CN114213882B - High-temperature-resistant heat-dissipation coating and preparation method thereof - Google Patents
High-temperature-resistant heat-dissipation coating and preparation method thereof Download PDFInfo
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Abstract
The invention provides a high-temperature-resistant heat-dissipation coating and a preparation method thereof, belonging to the technical field of coatings. The method comprises the following steps: s1, preparing metal oxide nano powder; s2, preparing polydopamine/metal oxide nano powder; s3, preparing modified polydopamine/metal oxide nano powder; s4, preparing organic silicon modified silica sol; s5, preparing the high-temperature-resistant heat-dissipation coating. The high-temperature-resistant heat-dissipation coating prepared by the invention has good mechanical property, high temperature resistance, wear resistance, good fracture resistance, good flexibility and elasticity, self-heat dissipation and far infrared release effects, can be applied to electronic devices, has a good heat dissipation effect, can tolerate higher temperature, and has a wide application prospect.
Description
Technical Field
The invention relates to the technical field of coatings, in particular to a high-temperature-resistant heat-dissipation coating and a preparation method thereof.
Background
With the precise design of electronic products, the operation process of electronic products is often accompanied by the generation of a large amount of heat energy, which can not effectively dissipate the heat energy, causing the problem of overheating of electronic products, and even affecting the quality and reliability of electronic products.
In order to avoid the foregoing problems, in the prior art, a heat source of an electronic product is mostly provided with a heat dissipation fin or a fan, so as to dissipate the heat source to the outside of the electronic product by increasing a surface area or increasing heat convection. However, the arrangement of the heat dissipation fins increases the overall size of the electronic product; besides, the fan increases the volume of the electronic product, and the fan can be driven to operate only by additionally introducing a power supply, so that the purpose of reducing the temperature of the electronic product is achieved.
However, the aforementioned solutions are not suitable for the development of electronic products with light weight and energy saving. In order to overcome the above limitations, the prior art turns to coating a heat dissipation coating on an electronic device to achieve the purpose of heat dissipation while meeting the requirements of light weight, thinness, and energy saving of electronic products.
Most of the materials of the heat dissipation coatings developed at present are chemically modified nanocarbon materials, and the shell structure of the chemically modified nanocarbon materials is damaged, so that the chemically modified nanocarbon materials cannot obtain sufficient heat resistance, and the heat dissipation coatings in the prior art cannot be suitable for exerting the required heat dissipation effect at the temperature of more than 400 ℃.
Disclosure of Invention
The invention aims to provide a high-temperature-resistant heat-dissipation coating and a preparation method thereof, which have the advantages of good mechanical property, high temperature resistance, wear resistance, good anti-cracking capability, good flexibility and elasticity, self-heat dissipation and far infrared release effects, good heat dissipation effect when applied to electronic devices, capability of tolerating higher temperature and wide application prospect.
The technical scheme of the invention is realized as follows:
the invention provides a preparation method of a high-temperature-resistant heat-dissipation coating, which comprises the following steps:
s1, preparing metal oxide nano powder: dissolving metal nitrate in water, adding citric acid, performing ultrasonic dispersion, heating to a first temperature, and evaporating the solvent to obtain sol; then raising the temperature to a second temperature, reducing the pressure intensity to form dry gel, taking out the dry gel, and igniting the dry gel to obtain metal oxide nano powder;
s2, preparing polydopamine/metal oxide nano powder: uniformly dispersing the metal oxide nano powder prepared in the step S1 in water, adding dopamine hydrochloride, adding a Tris-HCl solution, heating for reaction, centrifuging, washing and drying to obtain poly-dopamine/metal oxide nano powder;
s3, preparing modified polydopamine/metal oxide nano powder: uniformly dispersing the polydopamine/metal oxide nano powder prepared in the step S2 in an ethanol solution, adding a silane coupling agent, heating for reaction, centrifuging, washing and drying to obtain modified polydopamine/metal oxide nano powder;
s4, preparing organic silicon modified silica sol: uniformly mixing alkaline silica sol, water and crystal whisker silicon, adding organosilane and acetic acid, and carrying out mixing reaction to obtain organic silicon modified silica sol;
s5, preparing the high-temperature-resistant heat-dissipation coating: and (4) adding the modified polydopamine/metal oxide nano powder prepared in the step (S3) into the organic silicon modified silica sol prepared in the step (S4), homogenizing, standing and curing to obtain the high-temperature-resistant heat-dissipation coating.
As a further improvement of the invention, in the step S1, the metal nitrate in the step S1 is a mixture of iron nitrate, aluminum nitrate and cobalt nitrate, and the mass ratio of the iron nitrate, the aluminum nitrate, the cobalt nitrate and the citric acid is (4-12): 13: (1-5): (30-40); the first temperature is 45-55 ℃; the second temperature is 170-200 ℃; and reducing the pressure to a vacuum degree of 0.01-0.1MPa, wherein the mass ratio of the ferric nitrate to the aluminum nitrate to the cobalt nitrate to the citric acid is (4-12): 13: (1-5): (30-40); the first temperature is 45-55 ℃; the second temperature is 170-200 ℃; the pressure is reduced to the vacuum degree of 0.01-0.1 MPa.
As a further improvement of the present invention, the mass ratio of the metal oxide nano powder to the dopamine hydrochloride in step S2 is 10: (17-22); the pH value of the Tris-HCl solution is 8-8.5, the heating reaction temperature is 40-50 ℃, and the time is 3-5 h.
As a further improvement of the present invention, the mass ratio of the polydopamine/metal oxide nanopowder to the silane coupling agent in step S3 is 10: (0.5-1); the silane coupling agent is selected from at least one of KH550, KH560, KH570, KH580, KH590, KH602 and KH 792; the heating reaction temperature is 70-80 ℃, and the time is 1-3 h.
As a further improvement of the invention, the silane coupling agent is a compound mixture of KH550 and KH590, and the mass ratio is 5: (1-3).
As a further improvement of the invention, in step S4, the organosilane is methyltriethoxysilane, and the mass ratio of the alkaline silica sol, water, whisker silicon, methyltriethoxysilane and acetic acid is (30-40): (20-30): (10-20): (20-30): (0.5-1); the mixing reaction temperature is 25-35 ℃ and the time is 2-4 h.
As a further improvement of the invention, the mass ratio of the modified poly-dopamine/metal oxide nano powder to the organosilicon modified silica sol in the step S5 is (2-5): 12; the homogenization condition is 12000-15000r/min for 3-5 min; the curing time is 7-10 h.
As a further improvement of the invention, the method specifically comprises the following steps:
s1, preparing metal oxide nano powder: dissolving 4-12 parts by weight of ferric nitrate, 13 parts by weight of aluminum nitrate and 1-5 parts by weight of cobalt nitrate in water, adding 30-40 parts by weight of citric acid, performing ultrasonic dispersion, and heating to 45-55 ℃ to evaporate the solvent to obtain sol; then raising the temperature to 170-200 ℃ and the vacuum degree to 0.01-0.1MPa to form dry gel, taking out the dry gel, and igniting the dry gel to obtain metal oxide nano powder;
s2, preparing polydopamine/metal oxide nano powder: uniformly dispersing 10 parts by weight of the metal oxide nano powder prepared in the step S1 in water, adding 17-22 parts by weight of dopamine hydrochloride, adding 1-2 parts by weight of Tris-HCl solution with the pH value of 8-8.5, heating to 40-50 ℃, reacting for 3-5h, centrifuging, washing and drying to obtain poly-dopamine/metal oxide nano powder;
s3, preparing modified polydopamine/metal oxide nano powder: uniformly dispersing 10 parts by weight of the polydopamine/metal oxide nano powder prepared in the step S2 in an ethanol solution, adding 0.5-1 part by weight of a silane coupling agent, heating to 70-80 ℃, reacting for 1-3h, centrifuging, washing, and drying to obtain modified polydopamine/metal oxide nano powder;
the silane coupling agent is a compound mixture of KH550 and KH590, and the mass ratio is 5: (1-3);
s4, preparing organic silicon modified silica sol: uniformly mixing 30-40 parts by weight of alkaline silica sol, 20-30 parts by weight of water and 10-20 parts by weight of crystal whisker silicon, adding 20-30 parts by weight of methyltriethoxysilane and 0.5-1 part by weight of acetic acid, and carrying out mixing reaction at 25-35 ℃ for 2-4h to obtain organic silicon modified silica sol;
s5, preparing the high-temperature-resistant heat-dissipation coating: adding 2-5 parts by weight of the modified polydopamine/metal oxide nano powder prepared in the step S3 into 12 parts by weight of the organic silicon modified silica sol prepared in the step S4, homogenizing for 3-5min at 12000-15000r/min, and standing and curing for 7-10h to obtain the high-temperature-resistant heat-dissipation coating.
The invention further protects the high-temperature-resistant heat-dissipation coating prepared by the preparation method.
As a further improvement of the invention, the thermal conductivity coefficient of the coating is 12-21W/m.K, the pencil hardness is 4-6H, and the adhesion is 0-2 grade.
The invention has the following beneficial effects: in the present invention, since citric acid is a weak acid, multi-stage dissociation reaction occurs in the presence of metal ions Fe3+、Al3+、Co3+In the presence of a complex, the reaction is as follows:
Fe3++C6H5O7 3-＝FeC6H5O7
Fe3++C6H6O7 2-＝FeC6H6O7 +
Al3++C6H5O7 3-＝AlC6H5O7
Al3++C6H6O7 2-＝AlC6H6O7 +
Co3++C6H5O7 3-＝CoC6H5O7
Co3++C6H6O7 2-＝CoC6H6O7 +
at this time, the metal ions and the citric acid are equivalent, but since the citric acid is weak acid, chemical equilibrium shift exists in the reaction process, and only when the citric acid is excessive, the stable complexation of the metal ions and the citric acid can be ensured. The obtained xerogel is burnt to obtain metal oxide nano powder, namely nano powder containing aluminum oxide, iron oxide and cobalt oxide; the metal oxide powder enables the coating to have excellent heat dissipation and heat conduction performance and high temperature resistance, plays roles of self heat dissipation and far infrared release, has the far infrared release efficiency of more than 94 percent, and has a health care effect on human bodies;
furthermore, a layer of polydopamine is reacted and compounded on the surface of the metal oxide nano powder, and the polydopamine is rich in amino and hydroxyl, so that the surface wettability of the nano material is enhanced, tiny water drops are easy to penetrate into the surface of the nano material to play a role in evaporation and heat dissipation, and in addition, the polydopamine is also easy to be bonded with a silane coupling agent, so that the polydopamine can be modified and copolymerized with silica sol and organic silicon to obtain a uniform high-temperature-resistant heat dissipation coating;
after the prepared poly-dopamine/metal oxide nano powder is modified by a silane coupling agent, the surface of a nano material is connected with organic silicon alkoxy, so that the poly-dopamine/metal oxide nano powder is easy to copolymerize with silica sol and organic silicon in subsequent reaction to form a composite coating, and the silane coupling agent is preferably a compound mixture of KH550 and KH590, because an organic chain part has amino or sulfydryl and is easy to be in hydrogen bonding with the amino and hydroxyl of poly-dopamine on the surface of the poly-dopamine/metal oxide nano powder, and the more the number of alkoxy directly connected with silicon atoms is, the higher the hydrolytic activity is; in addition, the longer the organic chain of the silane is, the larger the steric hindrance is, the poorer the reactivity of the silane with the silica sol and the organosilicon in the copolymerization is, so that the prepared modified poly-dopamine/metal oxide nano powder can be uniformly and stably mixed with the organosilicon modified silica sol by selecting a proper silane coupling agent, and the high-temperature-resistant scattering coating with better performance is obtained. The organic group of siloxane can effectively enhance the flexibility and elasticity of the coating, thereby improving the anti-cracking capability of the coating, and the inorganic part enables the coating to have excellent mechanical property, high temperature resistance, wear resistance and other properties.
The high-temperature-resistant heat-dissipation coating prepared by the invention has good mechanical property, high temperature resistance, wear resistance, good fracture resistance, good flexibility and elasticity, self-heat dissipation and far infrared release effects, can be applied to electronic devices, has a good heat dissipation effect, can tolerate higher temperature, and has a wide application prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an SEM image of the polydopamine/metal oxide nanopowder prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The alkaline silica sol was purchased from Acksotbel under the trade name Bindzil 9950, having a silicon content of 50% and a pH of 9.0; methyltriethoxysilane, CAS No.: 2031-67-6, industrial grade, purchased from Quzhou Rayleigh Jie chemical Co., Ltd; dodecyl methyl dimethoxy silane, CAS No.: 3069-21-4, available from Hangzhou geochemistry Co., Ltd, with an effective component of more than 96%; the crystal whisker silicon, 2500 meshes, is purchased from Shanghai Hui Jing sub-nanometer new material Co. Other reagents are all chemically pure and purchased from chemical reagents of national drug group, Inc.
Example 1
The embodiment provides a preparation method of a high-temperature-resistant heat dissipation coating, which specifically comprises the following steps:
s1, preparing metal oxide nano powder: dissolving 4g of ferric nitrate, 13g of aluminum nitrate and 1g of cobalt nitrate in 100mL of water, adding 30g of citric acid, ultrasonically dispersing for 30min at 1000W, heating to 45 ℃, and evaporating for 1h to obtain sol; then raising the temperature to 170 ℃ and keeping the vacuum degree at 0.01MPa to form dry gel, taking out the dry gel, and igniting the dry gel to obtain metal oxide nano powder;
s2, preparing polydopamine/metal oxide nano powder: adding 10g of the metal oxide nano powder prepared in the step S1 into 100mL of water, carrying out 2000W ultrasonic dispersion for 30min, adding 17g of dopamine hydrochloride, adding 1g of Tris-HCl solution with the pH value of 8, heating to 40 ℃, stirring for reaction for 3h, centrifuging for 15min at 3000r/min, washing with deionized water, and drying for 4h at 70 ℃ to obtain poly-dopamine/metal oxide nano powder; fig. 1 is an SEM image of the prepared polydopamine/metal oxide nanopowder, and it can be seen from the figure that the particle size of the prepared polydopamine/metal oxide nanopowder is within 200 nm.
S3, preparing modified polydopamine/metal oxide nano powder: adding 10g of the polydopamine/metal oxide nano powder prepared in the step S2 into 50mL of ethanol solution, adding 0.5g of silane coupling agent, heating to 70 ℃, stirring for reaction for 1h, centrifuging at 3000r/min for 15min, washing with ethanol, and drying at 70 ℃ for 4h to obtain modified polydopamine/metal oxide nano powder;
the silane coupling agent is a compound mixture of KH550 and KH590, and the mass ratio is 5: 1;
s4, preparing organic silicon modified silica sol: uniformly mixing 30g of alkaline silica sol, 20g of deionized water and 10g of whisker silicon, adding 20g of methyltriethoxysilane and 0.5g of acetic acid, mixing and stirring at 25 ℃, and reacting for 2 hours to obtain organic silicon modified silica sol;
s5, preparing the high-temperature-resistant heat-dissipation coating: and (3) adding 2g of the modified polydopamine/metal oxide nano powder prepared in the step S3 into 12g of the organic silicon modified silica sol prepared in the step S4, homogenizing at 12000r/min for 3min, standing and curing for 7h to obtain the high-temperature-resistant heat-dissipation coating.
Example 2
The embodiment provides a preparation method of a high-temperature-resistant heat dissipation coating, which specifically comprises the following steps:
s1, preparing metal oxide nano powder: dissolving 12g of ferric nitrate, 13g of aluminum nitrate and 5g of cobalt nitrate in 100mL of water, adding 40g of citric acid, ultrasonically dispersing for 30min at 1000W, heating to 55 ℃, and evaporating for 1h to obtain sol; then raising the temperature to 200 ℃ and keeping the vacuum degree at 0.1MPa to form dry gel, taking out the dry gel, and igniting the dry gel to obtain metal oxide nano powder;
s2, preparing polydopamine/metal oxide nano powder: adding 10g of the metal oxide nano powder prepared in the step S1 into 100mL of water, carrying out 2000W ultrasonic dispersion for 30min, adding 22g of dopamine hydrochloride, adding 2g of Tris-HCl solution with the pH value of 8.5, heating to 50 ℃, stirring, reacting for 5h, centrifuging at 3000r/min for 15min, washing with deionized water, and drying at 70 ℃ for 4h to obtain poly-dopamine/metal oxide nano powder;
s3, preparing modified polydopamine/metal oxide nano powder: adding 10g of the polydopamine/metal oxide nano powder prepared in the step S2 into 50mL of ethanol solution, adding 1g of silane coupling agent, heating to 80 ℃, stirring for reaction for 3h, centrifuging at 3000r/min for 15min, washing with ethanol, and drying at 70 ℃ for 4h to obtain modified polydopamine/metal oxide nano powder;
the silane coupling agent is a compound mixture of KH550 and KH590, and the mass ratio is 5: 3;
s4, preparing organic silicon modified silica sol: uniformly mixing 40g of alkaline silica sol, 30g of deionized water and 20g of whisker silicon, adding 30g of methyltriethoxysilane and 1g of acetic acid, mixing and stirring at 35 ℃, and reacting for 4 hours to obtain organic silicon modified silica sol;
s5, preparing the high-temperature-resistant heat-dissipation coating: and (3) adding 5g of the modified polydopamine/metal oxide nano powder prepared in the step S3 into 12g of the organic silicon modified silica sol prepared in the step S4, homogenizing at 15000r/min for 5min, standing and curing for 10h to obtain the high-temperature-resistant heat-dissipation coating.
Example 3
The embodiment provides a preparation method of a high-temperature-resistant heat dissipation coating, which specifically comprises the following steps:
s1, preparing metal oxide nano powder: dissolving 8g of ferric nitrate, 13g of aluminum nitrate and 3g of cobalt nitrate in 100mL of water, adding 35g of citric acid, ultrasonically dispersing for 30min at 1000W, heating to 50 ℃, and evaporating for 1h to obtain sol; then raising the temperature to 185 ℃, and keeping the vacuum degree at 0.05MPa to form dry gel, taking out, and igniting the dry gel to obtain metal oxide nano powder;
s2, preparing polydopamine/metal oxide nano powder: adding 10g of the metal oxide nano powder prepared in the step S1 into 100mL of water, carrying out 2000W ultrasonic dispersion for 30min, adding 20g of dopamine hydrochloride, adding 1.5g of Tris-HCl solution with the pH value of 8.2, heating to 45 ℃, stirring for reaction for 4h, centrifuging at 3000r/min for 15min, washing with deionized water, and drying at 70 ℃ for 4h to obtain poly-dopamine/metal oxide nano powder;
s3, preparing modified polydopamine/metal oxide nano powder: adding 10g of the polydopamine/metal oxide nano powder prepared in the step S2 into 50mL of ethanol solution, adding 0.7g of silane coupling agent, heating to 75 ℃, stirring for reaction for 2h, centrifuging at 3000r/min for 15min, washing with ethanol, and drying at 70 ℃ for 4h to obtain modified polydopamine/metal oxide nano powder;
the silane coupling agent is a compound mixture of KH550 and KH590, and the mass ratio is 5: 2;
s4, preparing organic silicon modified silica sol: uniformly mixing 35g of alkaline silica sol, 25g of deionized water and 15g of whisker silicon, adding 25g of methyltriethoxysilane and 0.7g of acetic acid, mixing and stirring at 30 ℃, and reacting for 3 hours to obtain organic silicon modified silica sol;
s5, preparing the high-temperature-resistant heat-dissipation coating: and (3.5 g) the modified polydopamine/metal oxide nano powder prepared in the step S3 is added into 12g of the organic silicon modified silica sol prepared in the step S4, homogenized at 13500r/min for 4min, and kept stand and cured for 8h to obtain the high-temperature-resistant heat-dissipation coating.
Example 4
Compared with example 3, the silane coupling agent is KH550, and other conditions are not changed.
Example 5
Compared with example 3, the silane coupling agent is KH590, and other conditions are not changed.
Example 6
Compared with example 3, no ferric nitrate was added, and other conditions were not changed.
Wherein the metal nitrate comprises 21g of aluminum nitrate and 3g of cobalt nitrate.
Example 7
Compared with example 3, no aluminum nitrate was added, and other conditions were not changed.
Wherein the metal nitrate comprises 21g of ferric nitrate and 3g of cobalt nitrate.
Example 8
The amount of citric acid added was lower than in example 3, and only 10g of citric acid was added, and the other conditions were not changed.
Example 9
Compared with example 3, the amount of dopamine hydrochloride added was lower, only 5g of dopamine hydrochloride was added, and the other conditions were not changed.
Example 10
Compared with example 3, the methyltriethoxysilane was replaced by dodecylmethyldimethoxysilane, and the other conditions were not changed.
Comparative example 1
Step S2 was not performed, and other conditions were not changed, as compared with example 3.
S1, preparing metal oxide nano powder: dissolving 8g of ferric nitrate, 13g of aluminum nitrate and 3g of cobalt nitrate in 100mL of water, ultrasonically dispersing for 30min at 2000W, adding 35g of citric acid, ultrasonically dispersing for 30min at 1000W, heating to 50 ℃, and evaporating for 1h to obtain sol; then raising the temperature to 185 ℃, and forming dry gel under the vacuum degree of 0.05MPa, taking out, and igniting the dry gel to obtain metal oxide nano powder;
s2, preparing modified metal oxide nano powder: adding 10g of the metal oxide nano powder prepared in the step S1 into 50mL of ethanol solution, adding 0.7g of silane coupling agent, heating to 75 ℃, stirring for reaction for 2h, centrifuging at 3000r/min for 15min, washing with ethanol, and drying at 70 ℃ for 4h to obtain modified metal oxide nano powder;
the silane coupling agent is a compound mixture of KH550 and KH590, and the mass ratio is 5: 2;
s3, preparing organic silicon modified silica sol: uniformly mixing 35g of alkaline silica sol, 25g of deionized water and 15g of whisker silicon, adding 25g of methyltriethoxysilane and 0.7g of acetic acid, mixing and stirring at 30 ℃, and reacting for 3 hours to obtain organic silicon modified silica sol;
s4 preparation of the high-temperature-resistant heat-dissipation coating: and (3.5 g) adding the modified metal oxide nano powder prepared in the step S2 into 12g of the organic silicon modified silica sol prepared in the step S3, homogenizing at 13500r/min for 4min, standing and curing for 8h to obtain the high-temperature-resistant heat-dissipation coating.
Comparative example 2
Step S3 was not performed, and other conditions were not changed, as compared with example 3.
S1, preparing metal oxide nano powder: dissolving 8g of ferric nitrate, 13g of aluminum nitrate and 3g of cobalt nitrate in 100mL of water, ultrasonically dispersing for 30min at 2000W, adding 35g of citric acid, ultrasonically dispersing for 30min at 1000W, heating to 50 ℃, and evaporating for 1h to obtain sol; then raising the temperature to 185 ℃, and keeping the vacuum degree at 0.05MPa to form dry gel, taking out, and igniting the dry gel to obtain metal oxide nano powder;
s2, preparing polydopamine/metal oxide nano powder: adding 10g of the metal oxide nano powder prepared in the step S1 into 100mL of water, adding 20g of dopamine hydrochloride, adding 1.5g of Tris-HCl solution with the pH value of 8.2, heating to 45 ℃, stirring and reacting for 4h, centrifuging at 3000r/min for 15min, washing with deionized water, and drying at 70 ℃ for 4h to obtain poly-dopamine/metal oxide nano powder;
s3, preparing organic silicon modified silica sol: uniformly mixing 35g of alkaline silica sol, 25g of deionized water and 15g of whisker silicon, adding 25g of methyltriethoxysilane and 0.7g of acetic acid, mixing and stirring at 30 ℃, and reacting for 3 hours to obtain organic silicon modified silica sol;
s4, preparing the high-temperature-resistant heat-dissipation coating: and (3.5 g) adding 3.5g of the polydopamine/metal oxide nano powder prepared in the step S2 into 12g of the organic silicon modified silica sol prepared in the step S3, homogenizing at 13500r/min for 4min, standing and curing for 8h to obtain the high-temperature-resistant heat-dissipation coating.
Test example 1
The mechanical property test of the high temperature resistant heat dissipation coating prepared in the examples 1-10 and the comparative examples 1-2 of the invention is carried out, and the result is shown in table 1.
The adhesion test was carried out according to the standard of GB/T9286-1998 (test of adhesive tape grid after cutting into 1mm grid), and the secondary adhesion test was carried out according to the standard of GB/T9286-1998 (50 ℃, 95% relative humidity, adhesion test after 240 h); the pencil hardness test is carried out according to the standard determination of GB/T6739-2006 (45-degree angle of Mitsubishi pencil, five times of flaw judgment); abrasion resistance test the abrasion resistance test was carried out according to the standard of GB/T12721-2007 (using an eraser, a load of 4.9N, 600 times of reciprocating friction); the impact test was carried out according to the standard of GB/T5095.5-1997 (50cm, 500 g);
TABLE 1
As can be seen from the above table, the high temperature resistant heat dissipation coating prepared in embodiments 1 to 3 of the present invention has good wear resistance, high hardness, and good mechanical properties.
Test example 2
The high temperature resistant heat dissipation coatings prepared in examples 1-10 of the present invention and comparative examples 1-2 were subjected to comprehensive energy tests, and the results are shown in table 2.
The thermal conductivity was measured according to the GB/T10297-2015 standard (30 ℃).
The high temperature resistance test method comprises the following steps: after oven baking at 210 ℃/3h, oven baking at 145 ℃/15 days.
The weather resistance test is determined according to the standard of GB/T9276-1996 (after 500 hours of weather resistance, appearance evaluation).
The salt spray resistance test was carried out according to the standard of GB/T2423.17-1993 (35 ℃, 5 wt% NaCl, 500 h).
The solvent resistance test was carried out according to the standard of GB/T23989-2009 (cotton cloth was stained with solvent, then subjected to a load of 9.5N, wiped repeatedly 200 times, and evaluated for appearance).
TABLE 2
As can be seen from the above table, the high temperature resistant heat dissipation coating prepared in the embodiments 1 to 3 of the present invention has good high temperature resistance, high thermal conductivity of 31 to 34W/m.K, and good heat conductivity and heat dissipation performance.
In examples 4 and 5, compared with example 3, the silane coupling agent is KH550 or KH590, which slightly decreases the high temperature resistance, weather resistance and adhesion, and slightly decreases the thermal conductivity, because a single silane coupling agent has a poor effect on the copolymerization reaction of the modified poly-dopamine/metal oxide nano powder with the silica sol and the organosilane, resulting in the decrease of the high temperature resistance, weather resistance, thermal conductivity and the like of the coating. The amino or the sulfhydryl of the silane coupling agent is easy to bond with the amino and the hydroxyl on the surface of the polydopamine, and the addition of the amino or the sulfhydryl has a synergistic effect.
Compared with the example 3, the examples 6 and 7 have the advantages that the thermal conductivity coefficient is reduced, the hardness is reduced, the wear resistance is reduced, and the high temperature resistance of the example 7 is reduced, so that the iron and aluminum nano oxides are obvious in improving the heat conduction and radiation performance of the coating, wherein the aluminum oxide is obvious in improving the high temperature resistance of the coating, and the nano-scale powder containing the aluminum oxide, the iron oxide and the cobalt oxide enables the coating to have excellent heat dissipation and heat conduction performance and high temperature resistance, has the functions of self heat dissipation and far infrared release, has the far infrared release efficiency of more than 94 percent, and has a health care effect on human bodies.
Compared with the embodiment 3, the addition amount of citric acid is lower, only 10g of citric acid is added, and as the content of citric acid is reduced, a stable complex can not be formed with metal ions, only partial sol is formed, and a large amount of metal ions are still in water and are removed by washing, the content of metal oxide nano powder added in the coating is reduced, the heat conduction and heat dissipation performance of the coating is reduced, the high temperature resistance is reduced, the performances such as wear resistance and hardness are reduced, and as the citric acid is weak acid, chemical equilibrium shift exists in the reaction process, and only when the citric acid is excessive, the stable complex between the metal ions and the citric acid can be ensured.
In example 9, compared with example 3, the addition amount of dopamine hydrochloride is lower, only 5g of dopamine hydrochloride is added, so that the poly-dopamine covered on the surface of the metal oxide nano powder is less, the thermal conductivity is reduced, the high temperature resistance is reduced, a layer of poly-dopamine is reacted and compounded on the surface of the metal oxide nano powder, the surface wettability of the nano material is enhanced due to the fact that the poly-dopamine is rich in amino and hydroxyl, tiny water droplets are easy to penetrate into the surface of the nano material to achieve the effect of evaporation and heat dissipation, and in addition, the poly-dopamine is easy to be bonded with a silane coupling agent, so that the modified poly-dopamine is copolymerized with silica sol and organosilicon to obtain the uniform high temperature resistant heat dissipation coating.
Example 10 compared with example 3, the replacement of methyltriethoxysilane by dodecylmethyldimethoxysilane resulted in a decrease in mechanical properties and the like of the coating, because the higher the number of alkoxy groups directly bonded to silicon atoms in the organosiloxane monomer, the higher the hydrolytic activity, the longer the organic chain in the organosiloxane monomer, the greater the steric hindrance, the poorer the hydrolytic ability and water solubility, and the worse the copolymerization reaction of organosilane and silica sol in the coating, the poorer the coating properties.
Compared with the embodiment 3, the comparative example 1 has the advantages that the step S2 is not carried out, so that the surface of the metal oxide nano powder is not covered, the heat conductivity coefficient is obviously reduced, the high temperature resistance is obviously reduced, all properties are reduced, the surface wettability of the nano material is enhanced by compounding a layer of polydopamine on the surface of the metal oxide nano powder through reaction, tiny water drops are easy to penetrate into the surface of the nano material to play the effects of evaporation and heat dissipation, and in addition, the polydopamine is easy to bond with a silane coupling agent, so that the modified and silicon sol and organic silicon are copolymerized to obtain the uniform high temperature resistant heat dissipation coating.
Compared with the embodiment 3, the comparative example 2 does not carry out the step S3, the high temperature resistance, the weather resistance, the adhesive force, the heat conduction performance and the abrasion resistance are reduced, the surface of the nano material is connected with the organic silicon alkoxy after the poly dopamine/metal oxide nano powder is modified by the silane coupling agent, so that the poly dopamine/metal oxide nano powder is easy to copolymerize with the silica sol and the organic silicon in the subsequent reaction to form a uniform composite coating, and the poly dopamine/metal oxide nano powder has the advantages of good mechanical property, high temperature resistance, abrasion resistance, good fracture resistance, good flexibility and elasticity, self heat dissipation and far infrared release, good heat dissipation effect and high temperature resistance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. The preparation method of the high-temperature-resistant heat-dissipation coating is characterized by comprising the following steps of:
s1, preparing metal oxide nano powder: dissolving metal nitrate in water, adding citric acid, performing ultrasonic dispersion, heating to a first temperature, and evaporating the solvent to obtain sol; then raising the temperature to a second temperature, reducing the pressure intensity to form dry gel, taking out the dry gel, and igniting the dry gel to obtain metal oxide nano powder; the metal nitrate is a mixture of ferric nitrate, aluminum nitrate and cobalt nitrate, and the mass ratio of the ferric nitrate to the aluminum nitrate to the cobalt nitrate to the citric acid is (4-12): 13: (1-5): (30-40); the first temperature is 45-55 ℃; the second temperature is 170-200 ℃; the pressure is reduced to the vacuum degree of 0.01-0.1 MPa;
s2, preparing polydopamine/metal oxide nano powder: uniformly dispersing the metal oxide nano powder prepared in the step S1 in water, adding dopamine hydrochloride, adding a Tris-HCl solution, heating for reaction, centrifuging, washing and drying to obtain poly-dopamine/metal oxide nano powder;
s3, preparing modified polydopamine/metal oxide nano powder: uniformly dispersing the polydopamine/metal oxide nano powder prepared in the step S2 in an ethanol solution, adding a silane coupling agent, heating for reaction, centrifuging, washing and drying to obtain modified polydopamine/metal oxide nano powder; the silane coupling agent is a compound mixture of KH550 and KH590, and the mass ratio is 5: (1-3);
s4, preparing organic silicon modified silica sol: uniformly mixing alkaline silica sol, water and crystal whisker silicon, adding organosilane and acetic acid, and carrying out mixing reaction to obtain organic silicon modified silica sol;
s5, preparing the high-temperature-resistant heat-dissipation coating: adding the modified polydopamine/metal oxide nano powder prepared in the step S3 into the organic silicon modified silica sol prepared in the step S4, homogenizing, standing and curing to obtain the high-temperature-resistant heat-dissipation coating; the thermal conductivity coefficient of the coating is 12-21W/m multiplied by K, the pencil hardness is 4-6H, and the adhesive force is 0-2 grade.
2. The method for preparing the high-temperature-resistant heat-dissipation coating according to claim 1, wherein the mass ratio of the metal oxide nano powder to the dopamine hydrochloride in step S2 is 10: (17-22); the pH value of the Tris-HCl solution is 8-8.5, the heating reaction temperature is 40-50 ℃, and the time is 3-5 h.
3. The method for preparing the high-temperature-resistant heat-dissipation coating as claimed in claim 1, wherein the mass ratio of the poly-dopamine/metal oxide nano powder to the silane coupling agent in step S3 is 10: (0.5-1); the heating reaction temperature is 70-80 ℃, and the time is 1-3 h.
4. The method for preparing the high temperature resistant heat dissipation coating as recited in claim 1, wherein the organosilane is methyltriethoxysilane in step S4, and the mass ratio of the alkaline silica sol, water, whisker silicon, methyltriethoxysilane and acetic acid is (30-40): (20-30): (10-20): (20-30): (0.5-1); the mixing reaction temperature is 25-35 ℃ and the time is 2-4 h.
5. The method for preparing the high-temperature-resistant heat-dissipation coating according to claim 1, wherein the mass ratio of the modified poly-dopamine/metal oxide nano powder to the organosilicon modified silica sol in step S5 is (2-5): 12; the homogenization condition is 12000-15000r/min for 3-5 min; the curing time is 7-10 h.
6. The preparation method of the high-temperature-resistant heat-dissipation coating as claimed in claim 1, which is characterized by comprising the following steps:
s1, preparing metal oxide nano powder: dissolving 4-12 parts by weight of ferric nitrate, 13 parts by weight of aluminum nitrate and 1-5 parts by weight of cobalt nitrate in water, adding 30-40 parts by weight of citric acid, performing ultrasonic dispersion, and heating to 45-55 ℃ to evaporate the solvent to obtain sol; then raising the temperature to 170-200 ℃ and the vacuum degree to 0.01-0.1MPa to form dry gel, taking out the dry gel, and igniting the dry gel to obtain metal oxide nano powder;
s2, preparing polydopamine/metal oxide nano powder: uniformly dispersing 10 parts by weight of the metal oxide nano powder prepared in the step S1 in water, adding 17-22 parts by weight of dopamine hydrochloride, adding 1-2 parts by weight of Tris-HCl solution with the pH value of 8-8.5, heating to 40-50 ℃, reacting for 3-5h, centrifuging, washing and drying to obtain poly-dopamine/metal oxide nano powder;
s3, preparing modified polydopamine/metal oxide nano powder: uniformly dispersing 10 parts by weight of the polydopamine/metal oxide nano powder prepared in the step S2 in an ethanol solution, adding 0.5-1 part by weight of a silane coupling agent, heating to 70-80 ℃, reacting for 1-3h, centrifuging, washing, and drying to obtain modified polydopamine/metal oxide nano powder;
the silane coupling agent is a compound mixture of KH550 and KH590, and the mass ratio is 5: (1-3);
s4, preparing organic silicon modified silica sol: uniformly mixing 30-40 parts by weight of alkaline silica sol, 20-30 parts by weight of water and 10-20 parts by weight of crystal whisker silicon, adding 20-30 parts by weight of methyltriethoxysilane and 0.5-1 part by weight of acetic acid, and carrying out mixing reaction at 25-35 ℃ for 2-4h to obtain organic silicon modified silica sol;
s5, preparing the high-temperature-resistant heat-dissipation coating: adding 2-5 parts by weight of the modified polydopamine/metal oxide nano powder prepared in the step S3 into 12 parts by weight of the organic silicon modified silica sol prepared in the step S4, homogenizing for 3-5min at 12000-15000r/min, and standing and curing for 7-10h to obtain the high-temperature-resistant heat-dissipation coating.
7. A high-temperature resistant heat-dissipating coating material produced by the production method as claimed in any one of claims 1 to 6.
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