CN110540814B - High-permeability rare earth nano heat insulation slurry and preparation method thereof - Google Patents
High-permeability rare earth nano heat insulation slurry and preparation method thereof Download PDFInfo
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Abstract
The invention provides high-transparency rare earth nanometer heat insulation slurry and a preparation method thereof, wherein the high-transparency rare earth nanometer heat insulation slurry comprises the following components in parts by weight: 100 parts of dispersion medium, 2-50 parts of rare earth boride, 0.3-2 parts of anti-settling agent, 0.01-2.5 parts of dispersing agent and 1.13-8.5 parts of other auxiliary agent. The high-transmittance rare earth nanometer heat insulation slurry does not contain nanometer indium-doped tin oxide (ITO), nanometer antimony-doped tin oxide (ATO) and nanometer bismuth-doped tin oxide (BTO) with spectral selectivity, and the components are easy to disperse, low in cost and easy to construct a coating.
Description
Technical Field
The invention belongs to the field of energy-saving and environment-friendly materials, and particularly relates to a high-transparency rare earth nano heat insulation slurry and a preparation method thereof.
Background
In recent years, the problem of energy shortage is more and more emphasized, and energy conservation and emission reduction become the main melody of the times. The global greenhouse gas emission is related to the building energy consumption by statistics of about 1/3. In the case of using a large amount of glass for windows of buildings, ceilings, automobile windows, etc., the heat radiation of light will cause a large increase in energy consumption. The existing method mainly comprises heat insulation coating and glass film pasting which take inorganic functional materials such as ITO (indium tin oxide), ATO (antimony tin oxide) and the like as auxiliary agents, but the coating construction difficulty is high, and the film pasting is difficult to realize the contradiction between the heat insulation rate and the light transmittance. At present, a plurality of new glass products such as hollow glass, Low-e glass and the like exist, but the manufacturing cost is high, and the market is difficult to popularize. The invention provides a high-transmittance rare earth nanometer heat insulation slurry, which is added into a glue film to be used in glued laminated glass of buildings and automobile doors and windows, can effectively isolate a large amount of infrared rays and ultraviolet rays, can also give consideration to higher visible light transmittance, and does not influence the service life of the slurry.
At present, the research on the transparent heat insulating agent at home and abroad mainly focuses on the field of coatings, and some research results are available. Through patent retrieval, world patent WO2018103063 (a manufacturing process of a nano ATO transparent heat-insulating energy-saving glass coating) disperses nano ATO in water-based resin to form a heat-insulating coating, but the coating is difficult to be uniform and the construction difficulty is high. Chinese patent with application number CN201710243083.0, "a glass transparent heat-insulating nano-coating and a preparation method thereof" uses nano ATO-rare earth-polycrystalline silicon as a heat-insulating auxiliary agent, but the heat-insulating effect is very limited; the application number CN201610979211.3 'aqueous strippable transparent heat-insulating glass paint and the preparation method thereof' adopt aqueous nano ATO and ITO composite heat-insulating slurry, the cost is too high, and the mixed slurry is easy to agglomerate. Therefore, the invention of a novel heat insulation material which has the advantages of simple process, obvious effect, high transmittance and easy application and popularization is necessary.
Disclosure of Invention
In view of this, the invention aims to provide a high-transmittance rare earth nano thermal insulation slurry to overcome the defects of the prior art, and the slurry does not contain nano indium-doped tin oxide (ITO), nano antimony-doped tin oxide (ATO) and nano bismuth-doped tin oxide (BTO) with spectral selectivity, and has the advantages of easy dispersion of all components, low cost and easy coating construction.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a high-transparency rare earth nanometer thermal insulation slurry comprises the following components in parts by weight: 100 parts of dispersion medium, 2-50 parts of rare earth boride, 0.3-2 parts of anti-settling agent, 0.01-2.5 parts of dispersing agent and 1.13-8.5 parts of other auxiliary agent.
Preferably, the dispersion medium is one or more of deionized water, ethanol, tert-butanol, acetone, diisobutyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, petroleum ether, cyclohexane and toluene.
Preferably, the rare earth boride is one of praseodymium hexaboride, dysprosium hexaboride, lanthanum hexaboride, cerium hexaboride, rubidium hexaboride, ytterbium hexaboride, europium hexaboride and yttrium hexaboride.
Preferably, the anti-settling agent is one or more of polyolefin wax, modified hydrogenated castor oil, fumed silica, N-methyl pyrrolidone solution of modified polyurea and polyamide wax.
Preferably, the dispersant is one or more of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, tetrapropylammonium bromide, hexadecyltrimethylammonium bromide, ethylenediamine, sodium dodecylbenzene sulfonate, sodium dodecyl sulfate, sodium lignosulfonate, a silane coupling agent KH550, a silane coupling agent KH560, a silane coupling agent KH570 and a silane coupling agent KH 792.
Preferably, the other auxiliary agents comprise an ultraviolet absorbent and a cross-linking agent, and the weight ratio of the ultraviolet absorbent to the cross-linking agent is as follows: (0.05-0.2): (1-5).
Preferably, the other auxiliary agents also comprise light stabilizers, and the weight ratio of the ultraviolet absorber to the cross-linking agent to the light stabilizers is as follows: (0.05-0.2): (1-5): (0.05-0.3).
Preferably, the ultraviolet absorbent is one or more of phenyl salicylate, UV-P, UV-O, UV-9, UV531, UVP-327 and cerium dioxide.
Preferably, the light stabilizer is one or more of AM101, GW540, HPT, zinc oxide and titanium dioxide; the cross-linking agent is one or more than two of dicumyl peroxide, benzoyl peroxide and di-tert-butyl peroxide.
It should be noted that, in the present invention, in terms of the selection of each component, the selection of the dispersion medium component is intended to meet the requirements of downstream product production, the selection and the dosage of the dispersant are determined by the dispersion medium and whether the slurry is stable, and the addition of other additives is to improve the ultraviolet shielding of the slurry and to better adapt to the characteristics of downstream product addition.
Another objective of the present invention is to provide a method for preparing the high-permeability rare earth nano thermal insulation slurry, so as to prepare the high-permeability rare earth nano thermal insulation slurry.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a preparation method of high-transparency rare earth nanometer heat insulation slurry is characterized by comprising the following steps: the method comprises the following steps:
(1) adding the rare earth boride micron-sized powder, the anti-settling agent and the dilute dispersing agent in the formula amount into the dispersing medium in the formula amount, and uniformly mixing and stirring;
(2) shearing and dispersing the dispersion liquid obtained in the step (1) in a sand mill at a high speed for 0.5-3 h;
(3) adding other auxiliary agents in a formula amount into the dispersion liquid obtained in the step (2), wherein the weight ratio of the ultraviolet absorbent, the cross-linking agent and the light stabilizer in the other auxiliary agents is as follows: (0.05-0.2): (1-5): (0.05-0.3);
(4) and (4) uniformly mixing the slurry obtained in the step (3) and performing ultrasonic treatment for 2-30min to obtain uniformly dispersed high-transparency rare earth nanometer heat insulation slurry.
Compared with the prior art, the high-transparency rare earth nanometer heat insulation slurry has the following advantages:
(1) the rare earth boride is used as a raw material, can absorb and scatter heat radiation in a near infrared region, can more effectively utilize visible light and block heat energy, is used as a novel heat-insulating functional material, and has better performance than traditional transparent heat-insulating materials such as ATO (antimony tin oxide), ITO (indium tin oxide) and the like.
(2) Compared with ATO, ITO and other materials, the shielding effect can be achieved with a small addition amount, and the production cost is low. Specifically, the nano rare earth boride crystal structure selected by the invention has an LSPR (localized surface plasmon resonance) effect, and the nano particles have excellent permeability to visible light in sunlight and have absorption and shielding effects on near infrared thermal radiation with a wider wave band than ATO and ITO.
(3) Compared with the prior art, the production process is simple and easy to control and operate.
(4) The prepared slurry is convenient for the production and addition of downstream products due to good dispersibility and good mixing uniformity with the downstream products, can overcome the defects of difficult construction, uneven brushing and the like caused by a coating process, can be directly added into a glue film production process to be applied to transparent laminated glass, enhances the safety and prolongs the service life of the transparent laminated glass.
The method for preparing the high-permeability rare earth nanometer heat insulation slurry has the same advantages as the high-permeability rare earth nanometer heat insulation slurry compared with the prior art, and the detailed description is omitted.
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 conventional methods unless otherwise specified.
The present invention will be described in detail with reference to examples.
Example 1
A high-transparency rare earth nanometer thermal insulation slurry comprises the following components in parts by weight: 100 parts of ethanol, 10 parts of rare earth boride powder, 0.5 part of polyvinylpyrrolidone, 0.8 part of fumed silica and 3 parts of other additives. Wherein: the rare earth boride is lanthanum hexaboride; in other auxiliary agents, the ultraviolet absorbent is cerium dioxide, the light stabilizer is HPT, the cross-linking agent is di-tert-butyl peroxide, and the ratio of cerium dioxide: the weight ratio of HPT to di-tert-butyl peroxide was 2:2: 1.
The preparation method of the high-permeability rare earth nanometer heat insulation slurry comprises the following steps: fully mixing the rare earth boride micron-sized powder with polyvinylpyrrolidone and fumed silica in ethanol, adding the mixed solution into a sand mill, grinding and dispersing for 0.5h, taking out, uniformly mixing with other auxiliaries, and performing ultrasonic dispersion for 2min to obtain the nano rare earth transparent heat insulation slurry with the particle size of 30 nm.
The nano rare earth transparent heat insulation slurry of the embodiment is mixed with commercially available EVA master batch to be subjected to tape casting to form a film, and the laminated glass is prepared, and the test can obtain: the visible light transmittance is 87%, the infrared ray rejection rate is 92%, the ultraviolet rejection rate is 95.1%, and the temperature drop range of a heat insulation instrument is 12 ℃.
Example 2
A high-transparency rare earth nanometer thermal insulation slurry comprises the following components in parts by weight: 100 parts of mixed solution of tert-butyl alcohol and deionized water, 30 parts of rare earth boride powder, 1.5 parts of mixture of polyvinylpyrrolidone and sodium dodecyl sulfate, 0.5 part of fumed silica and 5 parts of other auxiliary agents. Wherein: the mixing weight ratio of the tertiary butanol to the deionized water is 1: 2; the rare earth boride is cerium hexaboride; the weight ratio of the polyvinylpyrrolidone to the sodium dodecyl sulfate is 1: 2; other additives include UV absorber and light stabilizer, the UV absorber is UV-9, the light stabilizer is GW540, and the weight ratio of UV-9 to GW540 is 2: 1.
The preparation method of the high-permeability rare earth nanometer heat insulation slurry comprises the following steps: fully mixing the rare earth boride micron-sized powder with polyvinylpyrrolidone, sodium dodecyl sulfate and fumed silica in a mixed solution of tert-butyl alcohol and deionized water, adding the mixed solution into a sand mill, grinding and dispersing for 1h, taking out, uniformly mixing with other auxiliaries, and performing ultrasonic dispersion for 15min to obtain the nano rare earth transparent heat insulation slurry with the particle size of 30 nm.
The nano rare earth transparent heat insulation slurry of the embodiment is mixed with commercially available EVA master batch to be subjected to tape casting to form a film, and the laminated glass is prepared, and the test can obtain: the visible light transmittance is 88%, the infrared ray rejection rate is 94%, the ultraviolet rejection rate is 96.2%, and the testing temperature drop range of the heat insulation instrument is 13 ℃.
Example 3
A high-transparency rare earth nanometer thermal insulation slurry comprises the following components in parts by weight: 100 parts of ethyl acetate, 20 parts of rare earth boride powder, 0.8 part of a mixture of polyethylene glycol and a silane coupling agent KH550, 1.5 parts of fumed silica and 4 parts of other additives. Wherein the rare earth boride is lanthanum hexaboride, and the mixing weight ratio of the polyethylene glycol to the silane coupling agent KH550 is 1: 2; the other auxiliary agents comprise an ultraviolet absorbent, a light stabilizer and a cross-linking agent, wherein the ultraviolet absorbent is UV531, the light stabilizer is titanium dioxide, the cross-linking agent is benzoyl peroxide, and the weight ratio of the UV531 to the titanium dioxide to the benzoyl peroxide is 4:3: 1.
The preparation method of the high-permeability rare earth nanometer heat insulation slurry comprises the following steps: fully mixing the rare earth boride micron-sized powder with polyethylene glycol, a silane coupling agent and fumed silica in ethyl acetate, adding the mixed solution into a sand mill, grinding and dispersing for 2h, taking out, uniformly mixing with an auxiliary agent, and performing ultrasonic dispersion for 30min to obtain the nano rare earth transparent heat insulation slurry with the particle size of 30 nm.
Mixing the nano rare earth transparent heat insulation slurry with commercially available EVA master batches, carrying out tape casting to form a film, preparing laminated glass, and testing to obtain: the visible light transmittance is 86%, the infrared ray rejection rate is 93%, the ultraviolet rejection rate is 95.8%, and the temperature drop range of the heat insulation instrument is 12 ℃.
Example 4
A high-transparency rare earth nanometer thermal insulation slurry comprises the following components in parts by weight: 100 parts of cyclohexane, 5 parts of rare earth boride powder, 1 part of a mixture of polyvinyl alcohol and sodium dodecyl benzene sulfonate, 2 parts of polyethylene wax and 1.5 parts of other additives. Wherein the rare earth boride is europium hexaboride; the mixing weight ratio of the polyvinyl alcohol to the sodium dodecyl benzene sulfonate is 2: 3; the other auxiliary agents comprise an ultraviolet absorber and a light stabilizer, wherein the ultraviolet absorber is UVP-327, the light stabilizer is zinc oxide, and the weight ratio of the UVP-327 to the zinc oxide is 3: 1.
The preparation method of the high-permeability rare earth nanometer heat insulation slurry comprises the following steps: fully mixing the rare earth boride micron-sized powder with polyvinyl alcohol, sodium dodecyl benzene sulfonate and polyethylene wax in cyclohexane, adding the mixed solution into a sand mill, grinding and dispersing for 3h, taking out, uniformly mixing with other auxiliary agents, and performing ultrasonic dispersion for 20min to obtain the nano rare earth transparent heat insulation slurry with the particle size of 30 nm.
Mixing the nano rare earth transparent heat insulation slurry with commercially available EVA master batches, carrying out tape casting to form a film, preparing laminated glass, and testing to obtain: the visible light transmittance is 85%, the infrared ray rejection rate is 91%, the ultraviolet rejection rate is 96%, and the testing temperature drop range of the heat insulation instrument is 11 ℃.
In examples 1 to 4, the commercially available EVA masterbatch was made of EA28150 EVA made by Korean LG chemistry, and the VA content was 28 wt%.
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. A preparation method of high-transparency rare earth nanometer heat insulation slurry is characterized by comprising the following steps: the method comprises the following steps:
(1) adding 2-50 parts of rare earth boride micron-sized powder, 0.3-2 parts of anti-settling agent and 0.01-2.5 parts of dilute dispersing agent into 100 parts of dispersing medium, and uniformly mixing and stirring;
(2) shearing and dispersing the dispersion liquid obtained in the step (1) in a sand mill at a high speed for 0.5-3 h;
(3) adding 1.13-8.5 parts of other auxiliary agents into the dispersion liquid obtained in the step (2), wherein the weight ratio of the ultraviolet absorbent, the cross-linking agent and the light stabilizer in the other auxiliary agents is as follows: (0.05-0.2): (1-5): (0.05-0.3);
(4) uniformly mixing the slurry obtained in the step (3) and carrying out ultrasonic treatment for 2-30min to obtain uniformly dispersed high-transparency rare earth nanometer heat insulation slurry,
the dispersing agent is one or more than two of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, tetrapropylammonium bromide, hexadecyltrimethylammonium bromide, ethylenediamine, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium lignosulfonate, a silane coupling agent KH550, a silane coupling agent KH560, a silane coupling agent KH570 and a silane coupling agent KH 792.
2. The preparation method of the high-permeability rare earth nano heat insulation slurry according to claim 1, characterized by comprising the following steps: the dispersion medium is one or more than two of deionized water, ethanol, tert-butyl alcohol, acetone, diisobutyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, propylene glycol methyl ether acetate, petroleum ether, cyclohexane and toluene.
3. The preparation method of the high-permeability rare earth nano heat insulation slurry according to claim 1, characterized by comprising the following steps: the rare earth boride is one of praseodymium hexaboride, dysprosium hexaboride, lanthanum hexaboride, cerium hexaboride, rubidium hexaboride, ytterbium hexaboride, europium hexaboride and yttrium hexaboride.
4. The preparation method of the high-permeability rare earth nano heat insulation slurry according to claim 1, characterized by comprising the following steps: the anti-settling agent is one or more than two of polyolefin wax, modified hydrogenated castor oil, fumed silica, N-methyl pyrrolidone solution of modified polyurea and polyamide wax.
5. The preparation method of the high-permeability rare earth nano heat insulation slurry according to claim 1, characterized by comprising the following steps: the ultraviolet absorbent is one or more than two of phenyl salicylate, UV-P, UV-O, UV-9, UV531, UVP-327 and cerium dioxide.
6. The preparation method of the high-permeability rare earth nano heat insulation slurry according to claim 1, characterized by comprising the following steps: the light stabilizer is one or more than two of AM101, GW540, HPT, zinc oxide and titanium dioxide; the cross-linking agent is one or more than two of dicumyl peroxide, benzoyl peroxide and di-tert-butyl peroxide.
7. A high-transparency rare earth nanometer thermal insulation slurry is characterized in that: obtained by the preparation method of any one of claims 1 to 6.
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| CN111285380B (en) * | 2020-02-04 | 2022-12-16 | 天津包钢稀土研究院有限责任公司 | Preparation method and application of multi-rare earth co-doped boride and nano heat insulation powder thereof |
| CN113956740A (en) * | 2021-12-04 | 2022-01-21 | 无锡市明江保温材料有限公司 | Thermal insulation slurry using aerogel and preparation method |
| CN114540974A (en) * | 2022-04-25 | 2022-05-27 | 天津包钢稀土研究院有限责任公司 | Infrared heat storage functional fiber and preparation method thereof |
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| US20150111063A1 (en) * | 2012-03-23 | 2015-04-23 | Massachusetts Institute Of Technology | Hydrophobic materials incorporating rare earth elements and methods of manufacture |
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