenum disilicide high emissivity phase.Also it is preferred that the low chemical catalysis of the high temperature Coefficient disperse phase is selected from least one of group being made up of tantalum silicide, silication mercury and tungsten silicide.
In some preferred embodiments, the continuous phase is that reaction curing glass sintering continuous phase is 1 parts by weight, The high emissivity is mutually that molybdenum disilicide high emissivity is mutually 0.4 to 0.6 parts by weight；The low chemical catalysis coefficient disperse of the high temperature It is mutually 0.4 to 0.6 parts by weight.
In some particularly preferred embodiments, the low chemical catalysis coefficient disperse phase of the high temperature comprises at least tungsten silicide And/or silication mercury.Inventors have surprisingly found that the tantalum silicide powder stated the low chemical catalysis coefficient disperse phase of high temperature and included End can use the materials such as tungsten silicide, silication mercury to substitute, and can play a part of reducing coating catalysic coefficient.
The present invention provides a kind of rigid thermal insulation tile multilayer materials in the third aspect, and the rigid thermal insulation tile multilayer is answered Condensation material includes：(1) Woelm Alumina fibrous matrix；(2) surface toughening aluminum oxide dense ceramic layers；(3) high emissivity aoxidizes Thing thermal barrier coating；(4) low chemical catalysis coefficient glass coating.
In some preferred embodiments, described matrix is made by alumina fibre and acidic silicasol；The surface Toughening aluminum oxide dense ceramic layers are coated as the surface toughening aluminum oxide ceramic of compact layer composition described in first aspect present invention； The high emissivity oxide thermal barrier coating is combined by the surface toughening aluminum oxide dense ceramic layers described in second aspect of the present invention Thing coats；And/or the low chemical catalysis coefficient glass coating is as the low chemical catalysis coefficient glass described in third aspect present invention Glass coating composition coats.
In some preferred embodiments, the mass ratio of the alumina fibre and the acidic silicasol is 1:195 To 205, more preferably 1:200.The concentration of the acidic silicasol is 8 mass % to 10 mass %, the matter of for example, 8,9 or 10 Measure %.
The present invention has no particular limits to each thickness degree, as long as estimated performance can be realized.It is but excellent at some In the embodiment of choosing, the thickness of the surface toughening aluminum oxide dense ceramic layers is 3mm to 5mm.The high emissivity oxidation The thickness of thing thermal barrier coating can be 100 microns to 200 microns, for example, 100,110,120,130,140,150,160,170, 180th, 190 or 200 microns.In addition, the thickness of the low chemical catalysis coefficient glass coating can be 100 microns to 200 microns, For example, 100,110,120,130,140,150,160,170,180,190 or 200 microns.
The present invention provides a kind of rigid thermal insulation tile MULTILAYER COMPOSITE manufactured described in fourth aspect present invention at the 5th aspect The method of material, methods described comprise the following steps：
(1) alumina fibre and the acidic silicasol are mixed and stirred for uniformly, filtering, by filter cake in wet mold Wet base is made in tool, wet base is freezed in freezing in mould, is made and freezes base, base will be frozen and dried, sintering, the porous oxidation is made Aluminum fiber matrix；
(2) the manufacture surface toughening aluminum oxide ceramic of compact layer composition is coated in the Woelm Alumina fiber base On the surface of body, dry and solidify, so as to form the surface toughening aluminum oxide dense ceramic layers；
(3) by using plasma sputtering method by the high emissivity oxide thermal barrier coating in the surface toughening On aluminum oxide dense ceramic layers, so as to form the high emissivity oxide thermal barrier coating；With
(4) by low chemical catalysis coefficient glass coating composition on the high emissivity oxide thermal barrier coating simultaneously Sintering, so as to form low chemical catalysis coefficient glass coating.
In some preferred embodiments, in the step (1), oar blade type shearing stirrer dispersed alumina is used Fiber, mixing speed are 2000 to 3000 revs/min (being, for example, 2000,2500 or 3000 revs/min), and mixing time control is 10 to 30 minutes, for example, 10,15,20,25 or 30 minutes.Too fast mixing speed or long mixing time can cause to aoxidize Aluminum fiber is beaten too short, and base substrate bulk density is too high after filtering, such as >=0.6g/cm3, be able to not may meet spacecraft every Requirement of the hot material to low-density.The present invention has no particular limits to filtering filter used, it is preferred that the mistake The mesh number for filtering device is 50 mesh.Filtering can be carried out using gravitational settling mode.
In some preferred embodiments, the freezing is freezed using liquid nitrogen, and liquid nitrogen did not had described cold during freezing Freeze die surface 15cm to 20cm, cooling time is 1 hour to 2 hours.Refrigerant is water contained in Ludox.
When being dried to freezing base, the jelly base can be in 120 DEG C of dryings.
The sintering temperature of the sintering be 1250 DEG C to 1500 DEG C (be, for example, 1250,1300,1350,1400,1450 or 1500 DEG C), the soaking time of sintering is 1 hour to 4 hours (being, for example, 1,2,3 or 4 hour).
In the step (2), it is preferred that the drying is carried out in room temperature, described to be solidificated in 200 DEG C to 400 DEG C (examples Such as 200,300 or 400 DEG C) carry out.
In the step (3), it is preferred that the technological parameter of the plasma sputtering method is as follows：Sputter carrier gas Using oxygen/propane flame, propane flow is 1150 to 1250 ls/h, and oxygen flow is 2200 to 2300 ls/h, injection The heat flow density of air-flow is 1.15 to 1.20MW/m2。
The high emissivity coating prepared in step (3) can not be very smooth, it is therefore desirable to further in surface recombination The glass coating D of low catalysic coefficient, to reduce coating surface catalysic coefficient, improve coating temperature tolerance.In the step (4), Preferably, the low chemical catalysis coefficient glass coating is coated using spraying method, nebulizer gas pressure be 0.2 to 0.5MPa.In addition, during sintering, the sintering temperature of the high emissivity coating can be 1200 to 1250 DEG C, during the insulation of sintering Between be 0.5 to 1.5 hour, such as 0.5,1 or 1.5 hour.
The present invention additionally provides a kind of thermal insulation tile rigid as made from fifth aspect present invention methods described at the 6th aspect Multilayer materials.
In some more specifically embodiment, the method described in fifth aspect present invention can be with following steps：
(1) alumina fibre rigidity thermal insulation tile multilayer materials matrix A is prepared using freezing gel injection molding method
Specifically, alumina fibre cotton and acidic silicasol can be pressed 1:195 to 205 mass ratio mixing, is placed in In dispersion bucket, the concentration for controlling Ludox is 8% to 10% mass fraction.It is fine using oar blade type shearing stirrer dispersed alumina Vinylon and cotton blend.Mixing speed control is 2000 to 3000 revs/min, and mixing time control is 10 to 30 minutes.Stirring will pottery after terminating Porcelain slurry is transferred in the frock with screen pack and filtered, and removes most Ludox.Alumina fibre is trapped, filter cake shape Into the wet base of alumina fibre thermal insulation tile.Screen pack used is 50 mesh wire nettings.The thermal insulation tile density wanted according to design, can be with Apply certain pressure to the wet base and be depressed into certain thickness, so as to reach expected density requirements.Wet base after compacting is turned Move in a freezing mould, mould screw lock will be freezed, be placed in household freezer, liquid nitrogen is poured into household freezer, make liquid Nitrogen liquid level is higher than freezing mould upper surface 15 to 20cm.Freezing mould should have enough cryomechanics intensity, to prevent oxygen Change the wet base of aluminium ceramic tile in refrigerating process because volumetric expansion trend caused by the crystallization of water causes mould spalling.Wait 1 to 2 is small Shi Hou, the liquid nitrogen in household freezer volatilize completely, take freezing mould apart, take out thermal insulation tile and freeze base, put and freeze base in stainless steel fixture On, according to required density domination fixture locating dowel height, with screw lock positioning fixture.Will freeze base put in microwave drying oven in 120 DEG C of rapid draings, it is placed in carborundum sintering saggar and is sintered after freezing base and being completely dried.Sintering temperature be 1250 DEG C extremely 1500 DEG C, soaking time is 1 to 4 hour, obtains alumina fibre rigidity thermal insulation tile multilayer materials fibrous matrix.Sintering Sintering processing of the method disclosed in referring also to such as CN201510632711.5 the applicant.In addition, in sintering end Afterwards, obtained Product processing can also will be sintered by Digit Control Machine Tool to required molding surface size, described matrix A is thus made.
(2) dense ceramic layers are prepared using brush coating process
Two kinds of colloidal sol continuous phases and at least one refractory ceramics powder disperse phase can be subjected to mixing and ball milling, being prepared into can With the ceramic sol suspension precursor of brushing, if desired, the viscosity modifier such as acrylamide can be used to adjust Save suspension viscosity so as to make its more suitable for brush.The suspension is brushed to needing to prepare described in dense ceramic layers B After matrix A surface, make its drying in room temperature, then further solidify in 200 DEG C to 400 DEG C baking ovens, form fine and close pottery Enamel coating B.
(3) high emissivity thermal barrier coating C is prepared using plasma sputtering method
High emissivity coating composition is applied to surface toughening aluminum oxide densification using plasma sputtering method On ceramic layer.Sputtering carrier gas uses oxygen/propane flame, and propane flow control is 1150 to 1250L/ hours, oxygen flux control For 2200 to 2300L/ hours, the heat flow density of jet-stream wind is 1.15 to 1.20MW/m2.High emissivity oxide thermal barrier coating Thickness control be 100 to 200 microns, glaze dosage be 0.02 to 0.03g/cm2。
(4) low chemical catalysis coefficient glass coating D is prepared using spraying-flash sintering method
The high emissivity coating prepared in step (3) can not be very smooth, therefore further in the low catalysis of surface recombination Coefficient glass coating D, to reduce coating surface catalysic coefficient, improve coating temperature tolerance.Low catalysic coefficient glass coating D sprays glaze It can be 0.04 to 0.06g/cm to expect dosage2.Nebulizer gas pressure control is 0.2 to 0.5MPa, and coating final thickness is 100 to 200 Micron.Coating sintering temperature is 1200 to 1250 DEG C, and soaking time is 0.5 to 1.5 hour.
The present invention will be hereafter further detailed by way of embodiment, but protection scope of the present invention is not It is limited to these embodiments.
Embodiment 1A prepares alumina fibre rigidity thermal insulation tile multilayer materials matrix A using freezing gel injection molding method
Alumina fibre cotton and acidic silicasol are pressed 1:200 mass ratio mixing, is placed in dispersion bucket, controls Ludox Concentration be 9 mass %.Using oar blade type shearing stirrer dispersed alumina cellucotton, mixing speed control is 2500 revs/min Clock, mixing time control are 20 minutes.After stirring terminates, ceramic slurry is transferred in the frock with screen pack and filtered, institute It is 50 mesh wire nettings with screen pack, the alumina fibre for impregnating the acidic silicasol is trapped, and filter cake forms alumina fibre The wet base of thermal insulation tile.According to design, the target density of required rigid thermal insulation tile multilayer materials is 0.40g/cm3, to this Wet base applies the thickness that pressure is depressed into 35mm, to reach expected density requirements.Wet base after compacting is transferred to cold Freeze in mould, mould screw lock will be freezed, be placed in household freezer, liquid nitrogen is poured into household freezer, be higher than liquid nitrogen liquid level Freeze mould upper surface 15cm.Wait 1.5 hours after, the liquid nitrogen in household freezer volatilizees completely, takes freezing mould apart, take out every Heat watt freezes base, puts and freezes base on stainless steel fixture, by the locating dowel High definition of fixture is 35mm according to required density, uses screw Locking positioning fixture.Base will be frozen to be put into microwave drying oven in 120 DEG C of dryings, after freezing base and being completely dried, be placed in carborundum burning In being sintered in Muffle furnace in knot saggar, sintering temperature is 1250 DEG C, and soaking time is 2.5 hours, obtains alumina fibre rigidity Thermal insulation tile multilayer materials fibrous matrix.It is (long to required molding surface size by obtained Product processing is sintered after terminating The wide 300mm X thickness 30mm of 300mm X), described matrix A is thus made, and obtained matrix A compressive strength is tested, as a result Referring to table 1 below.
Embodiment 2A to 5A
In addition to the content shown in table 1 below, embodiment 2 to 5. is carried out in the same manner as example 1
Embodiment 6A
In addition to the content shown in table 1 below, embodiment 2 to 5, difference are carried out with embodiment substantially similar way Also reside in, after filtering, wet mold tool is transferred on pressure forming machine, applies 2.5MPa pressure, it is heat-insulated to obtain ceramic fibre Watt wet base, wet base is put into microwave drying oven in 120 DEG C of dryings, after freezing base and being completely dried, is obtained dry body, is then carried out institute State and sinter and process.
The matrix A of table 1 preparation
Note：Mass ratio is the mass ratio of alumina fibre and acidic silicasol.
Embodiment 1B dense ceramic layers B's coats
The alkaline silica sol that composition is 25% for 1 part of mass fraction is prepared, the aluminum oxide that 0.7 part of mass fraction is 40% is molten Glue, the ceramic of compact layer composition for the aluminum nitride powder that 0.3 part of particle diameter is 1 micron, viscosity is adjusted using acrylamide, ceramics are made Collosol suspension liquid precursor.The suspension precursor is brushed to the institute for needing to prepare obtained by dense ceramic layers B embodiment 1 State (coating layer thickness 4mm) after matrix A surface, make its drying in room temperature, then further solidify in 300 DEG C of baking ovens, shape Into dense ceramic layers B, then measure coating B consistency, as a result referring to table 2 below.
Embodiment 2B
To implement embodiment 2B with embodiment 1B substantially similar ways, unlike, use quality fraction is 30% Zirconia sol replaces the alumina sol.
Embodiment 3B
To implement embodiment 3B with embodiment 2B substantially similar ways, unlike, replace institute using fused silica powder State aluminum nitride powder.
Embodiment 4B
To implement embodiment 4B with embodiment 1B substantially similar ways, unlike, replace the nitrogen using yittrium oxide Change aluminium powder.
Embodiment 5B
To implement embodiment 5B with embodiment 1B substantially similar ways, unlike, replace the base using matrix 6A Body 1A.
The ceramic layer B of table 2 formula
Embodiment 1C high emissivity coatings coat
High emissivity coating composition is applied to the coating coated to embodiment 2 using plasma sputtering method On B, coating composition by the yttria-stabilized zirconia powder of 1 parts by weight, the nickel oxide powder of 2 parts by weight and 3 parts by weight quartz Glass dust forms.Sputtering carrier gas use oxygen/propane flame, and it is 1150 to 1250L/ hours that propane flow, which controls, oxygen flow control It is made as 2200 to 2300L/ hours, the heat flow density of jet-stream wind is 1.15 to 1.20MW/m2.High emissivity oxide thermal boundary applies The thickness control of layer is 100 to 200 microns.Then, temperature tolerance is determined, as a result referring to table 3 below.
Embodiment 2C to 4C
In addition to the content shown in table 3 below, implement embodiment 2C to 4C in a manner of with embodiment 1C identicals.
The thermal barrier coating C of table 3 preparation
The low chemical catalysis coefficient glass coating D's of embodiment 1D coats
Prepare composition and sinter continuous phase, the molybdenum disilicide high emissivity of 0.5 parts by weight for the reaction curing glass of 1 parts by weight The low catalysic coefficient coating composition for glass of the low chemical catalysis coefficient disperse phase of phase, the high temperature of 0.5 parts by weight, passes through spraying-burning Knot method forms low chemical catalysis coefficient glass coating D, wherein, spraying glaze dosage can be 0.05g/cm2.Nebulizer gas pressure control 0.4MPa is made as, coating final thickness is 150 microns.Coating sintering temperature is 1220, and soaking time is 1.5 hours.And determine Emissivity, it as a result see the table below 4.
Embodiment 2D, 3D, 5D are to 8D
In addition to the content shown in table 4 below, implement in the same manner as in Example 1.
Embodiment 4D
To carry out embodiment 4D with embodiment 1D substantially similar ways, difference is, low catalysic coefficient glass applies The composition of layer composition：Reaction curing glass sintering continuous phase, the molybdenum disilicide high emissivity of 20 parts by weight of 77.5 parts by weight Four silicon borides of phase and 2.5 parts by weight.
The low chemical catalysis coefficient glass coating D of table 4 preparation

Claims (1)

  1. A kind of 1. surface toughening aluminum oxide ceramic of compact layer composition, it is characterised in that the fine and close pottery of the surface toughening aluminum oxide Enamel coating composition is one kind in following composition：(1) 1 mass parts mass fraction be 25% alkaline silica sol, 0.7 to 0.8 Mass parts mass fraction is 40% alumina sol, and 0.2 to 0.3 mass parts particle diameter is 1 to 2 micron of aluminum nitride powder；(2)1 Mass parts mass fraction is 25% alkaline silica sol, and the zirconium oxide that 0.7 to 0.8 mass parts mass fraction is 30% to 35% is molten Glue, 0.2 to 0.3 mass parts particle diameter are 1 to 2 micron of aluminum nitride powder；The alkaline silicon that (3) 1 mass parts mass fractions are 25% is molten Glue, 0.7 to 0.8 mass parts mass fraction are 30% to 35% zirconia sol, and 0.2 to 0.3 mass parts particle diameter is 1 to 2 micro- The fused silica powder of rice.
CN201610825929.7A 2016-09-14 2016-09-14 The alumina fibre rigidity thermal insulation tile multilayer materials of surface toughening, coating composition, preparation method and applications Active CN106630978B (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
CN201610825929.7A CN106630978B (en) 2016-09-14 2016-09-14 The alumina fibre rigidity thermal insulation tile multilayer materials of surface toughening, coating composition, preparation method and applications
CN201810298020.XA CN108455978B (en) 2016-09-14 2016-09-14 Surface-toughened alumina fiber rigid heat-insulating tile multilayer composite material, coating composition, preparation method and application thereof
CN201810295856.4A CN108383391B (en) 2016-09-14 2016-09-14 Surface-toughened alumina fiber rigid heat-insulating tile multilayer composite material, coating composition, preparation method and application thereof
CN201810292275.5A CN108467260B (en) 2016-09-14 2016-09-14 Surface-toughened alumina fiber rigid heat-insulating tile multilayer composite material, coating composition, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610825929.7A CN106630978B (en) 2016-09-14 2016-09-14 The alumina fibre rigidity thermal insulation tile multilayer materials of surface toughening, coating composition, preparation method and applications

Related Child Applications (3)

Application Number Title Priority Date Filing Date
CN201810295856.4A Division CN108383391B (en) 2016-09-14 2016-09-14 Surface-toughened alumina fiber rigid heat-insulating tile multilayer composite material, coating composition, preparation method and application thereof
CN201810292275.5A Division CN108467260B (en) 2016-09-14 2016-09-14 Surface-toughened alumina fiber rigid heat-insulating tile multilayer composite material, coating composition, preparation method and application thereof
CN201810298020.XA Division CN108455978B (en) 2016-09-14 2016-09-14 Surface-toughened alumina fiber rigid heat-insulating tile multilayer composite material, coating composition, preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN106630978A CN106630978A (en) 2017-05-10
CN106630978B true CN106630978B (en) 2018-03-23

Family

ID=58852879

Family Applications (4)

Application Number Title Priority Date Filing Date
CN201610825929.7A Active CN106630978B (en) 2016-09-14 2016-09-14 The alumina fibre rigidity thermal insulation tile multilayer materials of surface toughening, coating composition, preparation method and applications
CN201810295856.4A Active CN108383391B (en) 2016-09-14 2016-09-14 Surface-toughened alumina fiber rigid heat-insulating tile multilayer composite material, coating composition, preparation method and application thereof
CN201810292275.5A Active CN108467260B (en) 2016-09-14 2016-09-14 Surface-toughened alumina fiber rigid heat-insulating tile multilayer composite material, coating composition, preparation method and application thereof
CN201810298020.XA Active CN108455978B (en) 2016-09-14 2016-09-14 Surface-toughened alumina fiber rigid heat-insulating tile multilayer composite material, coating composition, preparation method and application thereof

Family Applications After (3)

Application Number Title Priority Date Filing Date
CN201810295856.4A Active CN108383391B (en) 2016-09-14 2016-09-14 Surface-toughened alumina fiber rigid heat-insulating tile multilayer composite material, coating composition, preparation method and application thereof
CN201810292275.5A Active CN108467260B (en) 2016-09-14 2016-09-14 Surface-toughened alumina fiber rigid heat-insulating tile multilayer composite material, coating composition, preparation method and application thereof
CN201810298020.XA Active CN108455978B (en) 2016-09-14 2016-09-14 Surface-toughened alumina fiber rigid heat-insulating tile multilayer composite material, coating composition, preparation method and application thereof

Country Status (1)

Country Link
CN (4) CN106630978B (en)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107434421B (en) * 2017-08-10 2019-12-10 航天特种材料及工艺技术研究所 antenna window component with wave-transmitting, heat-insulating and bearing performances and preparation method thereof
CN107892569B (en) * 2017-11-21 2020-08-28 淄博双马新材料科技股份有限公司 Composite submerged nozzle lining material for continuous casting
CN108929049A (en) * 2018-08-21 2018-12-04 徐培培 A method of Basalt fiber high-temperature resisting performance is promoted by surface modification
CN109320273A (en) * 2018-09-13 2019-02-12 南京鑫达晶体材料科技有限公司 A kind of improved alumina fibre plate and preparation method thereof
CN109626994B (en) * 2018-11-23 2021-12-28 昆明理工大学 Thermal barrier coating material with low infrared transmittance and preparation method thereof
CN111217620B (en) * 2018-11-26 2022-08-09 航天特种材料及工艺技术研究所 High-temperature-resistant coating on surface of nano porous heat-insulating material substrate, preparation method and substrate
CN111099909B (en) * 2019-12-30 2020-12-29 浙江大学 High-performance ceramic with surface modified polycrystalline mullite fiber compounded with rare earth lanthanum zirconate and preparation method thereof
CN112250450B (en) * 2020-09-15 2022-05-03 航天特种材料及工艺技术研究所 Preparation method of heat insulation tile blank capable of resisting high temperature of 2000 DEG C
CN113979769B (en) * 2021-11-29 2022-09-23 航天特种材料及工艺技术研究所 Rigid ultrathin heat insulation material and preparation method thereof
CN114622153B (en) * 2022-03-14 2023-07-11 西安热工研究院有限公司 Glass modified cerium oxide stabilized zirconia thermal barrier coating and preparation method thereof
CN114540740B (en) * 2022-03-14 2023-07-11 西安热工研究院有限公司 Borosilicate glass modified yttrium oxide stabilized zirconia thermal barrier coating and preparation method thereof
CN116161952B (en) * 2023-04-26 2023-08-18 淄博职业学院 High fracture toughness composite ceramic material and preparation method thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105314999A (en) * 2014-07-29 2016-02-10 金承黎 Nano porous high-temperature-insulating material taking thixotropic colloid as template agent and preparation method for high-temperature-insulating material

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0222480A (en) * 1988-07-12 1990-01-25 Nippon Steel Corp Coated metallic plate having superior workability and far infrared ray radiating property
US5741596A (en) * 1989-02-21 1998-04-21 Boeing North American, Inc. Coating for oxidation protection of metal surfaces
JPH05171261A (en) * 1991-12-18 1993-07-09 Nkk Corp Antioxidant coating material for steel material
US6969546B2 (en) * 2003-10-20 2005-11-29 The Boeing Company Thermal insulation system employing oxide ceramic matrix composites
US7767305B1 (en) * 2004-01-14 2010-08-03 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) High efficiency tantalum-based ceramic composite structures
US7381459B1 (en) * 2004-02-12 2008-06-03 The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration (Nasa) Toughened uni-piece, fibrous, reinforced, oxidization-resistant composite
CN100358832C (en) * 2005-11-22 2008-01-02 武汉理工大学 Mullite whisker-mullite composite coating and preparation process thereof
KR100676167B1 (en) * 2006-01-25 2007-02-01 주식회사 케이씨씨 A biodegradable ceramic fiber composition for a heat insulating material
US20070184204A1 (en) * 2006-01-25 2007-08-09 Shekar Balagopal Environmental and Thermal Barrier Coating to Protect a Pre-Coated Substrate
CN100408512C (en) * 2006-12-06 2008-08-06 中国科学院上海硅酸盐研究所 Method for preparing alumina porous ceramic using gelatin wrapping-freeze drying process
CN101712816B (en) * 2009-11-24 2012-07-04 武汉因福瑞新材料有限公司 Downconversion frequency shift infrared radiation enhanced coating and preparation method thereof
CN102417356B (en) * 2010-09-27 2013-03-20 中国科学院理化技术研究所 Nano silicon carbide series infrared radiation paint and its preparation method
CN103467074B (en) * 2013-08-19 2016-01-13 航天特种材料及工艺技术研究所 A kind of high-temperaure coating and preparation method thereof
CN104862687B (en) * 2015-04-29 2017-06-13 哈尔滨工业大学 A kind of preparation method of metal thermal protection struc ture face coat
CN105130500B (en) * 2015-08-27 2017-06-27 航天材料及工艺研究所 A kind of deformation control method in rigid thermal insulation tile coating forming process

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105314999A (en) * 2014-07-29 2016-02-10 金承黎 Nano porous high-temperature-insulating material taking thixotropic colloid as template agent and preparation method for high-temperature-insulating material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刚性陶瓷隔热瓦研究状况及启示;裴雨辰;《飞航导弹》;20120315(第3期);全文 *
隔热瓦表面高发射率涂层的制备与性能优化;郭金华;《优秀硕士论文全文数据库》;20130601;全文 *

Also Published As

Publication number Publication date
CN108455978B (en) 2021-01-22
CN106630978A (en) 2017-05-10
CN108455978A (en) 2018-08-28
CN108467260A (en) 2018-08-31
CN108383391A (en) 2018-08-10
CN108383391B (en) 2021-04-30
CN108467260B (en) 2020-10-27

Similar Documents

Publication Publication Date Title
CN106630978B (en) The alumina fibre rigidity thermal insulation tile multilayer materials of surface toughening, coating composition, preparation method and applications
US6013592A (en) High temperature insulation for ceramic matrix composites
CN105198492B (en) A kind of antioxidant coating and preparation method thereof
CN103588482B (en) Manufacture method of high porosity and high strength yttrium-silicon-oxygen porous ceramics
Tao et al. MoSi2-borosilicate glass coating on fibrous ceramics prepared by in-situ reaction method for infrared radiation
BRPI1015247A2 (en) method of smoothing the surface of a piece of ceramic matrix composite material.
CN109384475B (en) Combined improvement of SiCfMethod for high-temperature water and oxygen corrosion resistance of/SiC composite material
JPH07315966A (en) High temperature coating provided on ceramic base material and method for non-calcining for obtaining this
WO2022222778A1 (en) Fine ceramic material formed by means of ceramic precursor framework and preparation method therefor and use thereof
CN105780126B (en) A kind of preparation method of the porous mullite formed by generated in-situ whisker overlap joint
CAI Fabrication of Y2Si2O7 coating and its oxidation protection for C/SiC composites
CN108249944B (en) SiO (silicon dioxide)2Process for preparing base composite material
CN102424595B (en) Preparation method of hard erosion resistant alumina fiberboard hearth material
CN110483082A (en) A kind of micro-nano multi-scale nanometer heat insulation material and preparation method thereof
CN111792911B (en) Intelligent temperature-adjusting decorative ceramic plate and preparation method thereof
Tao et al. Effect of TaSi2 content on the structure and properties of TaSi2-MoSi2-borosilicate glass coating on fibrous insulations for enhanced surficial thermal radiation
JP2011236120A (en) CERAMIC COMPOSITE BASED ON β-EUCRYPTITE AND OXIDE, AND PROCESS OF MANUFACTURING THE COMPOSITE
CN108484149A (en) A kind of NaA molecular sieve film support preparation method
CN105517212B (en) A kind of embedded heating panel and preparation method thereof
Yu et al. Fabrication of Si3N4–SiC/SiO2 composites using 3D printing and infiltration processing
JPH07315969A (en) Two-layer high temperature coating provided on ceramic base material and method for forming it
CN110483081A (en) A kind of high-temperature resistant nano heat-barrier material and preparation method thereof
CN103664235B (en) Method for preparing compact O'-sialon/alpha-Si3N4 composite ceramic coating on surface of porous nitride ceramic base body
CN108017397A (en) Refractory brick containing quartz sand and preparation method thereof
CN102419094A (en) Method for preparing vertical intermediate-frequency furnace by integrally casting and compounding furnace pipe and thermal insulation layer

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
CB03 Change of inventor or designer information
CB03 Change of inventor or designer information

Inventor after: Lu Sheng

Inventor after: Pei Yuchen

Inventor after: Zhang Fan

Inventor after: Guo Hui

Inventor after: Wu Xian

Inventor after: Liu Bin

Inventor after: Zhao Yingmin

Inventor before: Lu Sheng

Inventor before: Zhang Fan

Inventor before: Guo Hui

Inventor before: Wu Xian

Inventor before: Liu Bin

Inventor before: Zhao Yingmin

GR01 Patent grant
GR01 Patent grant