CN105732005B - Flexible perovskite thermal control film and preparation method thereof - Google Patents
Flexible perovskite thermal control film and preparation method thereof Download PDFInfo
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- CN105732005B CN105732005B CN201610036562.0A CN201610036562A CN105732005B CN 105732005 B CN105732005 B CN 105732005B CN 201610036562 A CN201610036562 A CN 201610036562A CN 105732005 B CN105732005 B CN 105732005B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 17
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 10
- 239000000758 substrate Substances 0.000 claims abstract description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001723 curing Methods 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000010409 thin film Substances 0.000 claims description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 17
- 238000009413 insulation Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000010408 film Substances 0.000 claims description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 11
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 10
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000000137 annealing Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 6
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 6
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000015110 jellies Nutrition 0.000 claims description 4
- 239000008274 jelly Substances 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000007711 solidification Methods 0.000 claims description 4
- 230000008023 solidification Effects 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- -1 wherein Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 6
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052779 Neodymium Inorganic materials 0.000 abstract description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 229910052746 lanthanum Inorganic materials 0.000 abstract description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 abstract description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 2
- 239000011224 oxide ceramic Substances 0.000 abstract description 2
- 229910052712 strontium Inorganic materials 0.000 abstract description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 abstract description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 235000015165 citric acid Nutrition 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000002604 ultrasonography Methods 0.000 description 3
- 239000011240 wet gel Substances 0.000 description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000001360 synchronised effect Effects 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 1
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910004416 SrxMnO3 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JTCFNJXQEFODHE-UHFFFAOYSA-N [Ca].[Ti] Chemical compound [Ca].[Ti] JTCFNJXQEFODHE-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 229910000077 silane Inorganic materials 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- C04B35/016—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 manganites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3213—Strontium oxides or oxide-forming salts thereof
-
- 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
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
- C04B2235/3227—Lanthanum oxide or oxide-forming salts thereof
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
The invention discloses a flexible perovskite thermal control film and a preparation method thereof, wherein precursor powder of manganese, strontium, neodymium and lanthanum is modified by 3-aminopropyltriethoxysilane to obtain perovskite powder, then 4, 4' -diaminodiphenyl ether and the perovskite powder are added into dimethylacetamide at the temperature of-10-0 ℃, pyromellitic dianhydride is added while ultrasonic stirring is carried out, and after rapid stirring, vacuum pumping is carried out to obtain sol; transferring the obtained sol to a substrate material, and obtaining a cured film by a stepped heating curing method; the invention adopts 4, 4' -diaminodiphenyl ether and pyromellitic dianhydride as base materials, improves the emissivity of the perovskite-based flexible film in a high-temperature area by 8 percent, overcomes the implementation defect of a manganese oxide ceramic sheet and the problem of low yield caused by the brittleness of the ceramic sheet, and has the advantages of simple manufacturing process, easy control of the thickness of the film, no limitation on the specification of a test piece, easy mass production and large-area use.
Description
Technical field
The present invention relates to a kind of flexible perovskite heat controlled thin film and preparation method thereof, belong to heat radiation control technology field.
Background technology
There is the rare earth manganese oxide material for adulterating divalent alkaline-earth metal element thermic to change radiation characteristic.Suitably mixing
Under miscellaneous concentration conditions, Mn oxide material attribute varies with temperature generation ferromagnetic metal state-paramagnetic insulation state transformation and presents only
Special optics, electricity and magnetism characteristic, and itself radiation characteristic can be adjusted according to the temperature levels of system and equipment, control
System processed is exchanged with the emittance between equipment and external environment, is realized control and management to system and device temperature, is made
It has broad application prospects in national economy and national defence.In spacecraft thermal control technical field, using Mn oxide
The thermochromic properties that emissivity varies with temperature are realized and spacecraft surface temperature are automatically controlled.When spacecraft temperature raises
When, for the emissivity increase of the Mn oxide material on its surface, so as to by unnecessary heat dissipation to the outer space；And when boat
When its device handles cold environment, surface temperature drastically reduces, and the emissivity of its Mn oxide material used also correspondingly reduces, so that
Realize without the loss that spacecraft internal heat is prevented under the conditions of auxiliary device.Because it without additional auxiliary device has and efficiently may be used
The advantage leaned on.The application mode of current this material is mainly that the material is processed into the ceramic sheet (rule of submillimeter level thickness
Lattice are 40 × 40 × 0.3mm) and paste on corresponding base material, its process is comparatively laborious, and yield rate is relatively low；Secondly, sample
Product cause excessive spillage of material when processing flakiness, and stock utilization is relatively low；There is the characteristics of because of ceramic sheet poor toughness again, lead
Cause ceramic sheet thickness is thinner, its mechanical performance is poorer；Finally, when ceramic sheet is pasted in substrate, the company between thin slice
There are larger gap at the place of connecing so that material is difficult to large-area applications, and this thin slice can not be applied to complex-shaped component
Surface.
The content of the invention
In consideration of it, the present invention provides a kind of flexible perovskite heat controlled thin film and preparation method thereof, Mn oxide pottery is overcome
The defects of porcelain thin slice, solve the low temperature preparation problem of perovskite heat controlled thin film, expands the big face of Mn oxide heat control material
Product application and complex component surface applications, improve the utilization rate of material.
The technical scheme is that：A kind of flexibility perovskite heat controlled thin film and preparation method thereof, concretely comprises the following steps：
A. manganese nitrate, strontium nitrate, neodymium nitrate, lanthanum nitrate are made into certain density precursor solution, are placed in 60-80 DEG C of water
Heating stirring in bath；
B. citric acid and ethylene glycol are added in precursor solution, continues stirring to obtain presoma jelly, wherein, lemon
Sour quality is 0.8-1.15 times of metal ion, and the ratio of the metal ion in ethylene glycol and precursor solution is 10-15：
1ml/mol；
C. jelly step b obtained passes through low temperature calcination, and high annealing, grinding obtain particle diameter as 100~500 nanometers
Precursor powder, wherein, calcining heat is 400 DEG C~550 DEG C, and calcination time be 2.5h~4h, annealing temperature is 750 DEG C~
1000 DEG C, annealing time is 5h~10h；
D, three ethoxy of precursor powder and 3- aminopropyls that step c is obtained is added into the ethanol solution that concentration is 90wt%
Base silane, at a temperature of 20 DEG C~30 DEG C stirring 1~3 it is small when, be warming up to 65 DEG C~70 DEG C be stirred for 1~3 it is small when, through anhydrous second
After alcohol cleaning, it is dried in vacuo at 50 DEG C~60 DEG C and obtains perovskite powders, wherein, the 3- aminopropyl triethoxysilanes are
The 1.5~3% of perovskite powders quality；
E, under -10~0 DEG C of environment, add in 4,4 '-diaminodiphenyl ether and step d and obtain into dimethylacetylamide
Perovskite powders, first ultrasound 10~30 minutes, interior addition pyromellitic acid anhydride when 2~4 is small while stirring, with more than
After when quick stirring 1~2 is small under the mixing speed of 1000r/min, vacuumize 1~10 it is small when, obtain perovskite thin film colloidal sol；Its
In, 4, the mass ratio of 4 '-diaminodiphenyl ether and perovskite powders is 1：(0.74~6), 4,4 '-diaminodiphenyl ether and diformazan
The mass ratio of yl acetamide is 1：(8.4~19), the mass ratio of the dimethylacetylamide and pyromellitic acid anhydride is (7.6
~17.2)：1；
F, the perovskite thin film colloidal sol obtained in step e is transferred on substrate material, ladder-elevating temperature solidification method is consolidated
Change film；Wherein, the ladder-elevating temperature solidification method is from room temperature to 70 ± 5 DEG C, keeps the temperature 3h-6h, then 120 ± 5 DEG C successively
2h is kept the temperature, 180 ± 5 DEG C of insulation 2h, after 240 ± 5 DEG C keep the temperature 2h, and 290 ± 5 DEG C of insulation 2h, are cooled to room temperature.
In step a, the molar ratio of the lanthanum nitrate and manganese nitrate is (0.15~0.5)：1, neodymium nitrate and manganese nitrate rub
Your ratio is (0.15~0.55)：1, the molar ratio of strontium nitrate and manganese nitrate is (0.3~0.35)：1.
In step f, heating rate and cooldown rate are 3 DEG C/min.
Compared with prior art, beneficial effects of the present invention are：
1. contained neodymium rare-earth salts realizes the quick change of emissivity in the perovskite of the present invention.
2. the present invention uses 4,4 '-diaminodiphenyl ether and pyromellitic dianhydride are basis material, make perovskite-based flexibility
The high-temperature region emissivity of film improves 8%.
3. the present invention overcomes the defects of the implementation of Mn oxide ceramic sheet, overcoming ceramic sheet brittleness causes yield rate
The problem of low.
4. manufacture craft of the present invention is simple, film thickness is easily controllable, unrestricted to specimen size, is easy to scale metaplasia
Production, large area use, and have very big actual application value.
Brief description of the drawings
Fig. 1 is the preparation method flow chart of flexible perovskite heat controlled thin film of the invention.
Fig. 2 is the Main elements analysis figure and displaing micro picture of the hot powder of property perovskite of the present invention.
Embodiment
It is below for embodiments of the present invention and specifically real in order to make narration in the present disclosure more detailed with complete
The description of illustrating property of example is applied, wherein attached drawing 1 is synthesis technique flow of the invention.
Embodiment 1
Step 1: 20 grams of nitric acid are added in 70ml deionized waters, after being stirred at room temperature uniformly, 21.65 grams are sequentially added
Lanthanum nitrate, 39.45 grams of neodymium nitrates, 12.7 grams of strontium nitrates, the manganese nitrate of 71.58 grams of 50wt%, by temperature be increased to 65 DEG C and with
When 510r/min speed stirring 2.5 is small, 0.48mol citric acids are added, and continue to form colloidal sol when stirring 3 is small, add 11ml second
Glycol, continue under synchronized equality of temperature stirring 5 it is small when, stand at 65 DEG C 12 it is small when, obtain wet gel.It is placed on wet solidifying in high temperature furnace
Glue with the speed of 3.3 DEG C/min be increased to 420 DEG C insulation 3 it is small when removing glue after, with 5 DEG C/min be warming up to 750 DEG C insulation 5 it is small when,
Room temperature is cooled to 3.3 DEG C/min speed.Ground or ball milling obtains the perovskite powders that particle diameter is 150 nanometers, is shown in Fig. 2
In the present embodiment perovskite powders main components be neodymium, strontium, manganese, lanthanum.
Step 2: 10 grams of perovskite powders in step 1 are added into the concentration containing 0.15 gram of 3- aminopropyl triethoxysilane
In 90% ethanol solution, at 25 DEG C with 305r/min speed stirring 1.5 it is small when after, ethanol eccentric cleaning 4 times, at 50 DEG C
Vacuum drying obtains modified perovskite powder.
Step 3: 1 gram of 4,4 '-diaminodiphenyl ether and 0.74 gram of step 2 are added into 11.91 grams of dimethylacetylamides
In obtained perovskite powders, successively with the frequency ultrasound 10 minutes of 70KHz, it is small with the speed stirring 2.5 of 305r/min when into
Row it is dispersed, add 1.103 grams of pyromellitic acid anhydrides, at -5 DEG C with 1000r/min speed quickly stirring 1 it is small when after,
Vacuumize 8 it is small when, obtain perovskite thin film colloidal sol.
Step 4: the calcium titanium film colloidal sol in step 3 is transferred on flexible PI films substrate, ladder-elevating temperature curing process
Obtain cured film.The ladder-elevating temperature curing process is using 3 DEG C/min as the rate of temperature fall that heats up is cured, and setting successively cures temperature
When degree and soaking time are that 70 DEG C of insulations 6 are small, when 120 DEG C of insulations 1.5 are small, when 180 DEG C of insulations 1.5 are small, 240 DEG C of insulations 1.5 are small
When, when 290 DEG C of insulations 1.5 are small, after being cooled to room temperature, gained cured film is flexible perovskite heat controlled thin film.
A kind of flexible perovskite heat controlled thin film and preparation method thereof is present embodiments provided, using the perovskite powders containing neodymium
Heat controlled thin film phase transition temperature is basis material using 4,4 '-diaminodiphenyl ether and pyromellitic dianhydride, by calcium near room temperature
The emissivity of titanium ore heat controlled thin film high temperature section brings up to 0.88, with the prior art (Shen X, Xu G, Shao C, et
al.Temperature dependence of infrared emissivity of doped manganese oxides in
different wavebands(3–5and 8–14μm)[J].Journal of Alloys and Compounds,2009,
479(1):420-422) to Lal-xSrxMnO3(0.1≤x≤0.5) is compared, and emissivity improves 8%.
Embodiment 2
First three step of the present embodiment is same as Example 1, rises from all around from step different.
The step 4 is：It is hard not less than 300 DEG C that the perovskite thin film colloidal sol obtained in step 3 is transferred to heatproof
On matter substrate, such as：Glass, silicon chip.Ladder-elevating temperature curing process obtains cured film as described in the step four in embodiment 1, will
Cured film is peeled off from hard substrates in 70 DEG C of ethanol or ethanol water, is thin up to flexible perovskite thermal control after drying
Film, emissivity of the film in temperature 203K and 353K are respectively 0.45 and 0.75, and emissivity amplitude of variation is 0.3.
Embodiment 3
The present embodiment and the difference of embodiment 1 are step 1.
The step 1 is：20 grams of nitric acid are added in 70ml deionized waters, after being stirred at room temperature uniformly, are sequentially added
34.64 grams of lanthanum nitrates, 26.3 grams of neodymium nitrates, 12.7 grams of strontium nitrates, the manganese nitrate of 71.58 grams of 50wt%, 65 are increased to by temperature
DEG C and with 850r/min speed stirring 3 it is small when, add 0.48mol citric acids, and continue stirring 4 it is small when form colloidal sol, add
15ml ethylene glycol, continue under synchronized equality of temperature stirring 5 it is small when, stand at 65 DEG C 12 it is small when, obtain wet gel.It is placed in high temperature furnace
Wet gel with the speed of 5 DEG C/min be increased to 550 DEG C insulation 3 it is small when removing glue after, with 5 DEG C/min be warming up to 1000 DEG C insulation 10
Hour, room temperature is cooled to 5 DEG C/min speed.Ground or ball milling obtains the perovskite powders that particle diameter is 400 nanometers.
Other steps two with embodiment 1 are to four identical.Emissivity of the gained film in 373K is 0.89.
Embodiment 4
The present embodiment and the difference of embodiment 3 are step 3.
The step 3 is：1 gram of 4,4 '-diaminodiphenyl ether and 6 grams of steps are added into 11.91 grams of dimethylacetylamides
The perovskite powders obtained in two, successively with the frequency ultrasound 20 minutes of 70KHz, it is small with the speed stirring 4 of 400r/min when into
Row it is dispersed, add 1.2 grams of pyromellitic acid anhydrides, at -0.5 DEG C with 1000r/min speed quickly stirring 2 it is small when after,
Vacuumize 10 it is small when, obtain perovskite thin film colloidal sol.
Other steps one with embodiment 3, step 2 and step 4 are identical, and the emissivity of gained film is in 373K
0.87。
Claims (3)
1. a kind of flexibility perovskite heat controlled thin film, it is characterised in that the film is prepared by following steps：
A. manganese nitrate, strontium nitrate, neodymium nitrate, lanthanum nitrate are made into precursor solution, are placed in heating stirring in 60-80 DEG C of water-bath,
Wherein, the molar ratio of the lanthanum nitrate and manganese nitrate is（0.15~0.5）：1, the molar ratio of neodymium nitrate and manganese nitrate is（0.15~
0.55）：1, the molar ratio of strontium nitrate and manganese nitrate is（0.3~0.35）：1；
B. citric acid and ethylene glycol are added in precursor solution, continues stirring to obtain presoma jelly, wherein, citric acid matter
Measure as 0.8-1.15 times of metal ion, the ratio of the metal ion in ethylene glycol and precursor solution is 10-15：1 ml/
mol；
C. jelly low temperature calcination step b obtained, high annealing, grinding obtain the presoma that particle diameter is 100 ~ 500 nanometers
Powder, wherein, calcining heat is 400 DEG C ~ 550 DEG C, and calcination time is 2.5h ~ 4h, and annealing temperature is 750 DEG C ~ 1000 DEG C, annealing
Time is 5h ~ 10h；
D, the precursor powder and 3- aminopropyl-triethoxy silicon that step c is obtained are added into the ethanol solution that concentration is 90wt%
Alkane, at a temperature of 20 DEG C ~ 30 DEG C stirring 1 ~ 3 it is small when, be warming up to 65 DEG C ~ 70 DEG C be stirred for 1 ~ 3 it is small when, through washes of absolute alcohol
Afterwards, vacuum drying obtains perovskite powders at 50 DEG C ~ 60 DEG C, wherein, the 3- aminopropyl triethoxysilanes are perovskite
The 1.5 ~ 3% of powder quality；
E, under -10 ~ 0 DEG C of environment, obtained calcium is added in 4,4 '-diaminodiphenyl ether and step d into dimethylacetylamide
Titanium ore powder, elder generation is 10 ~ 30 minutes ultrasonic, while stirring interior addition pyromellitic acid anhydride when 2 ~ 4 is small, with more than 1000 r/
After when quick stirring 1 ~ 2 is small under the mixing speed of min, vacuumize 1 ~ 10 it is small when, obtain perovskite thin film colloidal sol, wherein, 4,4 '-
The mass ratio of diaminodiphenyl ether and perovskite powders is 1：（0.74~6）, 4,4 '-diaminodiphenyl ether and dimethylacetylamide
Mass ratio be 1：(8.4 ~ 19), the mass ratio of the dimethylacetylamide and pyromellitic acid anhydride are（7.6~17.2）：1；
F, the perovskite thin film colloidal sol obtained in step e is transferred on substrate material, ladder-elevating temperature solidification method obtains curing thin
Film；Wherein, the ladder-elevating temperature solidification method is from room temperature to 70 ± 5 DEG C, keeps the temperature 3h-6h, then 120 ± 5 DEG C of insulations successively
After 2h, 180 ± 5 DEG C of insulations 2h, 240 ± 5 DEG C of insulation 2h, and 290 ± 5 DEG C of insulation 2h, room temperature is cooled to.
2. flexibility perovskite heat controlled thin film as claimed in claim 1, it is characterised in that in step f, heating rate and cooling speed
Rate is 3 DEG C/min.
3. the preparation method of the flexible perovskite heat controlled thin film as described in claim 1-2 is any.
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| CN101457347A (en) * | 2008-12-22 | 2009-06-17 | 中国航天科技集团公司第五研究院第五一○研究所 | Film stress control method |
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| CN101457347A (en) * | 2008-12-22 | 2009-06-17 | 中国航天科技集团公司第五研究院第五一○研究所 | Film stress control method |
| CN102786688A (en) * | 2012-08-06 | 2012-11-21 | 江苏南方贝昇光电材料有限公司 | Preparation method for aureole resistant polyimide film |
| CN103232609A (en) * | 2013-04-25 | 2013-08-07 | 安徽朝日电子新能源有限公司 | Preparation method of coal ash modified nanometer aluminum oxide/polyimide composite film |
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