CN101445382B - Biomimetic self-healing phase-change heat-absorption A1 microcapsule/ceramic-base composite heat-proof material and preparation method thereof - Google Patents
Biomimetic self-healing phase-change heat-absorption A1 microcapsule/ceramic-base composite heat-proof material and preparation method thereof Download PDFInfo
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- CN101445382B CN101445382B CN200810242999A CN200810242999A CN101445382B CN 101445382 B CN101445382 B CN 101445382B CN 200810242999 A CN200810242999 A CN 200810242999A CN 200810242999 A CN200810242999 A CN 200810242999A CN 101445382 B CN101445382 B CN 101445382B
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- 239000003094 microcapsule Substances 0.000 title claims abstract description 78
- 239000000463 material Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title abstract description 13
- 238000010521 absorption reaction Methods 0.000 title abstract description 5
- 230000003592 biomimetic effect Effects 0.000 title abstract 2
- 239000000919 ceramic Substances 0.000 claims abstract description 85
- 239000000843 powder Substances 0.000 claims abstract description 50
- 238000005245 sintering Methods 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 9
- 230000001590 oxidative effect Effects 0.000 claims abstract description 5
- 239000011257 shell material Substances 0.000 claims description 43
- 239000004411 aluminium Substances 0.000 claims description 28
- 239000011159 matrix material Substances 0.000 claims description 27
- 239000012774 insulation material Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 19
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 10
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- 238000003980 solgel method Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 8
- 239000011224 oxide ceramic Substances 0.000 claims description 7
- 229910052574 oxide ceramic Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 5
- 238000007669 thermal treatment Methods 0.000 claims description 5
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 5
- 229910000737 Duralumin Inorganic materials 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- 229910021332 silicide Inorganic materials 0.000 claims description 2
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- HPNSNYBUADCFDR-UHFFFAOYSA-N chromafenozide Chemical compound CC1=CC(C)=CC(C(=O)N(NC(=O)C=2C(=C3CCCOC3=CC=2)C)C(C)(C)C)=C1 HPNSNYBUADCFDR-UHFFFAOYSA-N 0.000 description 7
- 239000010408 film Substances 0.000 description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
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- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 2
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
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- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910020968 MoSi2 Inorganic materials 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003542 behavioural effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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- 238000005728 strengthening Methods 0.000 description 1
- 210000000106 sweat gland Anatomy 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGWLTJRQYVEDMR-UHFFFAOYSA-F tetramagnesium;tetracarbonate Chemical compound [Mg+2].[Mg+2].[Mg+2].[Mg+2].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O OGWLTJRQYVEDMR-UHFFFAOYSA-F 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention relates to a biomimetic self-healing phase-change heat-absorption A1 microcapsule/ceramic-base composite heat-proof material and a preparation method thereof, and belongs to the high temperature resistance enhanced ceramic-base biomimetic-function composite material of a microcapsule with low melting point metal Al coated by a thin ceramic shell and a preparation method thereof. Thewall of the A1 microcapsule - the high temperature resistant thin ceramic shell can maintain the shape of the A1 microcapsule at a normal temperature and a high temperature; the low melting point metal Al core has the effect of self-healing similar to the effect that blood forms a scab to enclose the wound, and has the effects of phase-change heat absorption and temperature reduction similar to the effect that sweat is volatilized to reduce the temperature. The A1 microcapsule can be formed by pre-oxidizing commercial aluminum or other alloy powder and liquid-phase cladding or oxidizing in situ during the sintering process, and the composite material is molded through conventional cold pressing and pressure-less sintering or hot pressing sintering. The enhanced ceramic-base high-temperature self-healing composite material of the prepared A1 microcapsule has the advantages of light weight, strong toughness, self healing and phase-change heat absorption, thereby being used as the thermal protection material for aviation and related industries.
Description
Technical field
The present invention relates to a kind of decalescence, high temperature self-healing Al microcapsule that the reusable elevated temperature heat protective material of aerospace field uses and strengthen high temperature resistant compound heat insulation material of ceramic base and preparation method thereof.
Background of invention
The flight environment of vehicle situation that reenters of spacecraft is very extreme and harsh.Bore at least 15 minutes, temperature is returned up to the environmental test of 2000K smoothly, and the thermal protection system of spacecraft has been proposed strict more requirement.Yet existing multiple factor might damage the heat insulation material structure.The ice cube that falls when the for example collision in terrestrial operation, spacecraft emission or bump of other objects and micrometeor in the space and space junk or the like all can cause the heat insulation material structure is damaged.Under extremely abominable spacecraft reentry environment, even atomic little crack in the thermal protection struc ture or hole all can cause the inefficacy of whole heat-protection system, and then cause huge disaster and loss.On February 1st, 2003, U.S.'s shuttle Columbia has an accident in the Returning ball process, and all crews are all wrecked, makes whole world shock.And " arch-criminal " that cause this disaster the place in the space shuttle left wing windward side thermal protection struc ture is damaged just.Thereafter, NASA and European Aeronautics and Space Administration have successively carried out the research of bionical self-healing material and mechanism.
In many kind materials, the crackle self-healing progress of polymer matrix composites is the fastest.The crackle self-healing of polymer matrix composites research at present is about to store the s-generation self-healing structural research stage that the first-generation self-healing structure of repairing medium and solidifying agent gets into imitation capillary vessel clump in advance from microcapsule, hollow fiber, and the research of polymer matrix composites s-generation self-healing structure has begun to start.
The self-healing behavior of ceramic matric composite and polymer matrix composites a great difference arranged.At first, the service temperature of ceramic matric composite is far above polymer matrix composites; Secondly, the reparation medium in the resin base self-healing material needs and solidifying agent meets crosslinking curing could take place and self-healing, and ceramic self-healing often realizes through the high temperature oxidation of some active ingredient wherein; And the ceramic matric composite preparation temperature is high, and the preparation difficulty is big.Thereby crackle high temperature self-healing research lags far behind the resin base self-healing material in the stupalith both at home and abroad, still is in the starting stage at present.Current stupalith self-healing few in number research also more to be confined in strengthening carbon-carbon composite, add SiC, B4C and MoSi2 micro-nano granules; Form SiO2 through the micro-nano granules oxidation and wait to heal and strengthen the tiny crack in the carbon carbon material, and among the TiC/Si3N4, Mullite/ZrO2/SiCp diphase ceramic material because the caused crack healing behavioral study of micro-nano granules.Still there is not the report that the first-generation, s-generation self-healing structure applications are used in the stupalith, particularly ceramic base thermally protective materials.Increasingly mature along with the emission successively of China divine boat series space shuttle and manned spaceflight technology in recent years; Repeated use of realization spacecraft and guarantee spacecraft and cosmonaut's safety are returned, and the applied research in comprising the ceramic base thermally protective materials of rigid foams ceramic insulation tile of self-healing structure seems particularly urgent.
Summary of the invention
The present invention is directed to the harsh requirement that the reusable elevated temperature heat protective material of aerospace field is used; Propose a kind of molten o'clock decalescence Al microcapsule of aluminium that are applicable to and strengthen the compound heat insulation material of ceramic base high temperature self-healing, and its preparation method is provided to 1400 ℃ of TRs.
The compound heat insulation material of a kind of bionical self-healing decalescence Al microcapsule/ceramic base; Its spy is characterised in that: comprise ceramic matrix and be evenly distributed on the ceramic shell coating Al microcapsule in the ceramic matrix; Wherein ceramic shell coats the Al microcapsule diameter less than 80 μ m, and its volume parts accounts for the 5%-70% of sintered compact.
Above-mentioned pottery is one or more mixture in dystectic oxide compound, boride, silicide, carbide, the nitride basically.Its material of Al nuclear that above-mentioned ceramic shell coats in the Al microcapsule is fine aluminium or duraluminum.The outer ceramic shell material that coats of above-mentioned Al microcapsule is alumina-based ceramic or other oxide ceramics, and chemicalstability is good in sintering process and between the matrix pottery, and its shell thickness is 0.1-10 μ m.
The principle explanation: the self-healing function of the compound heat insulation material of bionical self-healing decalescence Al microcapsule/ceramic base is realized through following mechanism.Dissolve o'clock under 1400 ℃ hot environment at aluminium; Micro-crack extension in the ceramic matrix is in the Al microcapsule wall; And cause the Al microcapsules rupture; The Al metal core of high temperature melting is overflowed the microcapsule wall at Al---and the cracks in the ceramic shell contacts with oxygen, high temperature oxidation takes place directly generate fine and close alumina-based ceramic and form a scab mutually and cover crackle " wound ".
The decalescence function of the compound heat insulation material of bionical self-healing decalescence Al microcapsule/ceramic base realizes through following mechanism.The heat absorption in a large number in melting process of lower melting point Al nuclear in high-temperature pottery sheath, the temperature of ceramic matrix in the reduction system promptly has the function of the decalescence of sweat volatilization cooling in the similar sweat gland.The density that this matrix material can also be regulated material through the ratio of regulating Al, and the Al microcapsule can also improve the low-temperature flexibility of material greatly.This matrix material has possessed characteristics such as lightweight, tough, self-healing, decalescence.The thermally protective materials that can be used as aerospace and related industries.
The Al microcapsule diameter that ceramic shell coats in the matrix material material must not be greater than 80 μ m, and the volume parts that accounts for sintered compact must not be greater than 70%, otherwise can cause the reduction of matrix material comprehensive mechanical performance.In the matrix material its Al microcapsule volume parts account for sintered compact must not be less than 5%, otherwise self-healing and decalescence effect are not remarkable.The outer ceramic shell thickness that coats of Al microcapsule is 0.1-10 μ m, crosses to approach at sintering and in high temperature military service process the unexpected damaged of Al microcapsule pottery shell can take place; If thickness can cause Al microcapsule pottery shell disruptive to be postponed greater than 10 μ m, influence the timely healing of crackle.
Method 1: the preparation method of the compound heat insulation material of a kind of bionical self-healing decalescence Al microcapsule/ceramic base is characterized in that detailed process is following:
(1), preoxidation prepares ceramic shell coating Al microcapsule, detailed process:
Aluminium powder preoxidation: 200 orders sieve through being not less than, after the cleaning, suction filtration, oven dry, in oxidizing atmosphere, be heated to 800～1100 ℃ with aluminium powder, are incubated 0.5～5 hour, then directly form Al2O3 base thin layers of ceramic at the Al powder surface;
(2), ceramic shell that step (1) is made coats after Al microcapsule and ceramic matrix powder raw material and shaping assistant, sintering aid mix mutually, briquetting, sintering, its volume parts of Al microcapsule of wherein ceramic shell coating accounts for the 5%-70% of sintered compact.Above-mentioned sintering process is a normal pressure-sintered or hot pressed sintering in the atmosphere.
Method 2: the preparation method of the compound heat insulation material of a kind of bionical self-healing decalescence Al microcapsule/ceramic base is characterized in that comprising following process:
(1), sol-gel method prepares ceramic shell coating Al microcapsule, detailed process:
With aluminium or its alloy powder 200 orders sieve through being not less than, after the cleaning, suction filtration, oven dry; Add zero(ppm) water; And carry out ultrasonic dispersing, and adopt sol-gel method oxide coated ceramic shell on aluminium powder, filter then, clean; Oven dry just makes the oxide ceramics shell through 200-500 ℃ of thermal treatment again and coats Al microcapsule powder;
(2), the oxide ceramics shell that step (1) is made coats after Al microcapsule and ceramic matrix powder raw material and shaping assistant, sintering aid mix mutually; Briquetting, sintering, its volume parts of Al microcapsule that wherein ceramic shell coats accounts for the 5%-70% of sintered compact.
Sol-gel method is to prepare inorganic material film at present to use wider a kind of method, because its production cost is low, temperature required during plated film is also lower.Its principle is to be the colloidal sol of raw material system with suitable inorganic salt or organic salt, is coated in matrix surface, through hydrolysis and polycondensation etc. in substrate surface gelling film forming, again through dry, calcining and sintering acquisition surface film.Sol-gel method generally comprises by following steps to be formed: metal inorganic salt or alkoxide solution preparation; Substrate surface cleans; Form liquid film on the base material; The gelation of liquid film; Xerogel is converted into sull.
Different with above-mentioned direct oxidation method, its material of ceramic shell that sol-gel method prepares ceramic shell coating Al microcapsule can be the wherein a kind of and mixture between them of aluminum oxide, silicon oxide, titanium oxide, zirconium white or Natural manganese dioxide.Used identical in the preparation raw material of the used colloidal sol of above-mentioned materials sol-gel cladding process process and formulation parameter and commercial at present sol-gel method optics, ferroelectric function and the corrosion prevention thin film coated technological process.
Method 3: the preparation method of the compound heat insulation material of a kind of bionical self-healing decalescence Al microcapsule/ceramic base is characterized in that comprising following process:
(1), 200 orders sieve through being not less than, cleaning, suction filtration, oven dry with aluminium powder;
(2), the aluminium after step (1) handled or its alloy powder be with after Mg (NO3) 2, ceramic matrix powder raw material, shaping assistant, sintering aid mix mutually, briquetting, sintering; Wherein Mg (NO3) 2 with the mass ratio of aluminium or its alloy powder is: 1/40-1/4; Wherein the long-pending umber of Al powder accounts for the 5%-70% of sintered compact.
The in-situ oxidation method forms the mechanism of Al microcapsule: in sintering process, the multiple low-temperature that in 300～500 ℃ TR, takes place of magnesium nitrate decomposes, and forms the active MgO particulate, and the O that discharges
2With NO or NO
2, the Al powder can generate Al at the powder surface in-situ oxidation in this strong oxidizing property atmosphere
2O
3Shell, thus Al formed
2O
3The Al microcapsule that shell coats.
Description of drawings:
Fig. 1 is that decalescence Al microcapsule strengthen the tiny crack synoptic diagram in ceramic base high temperature self-healing matrix material and the high temperature healing ceramic matrix thereof; Wherein (a) and (b) with (c) be respectively crack initiation; The Al of high-temperature fusion overflows the filling tiny crack, and tiny crack is made in fusion Al high temperature oxidation incrustation self-healing up.
Label title among the figure: 1, ceramic matrix, 2, ceramic shell coats the Al microcapsule, 3, the Al of high-temperature fusion, 4, crackle, 5, the crackle after Al oxidation incrustation self-healing.
Embodiment:
Instance 1: preoxidation
Select commercial 6101 duraluminum powders for use, its staple is silicon 0.3-0.7%, and the maximum level 0.5% of magnesium 0.35-0.8% and iron is gone back amount and is 0.1% and just or less than 0.1% element comprises copper, zinc, boron, manganese and chromium.
Aluminium powder is sieved, confirms the aluminium powder particle diameter between the 300-350 order, then with aluminium powder with alcohol wash, suction filtration, oven dry, at 900 ℃, be incubated 1 hour and carry out preoxidation, form the Al microcapsule that ceramic shell coats.
The Al microcapsule that alumina substrate powder, magnesium basic carbonate sintering agent, ceramic shell coat are prepared raw material by 90%4%, 6% percent by volume ratio; Adopt the alumina balls mixing and ball milling, the ball milling time is 2 hours, the mixed powder material 25MPa compression molding in the mould of packing into behind the ball milling, and normal pressure-sintered in the atmosphere, temperature rise rate is 10 ℃/min, 1500 ℃ of sintering temperatures, soaking time are 60 minutes.The Al microcapsule that make/Al2O3 high temperature self-healing ceramic matric composite high temperature healing properties is good.
Instance 2: coating method
1) aluminium powder cleans, aluminium powder crosses the 400-425 mesh sieve, then with aluminium powder with alcohol/acetone, suction filtration, oven dry, it is 10% dilute suspension that adding zero(ppm) water is made into massfraction, and carries out ultrasonic dispersing.
2) be heated to predetermined temperature after, the liquor alumini chloridi with 20g/L in specific time slowly joins in the suspension-s, simultaneously dropping ammonia is to keep the pH value stabilization of suspension-s.After liquor alumini chloridi adds, 25 ℃ of insulation 2h times.Filter then, clean, 110 ℃ * 12h oven dry, thermal treatment just makes the alumina-coated Al microcapsule powder that mean diameter is about 50 microns through 500 ℃ * 3h again.Aluminum oxide shell mean thickness is about 1.1 microns.
3) batching: the alumina-coated Al microcapsule powder that makes is mixed with alumina-ceramic matrix powder raw material and shaping assistant, sintering aid in proportion mutually;
4) briquetting: with the 25MPa compression molding in the mould of packing into of middle mixed powder material;
5) sintering: the moulding powder is normal pressure-sintered in atmosphere, 1400 ℃ of insulations of sintering temperature 2 hours, 10 ℃/min of temperature rise rate does not see that in this process Al is wandering.The Al microcapsule that make/Al2O3 high temperature self-healing ceramic matric composite high temperature healing properties is good.
Instance 3: coating method
1) aluminium powder cleans, aluminium powder crosses the 400-425 mesh sieve, then with aluminium powder with alcohol/acetone, suction filtration, oven dry, it is 15% alcohols suspension-s that adding ethanol is made into massfraction, and carries out ultrasonic dispersing.
2) can get optimal conditions: TEOS: C2H5OH: H2O: NH3=1 by teos hydrolysis: 10: 4: 1 (mol ratio), the preparation silica sol adds ethanamide as additive in reaction process, and temperature of reaction is 20 ℃, and the reaction times is 5h.
3) with suspension filtered, cleaning, 110 ℃ * 12h oven dry, thermal treatment just makes alumina-coated Al microcapsule powder through 500 ℃ * 3h again.
3) batching: with the Al microcapsule powder that makes by 30: 60: 4: 6 volume ratio, mix mutually with silicon oxide ceramics matrix powder raw material and shaping assistant, sintering aid.
4) briquetting: with the 25MPa compression molding in the mould of packing into of middle mixed powder material;
5) sintering: the moulding powder is normal pressure-sintered in atmosphere, 1400 ℃ of insulations of sintering temperature 2 hours, 10 ℃/min of temperature rise rate does not see that in this process Al is wandering.The Al microcapsule that make/SiO2 high temperature self-healing ceramic matric composite high temperature healing properties is good.
What embodiment 3,4 adopted is sol-gel method oxide coated ceramic shell on aluminium powder.This invention is: 200 orders sieve through being not less than, after the cleaning, suction filtration, oven dry, add zero(ppm) water and tensio-active agent with aluminium powder,, ultrasonic dispersing is made into dilute suspension; With itself and inorganic salt or organic salt is that the colloidal sol of raw material system mixes, and colloidal sol is incubated 0.5-1 hour in substrate surface gelling film forming; Then with suspension filtered, and clean, oven dry, just make alumina-coated Al microcapsule powder through 300-500 ℃ of thermal treatment again.
Instance 4: in-situ oxidation method
With aluminum oxide, magnesium nitrate, mean diameter be 15 microns Al micro mist by 75%, 5%, 20%, volume percent batch mixing briquetting.Atmosphere pressureless sintering parameter is 8 ℃/min of temperature rise rate, 450 ℃ of insulations original position preoxidation in 4 hours, 1400 ℃ of insulations of sintering temperature 2 hours.The ceramic case of in-situ oxidation gained Al microcapsule is aluminum oxide and magnesian mixed structure, and mean thickness is 0.8 micron.The Al microcapsule that make/Al2O3 high temperature self-healing ceramic matric composite high temperature healing properties is good.
Above-mentioned decalescence Al microcapsule enhancing ceramic base high temperature self-healing matrix material of the present invention and four preparation embodiments thereof enumerated; But self-healing matrix material proposed by the invention and above-mentioned embodiment all can only be thought can not limit the present invention to explanation of the present invention, and claims have been pointed out scope of the present invention.Therefore, under the situation of not violating the invention basic thought,, all should think to belong to protection scope of the present invention as long as adopt the ceramic heat insulation material of Al microcapsule self-healing structure.
Claims (8)
1. compound heat insulation material of bionical self-healing decalescence Al microcapsule/ceramic base; It is characterized in that: comprise ceramic matrix (1) and be evenly distributed on the ceramic shell coating Al microcapsule (2) in the ceramic matrix; Wherein ceramic shell coats Al microcapsule (2) diameter less than 80 μ m; Its volume parts accounts for the 5%-70% of sintered compact, and the outer ceramic shell thickness that coats of Al microcapsule is 0.1-10 μ m.
2. the compound heat insulation material of the bionical self-healing decalescence of Al according to claim 1 Al microcapsule/ceramic base is characterized in that: said pottery basic (1) is one or more a mixture in dystectic oxide compound, boride, silicide, carbide, the nitride.
3. the compound heat insulation material of the bionical self-healing decalescence of Al according to claim 1 Al microcapsule/ceramic base is characterized in that: its material of Al nuclear that said ceramic shell coats in the Al microcapsule (2) is fine aluminium or duraluminum.
4. the compound heat insulation material of the bionical self-healing decalescence of Al according to claim 1 Al microcapsule/ceramic base; It is characterized in that: the outer ceramic shell material that coats of said Al microcapsule is alumina-based ceramic or other oxide ceramics or their mixture; And chemicalstability is good in sintering process and between the matrix pottery, and its shell thickness is 0.1-10 μ m.
5. the preparation method of the compound heat insulation material of bionical self-healing decalescence Al microcapsule/ceramic base is characterized in that detailed process is following:
(1), preoxidation prepares ceramic shell coating Al microcapsule, detailed process:
200 orders sieve through being not less than, after the cleaning, suction filtration, oven dry, in oxidizing atmosphere, be heated to 800～1100 ℃ with aluminium or its alloy powder, are incubated 0.5～5 hour, then directly form Al2O3 base thin layers of ceramic at the Al powder surface;
(2), the ceramic shell that step (1) is made coats after Al microcapsule and ceramic matrix powder raw material and shaping assistant, sintering aid mix mutually; Briquetting, sintering; Wherein ceramic shell coats Al microcapsule (2) diameter less than 80 μ m; Its volume parts accounts for the 5%-70% of sintered compact, and the outer ceramic shell thickness that coats of Al microcapsule is 0.1-10 μ m.
6. the preparation method of the compound heat insulation material of bionical self-healing decalescence Al microcapsule/ceramic base according to claim 5, it is characterized in that: sintering process described in (2) step is a normal pressure-sintered or hot pressed sintering in the atmosphere.
7. the preparation method of the compound heat insulation material of bionical self-healing decalescence Al microcapsule/ceramic base is characterized in that comprising following process:
(1), sol-gel method prepares ceramic shell coating Al microcapsule, detailed process:
With aluminium or its alloy powder 200 orders sieve through being not less than, after the cleaning, suction filtration, oven dry; Add zero(ppm) water; And carry out ultrasonic dispersing, and adopt sol-gel method oxide coated ceramic shell on aluminium powder, filter then, clean; Oven dry just makes the oxide ceramics shell through 200-500 ℃ of thermal treatment again and coats Al microcapsule powder;
(2), the oxide ceramics shell that step (1) is made coats after Al microcapsule and ceramic matrix powder raw material and shaping assistant, sintering aid mix mutually; Briquetting, sintering; Al microcapsule (2) diameter that wherein ceramic shell coats is less than 80 μ m; Its volume parts accounts for the 5%-70% of sintered compact, and the outer ceramic shell thickness that coats of Al microcapsule is 0.1-10 μ m.
8. the preparation method of the compound heat insulation material of bionical self-healing decalescence Al microcapsule/ceramic base is characterized in that comprising following process:
(1), 200 orders sieve through being not less than, cleaning, suction filtration, oven dry with aluminium or its alloy powder;
(2), the aluminium after step (1) handled or its alloy powder be with after Mg (NO3) 2, ceramic matrix powder raw material, shaping assistant, sintering aid mix mutually, briquetting, sintering; Wherein Mg (NO3) 2 with the mass ratio of aluminium or its alloy powder is: 1/40-1/4; Wherein the long-pending umber of Al powder accounts for the 5%-70% of sintered compact.
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| CN103739287B (en) * | 2013-12-29 | 2015-03-04 | 吉林大学 | Preparation method of bionic erosion-resisting composite material enhanced phase based on rose willow |
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| CN111196735B (en) * | 2020-01-20 | 2021-12-21 | 武汉科技大学 | Phase-change heat-storage self-flow type refractory castable and preparation method thereof |
| CN111718692A (en) * | 2020-07-04 | 2020-09-29 | 山西潞安矿业(集团)有限责任公司 | High-temperature composite phase change heat storage material with multi-core shell structure, preparation method and application thereof |
| CN111944491B (en) * | 2020-08-21 | 2022-04-01 | 中国矿业大学 | Preparation method and application of metal phase change microcapsule heat storage particles |
| CN113414082A (en) * | 2021-05-07 | 2021-09-21 | 龚海军 | Preparation process of high-barrier-property nano coating layer on surface of wood |
| CN116005056A (en) * | 2022-12-06 | 2023-04-25 | 宁波大学 | Ceramic-based metal microcapsule/organic phase change composite material and preparation method thereof |
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