CN115975453B - Flaky rare earth-based high-radiation heat dissipation coating and preparation method and application thereof - Google Patents
Flaky rare earth-based high-radiation heat dissipation coating and preparation method and application thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 82
- 238000000576 coating method Methods 0.000 title claims abstract description 74
- 239000011248 coating agent Substances 0.000 title claims abstract description 72
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 66
- 230000017525 heat dissipation Effects 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000843 powder Substances 0.000 claims abstract description 54
- 239000000243 solution Substances 0.000 claims abstract description 20
- -1 rare earth chloride Chemical class 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 230000032683 aging Effects 0.000 claims abstract description 8
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 7
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 13
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 13
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 239000011347 resin Substances 0.000 claims description 12
- 229920005989 resin Polymers 0.000 claims description 12
- 239000004576 sand Substances 0.000 claims description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 7
- 239000004925 Acrylic resin Substances 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 6
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002952 polymeric resin Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 229920003002 synthetic resin Polymers 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 2
- 230000005855 radiation Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 24
- 239000000463 material Substances 0.000 description 20
- VLOFLNGRXXADOF-UHFFFAOYSA-N cerium(3+) oxygen(2-) yttrium(3+) Chemical compound [Y+3].[O-2].[Ce+3].[O-2].[O-2] VLOFLNGRXXADOF-UHFFFAOYSA-N 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- XJWBDIIFHAUGDM-UHFFFAOYSA-N [O--].[O--].[O--].[Ce+3].[Sm+3] Chemical compound [O--].[O--].[O--].[Ce+3].[Sm+3] XJWBDIIFHAUGDM-UHFFFAOYSA-N 0.000 description 9
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 9
- 229910021389 graphene Inorganic materials 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 229910052746 lanthanum Inorganic materials 0.000 description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 5
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- ONLCZUHLGCEKRZ-UHFFFAOYSA-N cerium(3+) lanthanum(3+) oxygen(2-) Chemical compound [O--].[O--].[O--].[La+3].[Ce+3] ONLCZUHLGCEKRZ-UHFFFAOYSA-N 0.000 description 4
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- MAMCHKZYNGWYAS-UHFFFAOYSA-N [Sm].[Ce] Chemical compound [Sm].[Ce] MAMCHKZYNGWYAS-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- AZKVWQKMDGGDSV-BCMRRPTOSA-N Genipin Chemical compound COC(=O)C1=CO[C@@H](O)[C@@H]2C(CO)=CC[C@H]12 AZKVWQKMDGGDSV-BCMRRPTOSA-N 0.000 description 2
- 229920000881 Modified starch Polymers 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013530 defoamer Substances 0.000 description 2
- AZKVWQKMDGGDSV-UHFFFAOYSA-N genipin Natural products COC(=O)C1=COC(O)C2C(CO)=CCC12 AZKVWQKMDGGDSV-UHFFFAOYSA-N 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- LENJPRSQISBMDN-UHFFFAOYSA-N [Y].[Ce] Chemical compound [Y].[Ce] LENJPRSQISBMDN-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000006115 industrial coating Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- QVOIJBIQBYRBCF-UHFFFAOYSA-H yttrium(3+);tricarbonate Chemical compound [Y+3].[Y+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O QVOIJBIQBYRBCF-UHFFFAOYSA-H 0.000 description 1
- DEXZEPDUSNRVTN-UHFFFAOYSA-K yttrium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Y+3] DEXZEPDUSNRVTN-UHFFFAOYSA-K 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Abstract
The invention provides a flaky rare earth-based high-radiation heat dissipation coating and a preparation method and application thereof, wherein the raw materials of the coating comprise flaky rare earth powder, and the preparation method of the flaky rare earth powder comprises the following steps: heating a rare earth chloride solution with the pH value of 3-5 and the concentration of 60-100g/L to 40-60 ℃, adding an ammonium bicarbonate solution to prepare a mixed solution, when the pH value of the mixed solution is 6-7, after the reaction is finished, aging, filtering and washing, burning a solid substance, and the burning temperature is above 1000-1200 ℃, thus obtaining a flaky rare earth powder product. The flaky rare earth-based high-radiation heat dissipation coating provided by the invention has the emissivity of 0.97 at an atmospheric window of 8-13 mu m, is extremely close to the absolute blackbody emissivity of 1, provides excellent physical conditions for radiation heat dissipation, and has remarkable heat dissipation effect.
Description
Technical Field
The invention belongs to the field of heat dissipation coatings, and particularly relates to a flaky rare earth-based high-emissivity heat dissipation coating, and a preparation method and application thereof.
Background
At present, graphite or graphene is used as a main material of the heat dissipation coating, and high-heat conductivity fillers such as silicon nitride and silicon carbide are used as auxiliary materials to jointly play a role in heat dissipation, but pure graphene powder in the market is high in price and uneven in quality, the heat dissipation coating is unstable in quality and high in cost, and rare earth with a specific structure is rarely adopted as a main material in the market to manufacture the heat dissipation coating.
Patent CN104359091a discloses a heat-dissipating coating for cooling fins of Led lamps, which uses rare earth oxide, modified corn starch, purple sand, silicon nitride, boron nitride and the like as heat-dissipating materials, but the manufacturing process of the modified corn starch is complex, only the rare earth oxide is added, the material structure is too simple, and the important influence of the rare earth oxide structure on heat dissipation is not mentioned.
Patent CN10324910a discloses a heat-dissipating coating mainly comprising far-infrared ceramic powder, silicon carbide, cerium oxide and the like, but the rare earth addition amount is very small, the effect of rare earth oxide in the coating cannot be fully reflected, and meanwhile, the heat-dissipating test result at medium and low temperature is not ideal.
Patent CN109852235a discloses a nano material composite radiation heat dissipation cooling coating, wherein the double-component heat dissipation coating is mainly processed by adopting high heat conduction wear-resistant ceramic, graphene, nano carbon tube, rare earth oxide and other materials, but the pure graphene has very high market price, complex processing technology, extremely small rare earth oxide addition amount and too simple structure, and no practical experimental data is used for supporting the theory of the coating.
Patent CN114316718A discloses an industrial coating with strong weather resistance and infrared radiation and heat dissipation and a preparation method thereof, wherein rare earth oxide and graphene are adopted as main radiation materials, but the graphene materials are expensive, the production cost is greatly increased, and meanwhile, yttrium oxide is easy to hydrolyze in the water-based coating to generate yttrium hydroxide and yttrium carbonate, so that the instability of the coating is caused. Therefore, the existing heat dissipation coating in the current market has no fully developed effect on rare earth heat dissipation and has poor heat dissipation effect on low and medium temperature.
Disclosure of Invention
In view of the above, the present invention aims to overcome the defects in the prior art, and provides a flaky rare earth-based high-emissivity heat dissipation coating, and a preparation method and application thereof.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a flaky rare earth-based high-radiation heat dissipation coating comprises the following components in percentage by mass:
45-55% of flaky rare earth powder, 0-3% of silicon nitride powder, 15-40% of high polymer resin, 6-10% of solvent and 2-8% of auxiliary agent; the flaky rare earth powder is La x Ce 1-x O 2 、Y x Ce 1-x O 2 、Sm x Ce 1-x O 2 Wherein x = 0.1-0.5;
the preparation method of the flaky rare earth powder comprises the following steps:
heating a rare earth chloride solution with the pH value of 3-5 and the concentration of 60-100g/L to 40-60 ℃, adding an ammonium bicarbonate solution to prepare a mixed solution, when the pH value of the mixed solution is 6-7, after the reaction is finished, aging, filtering and washing, burning a solid substance, and the burning temperature is 1000-1200 ℃, thus obtaining a flaky rare earth powder product.
Preferably, the solute in the rare earth chloride solution comprises one or more of lanthanum chloride, samarium chloride, yttrium chloride and cerium chloride.
Preferably, the molar percentage of cerium chloride in the solute of the rare earth chloride solution is 50% -90%.
Preferably, the polymer resin is one or more of acrylic resin, fluorocarbon resin or organic silicon resin.
Preferably, the solvent is one or more of cyclohexanone, isopropanol, butyl acetate, n-butanol and propyl acetate.
Preferably, the auxiliary agent is one or more of dispersing agent, leveling agent and defoaming agent.
The invention also provides a preparation method of the flaky rare earth-based high-radiation heat dissipation coating, which comprises the following steps:
stirring the flaky rare earth powder, the solvent and the dispersing agent for pre-dispersing, grinding by a sand mill, stirring and mixing the ground slurry, the high polymer resin and the auxiliary agent in a dispersing machine at a high speed until the mixture is uniform, and finally obtaining the rare earth heat-dissipating coating.
Preferably, the particle diameter D90 of the flaky rare earth powder ground by the sand mill in the step is 1.0-3.0 mu m.
The invention also provides application of the flaky rare earth-based high-emissivity heat dissipation coating in heat dissipation products of power electronic equipment, building heat management, photovoltaic equipment and wearing equipment.
Compared with the traditional rare earth oxide, the flaky rare earth powder of the invention adds lanthanum, yttrium and samarium rare earth elements into cerium oxide in a doping way, thereby respectively obtaining lanthanum cerium (La) of flaky structure x Ce 1-x O 2 ) Yttrium cerium oxide (Y) x Ce 1- x O 2 ) Samarium cerium (Sm) x Ce 1-x O 2 ) The rare earth compound (wherein x=0.1-0.5) has higher heat emissivity and better heat conduction efficiency than the conventional rare earth oxide by doping the obtained rare earth compound with a sheet structure.
Compared with the traditional block or spherical structure of rare earth powder, the flaky structure rare earth applied by the invention has better heat radiation rate and larger heat radiation area, and meanwhile, the structure has extremely high heat radiation rate at normal temperature, and can better radiate the heat at medium and low temperature; as the flaky rare earth is adopted as the main material, the coating has stronger mechanical property after being solidified into a film to cope with the plastic and strength change generated after the base material heats. The silicon nitride auxiliary material in the formula not only can improve the heat conductivity of the material, but also can protect rare earth.
Compared with the prior art, the invention has the following advantages:
(1) The flaky rare earth-based high-emissivity heat-dissipation coating provided by the invention has an emissivity of 0.97 (a testing instrument is a dual-band emissivity tester of Shanghai Chengbo photoelectric technology Co., ltd.) at an atmospheric window of 8-13 μm, is extremely close to an absolute blackbody emissivity of 1, provides excellent physical conditions for radiation heat dissipation, and has a remarkable heat dissipation effect.
(2) Compared with the traditional cerium oxide, lanthanum, yttrium and samarium doping, the flaky rare earth powder can form extremely stable compounds for the crystal lattices of the cerium oxide, and improve the heat conductivity and the heat emissivity of the heat dissipation coating, so that the long-term stability of the heat dissipation coating is ensured.
(3) After the film is formed, the rare earth material with the flaky structure can improve the mechanical property of the heat dissipation coating, wherein the flexibility of the coating is implemented according to the national standard GB/T1731-93, and the result is 1 mm, and the flexibility is good; the adhesive force of the coating is implemented according to the national standard GB/T1720-2020, the result is grade 1, the coating is excellent, and when the base material is heated to change the plasticity and strength, the heat-dissipating coating can be better attached to the base material, so that the base material is protected.
(4) The coating has obvious low and medium temperature heat dissipation effect, and the heat dissipation efficiency of the radiator coated with the rare earth heat dissipation coating is improved by 10-20% compared with that of a radiator without the heat dissipation coating for low temperature heat dissipation (0-200 ℃). For medium-temperature heat dissipation (200-600 ℃), the heat dissipation efficiency of the heat dissipation fin coated with the rare earth heat dissipation coating can be improved by 20% -30%.
(5) The flaky rare earth-based high-radiation heat dissipation coating disclosed by the invention is simple and convenient in process, and can greatly save the production time cost; meanwhile, the construction is convenient, and the paint can be sprayed, rolled or dip-coated; meanwhile, the rare earth heat dissipation coating has good ageing resistance, and is implemented according to the national standard GB/T1865-2009, and the artificial climate ageing resistance is more than 2000 hours.
(6) The flaky rare earth-based high-radiation heat dissipation coating can be applied to various fields, such as heat dissipation devices in the electronic industry, and is beneficial to the future development of electronic products; for example, the solar backboard can radiate heat, so that the photovoltaic power generation efficiency can be greatly improved.
Drawings
FIG. 1 is an electron microscope image of a flaky lanthanum cerium oxide powder according to example 1 of the present invention;
FIG. 2 is an XRD pattern of the flaky lanthanum cerium oxide powder according to example 1 of the present invention;
FIG. 3 is an electron microscope image of the flaky samarium cerium oxide powder according to example 2 of the present invention;
FIG. 4 is an XRD pattern of the flaky samarium cerium oxide powder according to example 2 of the present invention;
FIG. 5 is an electron microscope image of a flaky yttrium cerium oxide powder according to example 3 of the present invention;
fig. 6 is an XRD pattern of the flaky yttrium cerium oxide powder according to example 4 of the present invention.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts pertain. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The invention will be described in detail with reference to examples.
Example 1
(1) Preparation of flake lanthanum cerium acid powder La 0.4 Ce 0.6 O 2
Heating a rare earth chloride solution with a pH value of 3.5 and a concentration of 70 g/L to 50 ℃, adding an ammonium bicarbonate solution with a concentration of 160 g/L to prepare a mixed solution, wherein the molar ratio of lanthanum chloride to cerium chloride in the rare earth chloride solution is 2:3, and when the pH value of the mixed solution is 6.5, aging, filtering and washing, and then burning a solid substance to obtain a sheet lanthanum cerium acid powder product at a burning temperature of 1100 ℃. The electron microscope diagram of the prepared flaky lanthanum cerium acid powder product is shown in figure 1, and the XRD diagram is shown in figure 2.
(2) Preparing flaky rare earth-based high-radiation heat dissipation coating
Stirring the flaky lanthanum cerium oxide powder, silicon nitride, cyclohexanone and a dispersing agent prepared in the step (1) for pre-dispersing, grinding by a sand mill, and stirring and mixing the ground slurry, acrylic resin and an auxiliary agent in a dispersing machine at a high speed until the mixture is uniform, thereby obtaining the rare earth heat-dissipating coating. Wherein, the weight percentages of the flaky lanthanum cerium oxide powder, silicon nitride, acrylic resin, cyclohexanone, dispersing agent, leveling agent and defoamer are as follows: 50%, 2%, 30%, 10%, 5%:1.2% and 1.8%.
The paint prepared by the test example of the dual-band emissivity tester of Shanghai Chengbo photoelectric technology science and technology Co is 0.93 in the atmospheric window with the emissivity of 8-13 mu m.
Example 2
(1) Preparation of sheet-shaped samarium cerium acid powder Sm 0.3 Ce 0.7 O 2
Heating a rare earth chloride solution with the pH value of 4 and the concentration of 80g/L to 60 ℃, adding an ammonium bicarbonate solution with the concentration of 150g/L to prepare a mixed solution, wherein the molar ratio of samarium chloride to cerium chloride in the rare earth chloride solution is 3:7, and when the pH value of the mixed solution is 6, after the reaction is finished, aging, filtering and washing, burning a solid substance to obtain a sheet-shaped samarium cerium oxide powder product with the burning temperature of 1150 ℃. The electron microscope diagram of the prepared flaky samarium cerium oxide powder product is shown in figure 3, and the XRD diagram is shown in figure 4.
(2) Preparing flaky rare earth-based high-radiation heat dissipation coating
Stirring the flaky samarium cerium oxide powder prepared in the step (1), butyl acetate and a dispersing agent for pre-dispersing, grinding by a sand mill, and stirring and mixing the ground slurry, fluorocarbon resin and an auxiliary agent in a dispersing machine at a high speed until the mixture is uniform, thereby finally obtaining the rare earth heat-dissipating coating. Wherein, the mass percentages of the flaky samarium cerium oxide powder, fluorocarbon resin, butyl acetate, dispersing agent, leveling agent and defoamer are 55%, 31%, 6%, 5.6%, 1.2% and 1.2% in sequence.
The paint prepared by the test example of the dual-band emissivity tester of Shanghai Chengbo photoelectric technology science and technology Co is 0.95 in the atmospheric window with the emissivity of 8-13 mu m.
Example 3
(1) Preparation of flake Yttrium cerium acid powder Y 0.5 Ce 0.5 O 2
Heating a rare earth chloride solution with the pH value of 4.5 and the concentration of 90g/L to 40 ℃, and then adding an ammonium bicarbonate solution with the concentration of 170 g/L to prepare a mixed solution, wherein the molar ratio of yttrium chloride to cerium chloride in the rare earth chloride solution is 50%:50%, when the pH value of the mixed solution is 7, after the reaction is finished, the solid substances are burned after aging, filtering and washing, and the burning temperature is 1200 ℃, so that the flaky yttrium cerium oxide powder product is obtained. The electron microscope diagram of the obtained flaky yttrium cerium oxide powder product is shown in figure 5, and the XRD diagram is shown in figure 6.
(2) Preparing flaky rare earth-based high-radiation heat dissipation coating
And (3) pre-dispersing the flaky yttrium cerium oxide powder, silicon nitride powder, isopropanol dispersant and stirring, grinding by a sand mill, and stirring and mixing the ground slurry, the organic silicon resin and the auxiliary agent in a dispersing machine at a high speed until the mixture is uniform, thereby obtaining the rare earth heat-dissipating coating. Wherein, the mass percentages of the flaky yttrium cerium oxide powder, the silicon nitride powder, the organic silicon resin, the isopropanol, the dispersing agent, the leveling agent and the defoaming agent are 49%, 1%, 37%, 7%, 4.2%, 0.8% and 1% in sequence.
The paint prepared by the test example of the dual-band emissivity tester of Shanghai Chengbo photoelectric technology science and technology Co is 0.97 in the atmospheric window with the emissivity of 8-13 mu m.
Comparative example 1
Preparing a rare earth-based heat dissipation coating:
stirring lanthanum ceric acid powder, silicon nitride powder and a dispersing agent for pre-dispersing, grinding by a sand mill, stirring and mixing the ground slurry, acrylic resin and an auxiliary agent in a dispersing machine at a high speed until the mixture is uniform, and finally obtaining the rare earth heat-dissipating coating. Wherein, lanthanum ceric acid powder, silicon nitride, acrylic resin, cyclohexanone, dispersing agent, leveling agent and defoaming agent are sequentially as follows by mass percent: 50%, 2%, 30%, 10%, 5%, 1.2%, 1.8%. Lanthanum ceric acid used in this comparative example was commercially available as lanthanum doped lanthanum ceric acid of spherical structure, available from genipin materials, inc.
Comparative example 2
Preparing a rare earth-based heat dissipation coating:
stirring the samarium cerium acid powder and the dispersing agent for pre-dispersing, grinding by a sand mill, stirring and mixing the ground slurry, fluorocarbon resin and auxiliary agent in a dispersing machine at a high speed until the mixture is uniform, and finally obtaining the rare earth heat-dissipating coating. Wherein, the mass percentages of the samarium cerium oxide powder, the fluorocarbon resin, the butyl acetate, the dispersing agent, the leveling agent and the defoaming agent are 55%, 31%, 6%, 5.6%, 1.2% and 1.2% in sequence. The samarium cerium oxide used in this comparative example was a commercially available samarium cerium oxide doped with a spherical structure, commercially available from genius materials, inc.
Comparative example 3
Preparing a rare earth-based heat dissipation coating:
stirring and pre-dispersing the flaky yttrium cerium oxide powder, silicon nitride powder and a dispersing agent, grinding by a sand mill, and stirring and mixing the ground slurry, the organic silicon resin and the auxiliary agent in a dispersing machine at a high speed until the mixture is uniform, thereby finally obtaining the rare earth heat-dissipating coating. Wherein, the mass percentage of the yttrium cerium oxide powder, the silicon nitride powder, the organic silicon resin, the isopropanol, the dispersing agent, the flatting agent and the defoaming agent is 49 percent: 1%:37%:7%:4.2%:0.8%:1%. The yttrium cerium oxide used in this comparative example was a commercially available bulk-structured yttrium doped yttrium cerium oxide available from genipin materials, inc.
The rare earth-based heat-dissipating coatings of examples 1 to 3 and comparative examples 1 to 3 were tested for heat-dissipating performance, while the graphene heat-dissipating coating purchased from Shenzhen materials science and technology Co., ltd was tested as comparative example 4 and the heat-dissipating coating prepared in example 1 of application No. 201710159995.X was tested as comparative example 5, and the specific operation steps were as follows:
carrying out oil removal and dust removal treatment on the surface of an aluminum radiator, and spraying rare earth heat dissipation paint on the radiator, wherein the spraying thickness is 50 mu m; the heat dissipation effects of the radiator were measured for the non-sprayed coating and the sprayed coating, respectively, and the experimental results are shown in table 1.
Table 1 low temperature heat dissipation performance test results
| Project | Uncoated heat sink temperature (. Degree. C.) | Coating heat sink temperature (DEG C) | Temperature difference (DEG C) |
| Example 1 | 145 | 124 | 21 |
| Example 2 | 145 | 122 | 23 |
| Example 3 | 145 | 121 | 24 |
| Comparative example 1 | 145 | 131 | 14 |
| Comparative example 2 | 145 | 134 | 11 |
| Comparative example 3 | 145 | 130 | 15 |
| Comparative example 4 | 145 | 129 | 16 |
| Comparative example 5 | 145 | 127 | 18 |
Table 2 results of medium temperature heat dissipation performance test
| Project | Uncoated heat sink temperature (. Degree. C.) | Coating heat sink temperature (DEG C) | Temperature difference (DEG C) |
| Example 1 | 310 | 247 | 63 |
| Example 2 | 310 | 245 | 65 |
| Example 3 | 310 | 241 | 69 |
| Comparative example 1 | 310 | 259 | 51 |
| Comparative example 2 | 310 | 262 | 48 |
| Comparative example 3 | 310 | 254 | 56 |
| Comparative example 4 | 310 | 258 | 52 |
| Comparative example 5 | 310 | 255 | 55 |
As can be seen from tables 1 and 2, when the temperature gradually became constant, the temperature of the heat sink coated with the flaky rare earth-based high-emissivity heat sink coating was significantly lower than that of the heat sink without the heat sink coating.
TABLE 3 mechanical test results
| Project | Flexibility (millimeter) | Adhesion (grade) |
| Example 1 | 1 | 1 |
| Example 2 | 1 | 1 |
| Example 3 | 1 | 1 |
| Comparative example 1 | 5 | 3 |
| Comparative example 2 | 5 | 3 |
| Comparative example 3 | 5 | 3 |
| Comparative example 4 | 5 | 4 |
| Comparative example 5 | 2 | 3 |
From table 3, it can be seen that the flexibility and adhesion of the flaky rare earth-based high-emissivity coating of the present invention are significantly improved compared with those of the spherical rare earth-based high-emissivity coating, the graphene heat-emissivity coating, and the heat-emissivity coating prepared in example 1 with application No. 201710159995.X, and it can be obtained that the heat-emissivity coating can be better attached to the substrate to protect the substrate after the substrate is heated to change the plasticity and strength.
The above embodiments are merely preferred embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A flaky rare earth-based high-emissivity heat-dissipating coating is characterized in that: comprises the following components in percentage by mass:
45-55% of flaky rare earth powder, 0-3% of silicon nitride powder, 15-40% of high polymer resin, 6-10% of solvent and 2-8% of auxiliary agent; the flaky rare earth powder is La x Ce 1-x O 2 、Y x Ce 1-x O 2 、Sm x Ce 1-x O 2 Wherein x = 0.1-0.5;
the preparation method of the flaky rare earth powder comprises the following steps:
heating a rare earth chloride solution with the pH value of 3-5 and the concentration of 60-100g/L to 40-60 ℃, adding an ammonium bicarbonate solution to prepare a mixed solution, wherein the concentration of the ammonium bicarbonate solution is 150-180g/L, when the pH value of the mixed solution is 6-7, after the reaction is finished, aging, filtering and washing, burning a solid substance, and the burning temperature is 1000-1200 ℃, thus obtaining a flaky rare earth powder product; the solute in the rare earth chloride solution comprises one or more of lanthanum chloride, samarium chloride and yttrium chloride and cerium chloride.
2. The flaky rare earth-based high-emissivity heat-dissipating coating of claim 1, wherein: the molar percentage of cerium chloride in the solute of the rare earth chloride solution is 50% -90%.
3. The flaky rare earth-based high-emissivity heat-dissipating coating of claim 1, wherein: the high polymer resin is one or more of acrylic resin, fluorocarbon resin or organic silicon resin.
4. The flaky rare earth-based high-emissivity heat-dissipating coating of claim 1, wherein: the solvent is one or more of cyclohexanone, isopropanol, n-butanol and butyl acetate.
5. The flaky rare earth-based high-emissivity heat-dissipating coating of claim 1, wherein: the auxiliary agent is one or more of dispersing agent, leveling agent and defoaming agent.
6. The method for preparing the flaky rare earth-based high-emissivity heat dissipation coating as claimed in any one of claims 1 to 5, characterized by: the preparation method comprises the following steps:
stirring the flaky rare earth powder, the solvent and the dispersing agent for pre-dispersing, grinding by a sand mill, stirring and mixing the ground slurry, the high polymer resin and the auxiliary agent in a dispersing machine at a high speed until the mixture is uniform, and finally obtaining the flaky rare earth-based high-radiation heat-dissipation coating.
7. The method for preparing the flaky rare earth-based high-emissivity heat dissipation coating of claim 6, wherein: the particle diameter D90 of the flaky rare earth powder ground by the sand mill in the step is 1.0-3.0 mu m.
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