Flaky rare earth-based high-radiation heat-dissipation coating and preparation method and application thereof
Technical Field
The invention belongs to the field of heat dissipation coatings, and particularly relates to a flaky rare earth-based high-radiation heat dissipation coating as well as a preparation method and application thereof.
Background
In the prior art, graphite or graphene heat dissipation is taken as a main material of the heat dissipation coating, and high-thermal-conductivity fillers such as silicon nitride and silicon carbide are taken as auxiliary materials to jointly play a role in heat dissipation, but the pure graphene powder in the market is high in price, uneven in quality, unstable in quality and high in cost, and rare earth with a specific structure is rarely adopted as a main material to prepare the heat dissipation coating in the market.
Patent CN104359091A discloses a heat sink heat dissipation coating for Led lamps, which uses rare earth oxide, modified corn starch, purple sand, silicon nitride, boron nitride and the like as heat dissipation materials, but the modified corn starch is complex in manufacturing process, only 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 dissipation coating using far infrared ceramic powder, silicon carbide, cerium oxide, etc. as main components, but the addition amount of rare earth therein is very small, and the effect of rare earth oxide in the coating cannot be fully reflected, and meanwhile, the heat dissipation test result for medium and low temperature is not ideal.
Patent CN109852235A discloses a nano-material composite radiation heat-dissipation cooling coating, wherein a high-thermal-conductivity wear-resistant ceramic, graphene, carbon nanotubes and a very small amount of rare earth oxide are mainly used to process a two-component heat-dissipation coating, but the market price of pure graphene is very expensive, the processing technology is complex, the addition amount of rare earth oxide is very small, the structure is too simple, and there is no theory that actual experimental data supports the coating.
Patent CN114316718A discloses a weather-resistant strong infrared radiation heat dissipation industrial coating and a preparation method thereof, wherein rare earth oxide and graphene are used as main radiation materials, but the graphene material is expensive, the production cost is greatly increased, and meanwhile, yttrium oxide in the coating is very easy to hydrolyze in an aqueous coating to generate yttrium hydroxide and yttrium carbonate, which causes instability of the coating. Therefore, the existing heat dissipation coating in the current market has no complete development on the heat dissipation effect of the rare earth and has poor heat dissipation effects on low and medium temperatures.
Disclosure of Invention
In view of the above, the present invention provides a sheet-like rare earth-based high-radiation heat-dissipation coating, a preparation method thereof and an application thereof, aiming at overcoming the defects in the prior art.
In order to achieve the 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, wherein the concentration of the ammonium bicarbonate solution is 150-180g/L, when the pH value of the mixed solution is 6-7, finishing the reaction, aging, filtering and washing, then burning the solid matter, and the burning temperature is 1000-1200 ℃, thus obtaining the flaky rare earth powder product.
Preferably, the solute in the rare earth chloride solution comprises cerium chloride and one or more of lanthanum chloride, samarium chloride and yttrium 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 a dispersing agent, a leveling agent and a 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-dispersion, grinding by using a sand mill, and stirring and mixing the ground slurry, the high-molecular resin and the auxiliary agent in a dispersing machine at a high speed until the mixture is uniform to finally obtain the rare earth heat-dissipation coating.
Preferably, the particle size D90 of the flaky rare earth powder ground by the sand mill in the step is 1.0-3.0 μm.
The invention also provides application of the flaky rare earth-based high-radiation heat dissipation coating in power electronic equipment heat dissipation products, building heat management products, photovoltaic equipment heat dissipation products and wearable equipment heat dissipation products.
Compared with the traditional rare earth oxide, the flaky rare earth powder disclosed by the invention has the advantages that the rare earth elements such as lanthanum, yttrium and samarium are respectively added into cerium oxide in a doping mode, so that lanthanum cerate (La) with a flaky structure is respectively obtained x Ce 1-x O 2 ) Yttrium cerium (Y) x Ce 1- x O 2 ) Samarium ceric acid (Sm) x Ce 1-x O 2 ) The rare earth compound (wherein x = 0.1-0.5) has higher thermal emissivity and better temperature conduction efficiency than the conventional rare earth oxide, and has a sheet structure obtained by doping.
Compared with the traditional blocky or spherical structure of the rare earth powder, the rare earth with the flaky structure has better thermal emissivity and larger heat dissipation area, and meanwhile, the structure has extremely high thermal emissivity at normal temperature and can better dissipate heat at medium and low temperature; because the flaky rare earth is used as the main material, after the coating is cured to form a film, the coating has stronger mechanical property to deal with the plasticity and strength change generated after the substrate is heated. The silicon nitride auxiliary material in the formula not only can improve the heat conductivity of the material, but also can protect the rare earth.
Compared with the prior art, the invention has the following advantages:
(1) The emissivity of the flaky rare earth-based high-radiation heat-dissipation coating in an atmospheric window of 8-13 mu m is 0.97 (a test instrument is a dual-band emissivity tester of Shanghai Chengchenbo optoelectronic technology and science and technology Limited), the emissivity is extremely close to an absolute blackbody emissivity of 1, excellent physical conditions are provided for radiation heat dissipation, and the obtained coating has a remarkable heat dissipation effect.
(2) Compared with the traditional cerium oxide, the doping of lanthanum, yttrium and samarium in the flaky rare earth powder disclosed by the invention can form a very stable compound on the crystal lattice of the cerium oxide, so that the thermal conductivity and the thermal radiance of the heat-dissipation coating are improved, and the long-term stability of the heat-dissipation coating is ensured.
(3) The rare earth material with a sheet structure can improve the mechanical property of the heat-dissipating coating after film forming, wherein the flexibility of the coating is executed according to the national standard GB/T1731-93, and the result is 1 mm, so that 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 and excellent, and after the substrate is heated and the plasticity and the strength of the substrate are changed, the heat dissipation coating can be better attached to the substrate to protect the substrate.
(4) The coating has obvious heat dissipation effect at low and medium temperature, and for low-temperature heat dissipation (0 to 200 ℃), the heat dissipation efficiency of the radiator coated with the rare earth heat dissipation coating is improved by 10 to 20 percent compared with the heat dissipation effect of the radiator without the heat dissipation coating. For medium-temperature heat dissipation (200 to 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 is simple and convenient in process, and can greatly save the production time and cost; meanwhile, the construction is convenient, and the paint can be sprayed, roll-coated or dip-coated; meanwhile, the rare earth heat dissipation coating has good aging resistance, is executed according to the national standard GB/T1865-2009, and has the artificial climate aging resistance of more than 2000 hours.
(6) The flaky rare earth-based high-radiation heat dissipation coating can be applied to a plurality of fields, such as heat dissipation devices in the electronic industry, and is beneficial to future development of electronic products; for example, the solar backboard dissipates heat, so that the photovoltaic power generation efficiency can be greatly improved.
Drawings
FIG. 1 is an electron microscope image of the flaky lanthanum cerate powder in example 1 of the present invention;
FIG. 2 is an XRD pattern of the flaky lanthanum cerate powder in example 1 of the present invention;
FIG. 3 is an electron micrograph of a sheet-like samarium cerate powder according to example 2 of the present invention;
fig. 4 is an XRD pattern of the flaky samarium cerate powder in example 2 of the present invention;
FIG. 5 is an electron microscope image of the flaky yttrium cerate powder in example 3 of the present invention;
fig. 6 is an XRD pattern of the flaky yttrium cerate powder in example 4 of the present invention.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are all conventional methods unless otherwise specified.
The invention will be described in detail with reference to the following examples.
Example 1
(1) Preparation of flaky lanthanum cerate powder La 0.4 Ce 0.6 O 2
Heating a rare earth chloride solution with the pH value of 3.5 and the concentration of 70 g/L to 50 ℃, adding an ammonium bicarbonate solution with the 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. The electron micrograph of the prepared flaky lanthanum cerate powder product is shown in figure 1, and the XRD map is shown in figure 2.
(2) Preparation of flaky rare earth-based high-radiation heat-dissipation coating
Stirring the flaky lanthanum cerate powder prepared in the step (1), silicon nitride, cyclohexanone and a dispersing agent for pre-dispersion, grinding by using 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 finally obtaining the rare earth heat-dissipation coating. Wherein, the flaky lanthanum cerate powder, the silicon nitride, the acrylic resin, the cyclohexanone, the dispersant, the flatting agent and the defoaming agent are sequentially prepared from the following components in percentage by mass: 50%, 2%, 30%, 10%, 5%:1.2 percent and 1.8 percent.
The emissivity of the coating prepared by the test example of the two-waveband emissivity tester of Shanghai Chengcong wave photoelectric technology science and technology Limited company is 0.93 in an atmospheric window of 8 to 13 mu m.
Example 2
(1) Preparation of sheet samarium cerate 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, when the pH value of the mixed solution is 6, finishing the reaction, aging, filtering and washing, and then burning solid substances at the burning temperature of 1150 ℃ to obtain the flaky samarium ceric acid powder product. The electron micrograph of the prepared sheet samarium ceric acid powder product is shown in figure 3, and the XRD micrograph is shown in figure 4.
(2) Preparation of flaky rare earth-based high-radiation heat-dissipation coating
Stirring the flaky samarium ceric acid powder prepared in the step (1), butyl acetate and a dispersing agent for pre-dispersion, grinding by using 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 ceric acid powder, the fluorocarbon resin, the butyl acetate, the dispersing agent, the flatting agent and the defoaming agent are 55%, 31%, 6%, 5.6%, 1.2% and 1.2% in sequence.
The emissivity of the coating prepared by the test example of the two-waveband emissivity tester of Shanghai Chengcong wave photoelectric technology science and technology Limited company is 0.95 in an atmospheric window of 8 to 13 mu m.
Example 3
(1) Preparation of flake yttrium ceric 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 ℃, 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 percent, when the pH value of the mixed solution is 7, finishing the reaction, and burning the solid matter after aging, filtering and washing, wherein the burning temperature is 1200 ℃, thus obtaining the sheet yttrium cerate powder product. The obtained flaky yttrium cerate powder product has an electron microscope image shown in fig. 5 and an XRD image shown in fig. 6.
(2) Preparation of flaky rare earth-based high-radiation heat-dissipation coating
Stirring the flaky yttrium cerate powder prepared in the step (1), silicon nitride powder and an isopropanol dispersant for pre-dispersion, grinding by using a sand mill, and stirring and mixing the ground slurry, organic silicon 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-dissipation coating. Wherein the mass percentages of the flaky yttrium cerate powder, the silicon nitride powder, the organic silicon resin, the isopropanol, the dispersing agent, the flatting agent and the defoaming agent are 49%, 1%, 37%, 7%, 4.2%, 0.8% and 1% in sequence.
The emissivity of the coating prepared by the test example of the two-waveband emissivity tester of Shanghai Chengcong wave photoelectric technology science and technology Limited company is 0.97 in an atmospheric window of 8 to 13 mu m.
Comparative example 1
Preparing the rare earth-based heat dissipation coating:
and stirring lanthanum cerate powder, silicon nitride powder and a dispersing agent for pre-dispersion, grinding by using 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 finally obtaining the rare earth heat-dissipation coating. Wherein, the lanthanum cerate powder, the silicon nitride, the acrylic resin, the cyclohexanone, the dispersant, the flatting agent and the defoaming agent are sequentially in mass percentage: 50%, 2%, 30%, 10%, 5%, 1.2%, 1.8%. The lanthanum cerate used in this comparative example was a commercially available lanthanum-doped lanthanum cerate of spherical structure, available from kyoto new materials ltd.
Comparative example 2
Preparing the rare earth-based heat dissipation coating:
and stirring the samarium ceric acid powder and the dispersing agent for pre-dispersion, grinding by using a sand mill, and stirring and mixing the ground slurry, the fluorocarbon 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 samarium ceric acid powder, the fluorocarbon resin, the butyl acetate, the dispersing agent, the flatting agent and the defoaming agent are 55%, 31%, 6%, 5.6%, 1.2% and 1.2% in sequence by mass percent. The samarium ceric acid used in this comparative example was a commercially available samarium-doped samarium ceric acid having a spherical structure, which was obtained from kyoto new materials ltd.
Comparative example 3
Preparing the rare earth-based heat dissipation coating:
stirring the flaky yttrium cerate powder, the silicon nitride powder and the dispersing agent for pre-dispersion, grinding by using 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 cerate powder, the silicon nitride powder, the organic silicon resin, the isopropanol, the dispersant, the flatting agent and the defoaming agent is 49%:1%:37%:7%:4.2%:0.8%:1 percent. The yttrium cerate used in this comparative example was a commercially available yttrium-doped yttrium cerate in a bulk structure, available from kyoto new materials ltd.
The rare earth-based heat dissipation coatings of examples 1 to 3 and comparative examples 1 to 3 were subjected to a heat dissipation performance test, and a graphene heat dissipation coating purchased from hezhen saw teaching materials limited as comparative example 4 and a heat dissipation coating prepared in example 1 with application number 201710159995.X as comparative example 5 were subjected to a test, specifically including the following steps:
carrying out oil removal and dust removal treatment on the surface of an aluminum radiator, and spraying rare earth heat dissipation coating on a heat sink, wherein the spraying thickness is 50 microns; the heat dissipation effects of the heat sinks of the non-sprayed coating and the sprayed coating were measured, respectively, and the experimental results are shown in table 1.
Table 1 low temperature heat dissipation performance test results
Item
|
Temperature of uncoated Heat sink (. Degree. C.)
|
Temperature of coated fin (. Degree.C.)
|
Temperature difference (. Degree. 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 test results of medium-temperature heat dissipation performance
Item
|
Temperature of uncoated Fin (. Degree. C.)
|
Temperature of coated fin (. Degree.C.)
|
Temperature difference (. Degree. 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, the temperature of the heat sink coated with the sheet-like rare earth-based high-emissivity heat-dissipating coating is significantly lower than that of the heat sink not coated with the heat-dissipating coating as the temperature gradually approaches constant.
TABLE 3 mechanical Property test results
Item
|
Flexibility (millimeter)
|
Adhesion (grade)
|
Example 1
|
1
|
1
|
Examples2
|
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 |
As can be seen from table 3, the flexibility and adhesion of the flaky rare earth-based high-radiation heat-dissipation coating of the present invention are significantly improved compared to the heat-dissipation coating using a spherical rare earth-based heat-dissipation coating, a graphene heat-dissipation coating, and the heat-dissipation coating prepared in example 1 with application No. 201710159995. X.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and should not be taken as limiting the invention, and any modifications, equivalents, improvements and the like that are made within the spirit and principle of the present invention should be included in the scope of the present invention.