CN111285380B - Preparation method and application of multi-rare earth co-doped boride and nano heat insulation powder thereof - Google Patents
Preparation method and application of multi-rare earth co-doped boride and nano heat insulation powder thereof Download PDFInfo
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Abstract
The invention provides a preparation method and application of a multi-rare earth co-doped boride and a nano heat insulation powder thereof, wherein the chemical formula is R x R’ 1‑x B 6 Wherein: r, R' is different rare earth elements, B is boron element, 0<x<1; r, R' is selected from two of praseodymium, dysprosium, lanthanum, cerium, rubidium, ytterbium, europium, gadolinium or yttrium. According to the multi-rare earth co-doped boride disclosed by the invention, due to the doping of multi-rare earth, the spectral absorption wave of the material is red-shifted, so that a better heat insulation effect is achieved; the preparation method adopts a microwave solid phase method, and the particle size of the powder is smaller and can reach below hundred nanometers.
Description
Technical Field
The invention belongs to the field of energy-saving and environment-friendly materials, and particularly relates to a multi-rare earth co-doped boride and a preparation method thereof, as well as high-permeability rare earth nano heat-insulating powder containing the multi-rare earth co-doped boride, a preparation method and application 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. According to statistics, nearly 1/3 of global greenhouse gas emission is related to building energy consumption. 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. Many new glass products such as hollow glass, low-e glass and the like exist in the market, but the manufacturing cost is high, and the market is difficult to popularize. The existing solution mainly includes heat-insulating coating and glass film using inorganic functional materials such as ITO (indium tin oxide), ATO (antimony tin oxide) and the like as additives, but compatibility between heat-insulating medium and auxiliary materials often affects the effect. Compared with a heat insulation medium and a heat insulation coating, the high-permeability rare earth nano heat insulation powder provided by the invention has stable properties, is easy to add, and is convenient to store and transport. The product can be added into rubber film for laminated glass of buildings and doors and windows of automobiles; the glass can be added into a glass melting step to be made into heat insulation glass; can be added into ink for screen printing of glass; can be added into a coating medium to prepare the heat-insulating coating. The product 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 product.
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, PCT international application 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 requirements on the dispersibility and compatibility of nano materials are high, the coating is difficult to be uniform, and the construction difficulty is high. The Chinese patent with the application number of CN201710243083.0, namely 'a glass transparent heat-insulating nano coating and a preparation method thereof', takes nano ATO-rare earth-polycrystalline silicon as a heat-insulating auxiliary agent, but has very limited heat-insulating effect; the Chinese patent with the application number of CN201610979211.3, namely the water-based strippable transparent heat-insulating glass coating and the preparation method thereof, adopts water-based nano ATO and ITO composite heat-insulating slurry, so that the cost is too high, and the mixed slurry is easy to agglomerate. The Chinese patent with the application number of CN201721118368.3, namely 'heat insulation energy-saving glass', comprises outer layer glass and inner layer glass, wherein the two layers of glass are separated by a certain distance, a heat insulation cavity is formed between the two layers of glass, the outer layer glass comprises a heat insulation layer containing nano tungsten oxide and/or nano tin antimony oxide heat insulation powder, and the heat insulation glass has a complex process and strict requirements. Chinese patent CN201711114822.2, a high-strength nano waterproof heat-insulating powder and a preparation method thereof, prepares powder with excellent waterproof performance and heat-insulating performance by adopting nano calcium carbonate and the like, but cannot meet the requirement of transmittance, and is an opaque heat-insulating powder material. Therefore, the invention of the novel heat-insulating powder material which has the advantages of simple process, easy dispersion, storage and transportation, obvious effect, high transmittance and convenient application and popularization is necessary.
At present, the rare earth boride nano synthesis cost is high, the yield is low, and large-scale industrial production is difficult. The traditional sintering method of rare earth boride micron powder needs to synthesize at a high temperature of more than 1000 ℃, and the energy consumption is higher.
Disclosure of Invention
In view of the above, the present invention is directed to provide a multiple rare earth co-doped boride to overcome the defects of the existing materials and technologies, and the multiple rare earth co-doped boride enables the spectral absorption wave of the material to be red-shifted, so as to achieve a better infrared absorption effect.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
multiple rare earth co-doped boride of the formula R x R’ 1-x B 6 Wherein: r, R' is a different rare earth element, B is boron, 0<x<1。
Preferably, R, R' is selected from two of praseodymium, dysprosium, lanthanum, cerium, rubidium, ytterbium, europium, gadolinium or yttrium.
The second purpose of the invention is to provide a method for preparing the above-mentioned multiple rare earth co-doped boride, which adopts a microwave solid phase method, and has low reaction temperature, less impurities and smaller powder particle size, and the central particle size can reach below hundred nanometers.
The preparation method of the multi-rare earth co-doped boride comprises the steps of drying a rare earth source containing two rare earth elements and a boron source, mixing the dried rare earth source and boron source with an auxiliary agent, performing ball milling, and performing microwave radiation treatment on the mixture.
Preferably, the rare earth source is one or more of rare earth carbonate, rare earth chloride and rare earth oxide.
Preferably, the rare earth elements in the rare earth source are two of praseodymium, dysprosium, lanthanum, cerium, rubidium, ytterbium, europium, gadolinium or yttrium.
Preferably, the boron source is one or more than two of boron powder, potassium borohydride, sodium borohydride and boric acid.
Preferably, the auxiliary agent is one or more than two of magnesium powder, aluminum powder, iron powder, sodium metal and potassium metal.
Preferably, the rare earth source: a boron source: the molar ratio of the auxiliary agent is 1: (3-10): (5-9).
Preferably, the temperature of the microwave radiation treatment is 500-1000 ℃, and the heat preservation time is 4-10h.
Preferably, the microwave irradiation treatment is performed in a microwave laboratory oven.
Preferably, the preparation method of the multi-rare earth co-doped boride also comprises the steps of purifying and purifying the powder treated by microwave radiation, and drying in vacuum to obtain the multi-rare earth co-doped boride powder.
Preferably, the purification method comprises acid leaching and distilled water washing and suction filtering.
Further preferably, the temperature of the acid leaching is 40-100 ℃, and the acid used for the acid leaching is diluted hydrochloric acid.
The third purpose of the invention is to provide the high-transparency rare earth nano heat-insulating powder, so that the high-transparency rare earth nano heat-insulating powder contains the multi-rare earth co-doped boride powder prepared by the preparation method of the multi-rare earth co-doped boride.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
the nano heat insulation powder containing the multi-rare earth co-doped boride further comprises a dispersing agent and a dispersion medium; the content of the dispersing medium is 100 parts by weight, the content of the multi-rare earth co-doped boride is 5-30 parts by weight, and the content of the dispersing agent is 0.05-1.5 parts by weight.
Preferably, the dispersing agent is one or more than two of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, tetrapropylammonium bromide, hexadecyl trimethyl ammonium bromide, ethylenediamine, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium lignin sulfonate, polyether modified silicone oil, modified acrylate copolymer, silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570 and silane coupling agent KH 792.
Preferably, the dispersion medium is one or more of deionized water, ethanol, tert-butanol, acetone, diisobutyl ketone, methyl isobutyl ketone, ethyl acetate, propylene glycol methyl ether acetate, cyclohexane and toluene.
The fourth purpose of the present invention is to provide a method for preparing the nanometer thermal insulation powder, so as to prepare the high-permeability rare earth nanometer thermal insulation powder.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a method for preparing the nano heat-insulating powder, which comprises the following steps:
(1) Fully mixing the multi-rare earth co-doped boride and a dispersing agent in a dispersion medium to obtain a dispersion liquid;
(2) Preparing uniformly dispersed high-permeability rare earth nanometer heat insulation slurry after sanding the dispersion liquid;
(3) And (4) carrying out freeze-drying treatment on the heat insulation slurry to obtain the high-permeability rare earth nanometer heat insulation powder.
Preferably, in the step (2), the dispersion liquid is subjected to high-speed shearing dispersion in a sand mill for 0.5 to 24 hours, and then the obtained slurry is uniformly mixed and subjected to ultrasonic treatment for 2 to 60 minutes to obtain the uniformly dispersed high-permeability rare earth nanometer heat insulation slurry.
Preferably, in step (2), the shear dispersion speed of the dispersion liquid in the grinding machine is 2000-4000r/min.
Preferably, in the step (3), the lyophilization process comprises: and (3) putting the heat insulation slurry into a collection container, pre-freezing at (-50) - (-30) DEG C for 1-3h, drying at (-50) - (-30) DEG C for 2-10h for the first time, then keeping at (-30) - (-10) DEG C for 5-25h, drying at 25-45 ℃ for the second time for 2-10h, and finally obtaining the loose and uniform high-permeability rare earth nanometer heat insulation powder.
Preferably, the pre-freezing is carried out for 2h at-40 ℃, the primary drying temperature is-40 ℃, the temperature is kept for 5-25h at-20 ℃, and the secondary drying is carried out for 2-10h at 35 ℃.
Preferably, the collection vessel is a valve bag.
The invention also relates to application of the nano heat-insulating powder in production of glue films, cloth, coatings and sticking films.
Compared with the prior art, the multi-rare earth co-doped boride has the following advantages:
the multi-rare earth co-doped boride powder synthesized by the invention is doped with multi-rare earth, so that the spectral absorption wave of the material is red-shifted, a better infrared absorption effect is achieved, a better heat insulation effect is achieved, and the granularity of the powder is smaller than that of the rare earth boride powder after being screened in the market, and is less than hundred nanometers.
The preparation method of the multi-rare-earth co-doped boride adopts a microwave solid phase method, adopts a special dielectric heating mechanism, can enable substance molecules to uniformly and effectively absorb energy inside and outside a radiation field to generate a thermal effect, is called an internal heating mode, does not depend on the promotion of temperature gradient, can uniformly penetrate into the sample in a very short time, almost simultaneously heats the whole sample, can enable reactant molecules to obtain energy required by reaction and accelerated diffusion under the low-heat condition, and has the advantages of quick reaction, uniform heating, low energy consumption and the like compared with the traditional sintering method. And the rapid temperature rise of the microwave can inhibit the growth of the grain structure, thereby being beneficial to the formation of fine grains.
According to the nanometer heat insulation powder, the multiple rare earth co-doped boride is used as an effective component, and the rare earth boride has a CsCl structure, so that the local surface plasma resonance effect of free electrons enables the rare earth boride to have a strong absorption effect on photon energy, can absorb and scatter heat radiation in a near infrared region, and can more effectively utilize visible light and block heat energy; and a plurality of rare earths are doped in boride crystal lattices, so that the spectrum absorption wave of the boride crystal lattice is red-shifted, and the infrared absorption of the boride crystal lattice is effectively enhanced. As a novel heat insulation functional material, the material has better performance than the traditional transparent heat insulation materials such as ATO, ITO and the like.
Compared with the prior art, the preparation method of the nanometer heat-insulating powder obtains the nanometer rare earth boride powder through a freeze-drying mode. The freeze drying mode only causes weak bond agglomeration, can prevent hard agglomeration from forming in the powder, and has simple production process and easy control and operation. In addition, the prepared powder is convenient to store and transport and is added in the production of downstream products, the defects of compatibility and the like of liquid material addition can be overcome, the powder can be directly added into production processes such as adhesive films, cloth, coatings, film pasting and the like, the process flow is simplified, and the expected effect can be achieved.
Drawings
FIG. 1 is a process flow for preparing a multi-rare earth co-doped boride according to the present invention;
FIG. 2 is a process flow of preparing rare earth nano heat-insulating powder according to the present invention;
FIG. 3 (a) is an XRD pattern of the multi-rare earth co-doped boride and the rare earth boride lanthanum hexaboride in example 1 of the present invention;
FIG. 3 (b) is an enlarged view of the diffraction of the multi-rare earth co-doped boride and the rare earth boride (211) in example 1 of the present invention;
FIG. 4 shows La prepared by the method for preparing multi-rare earth co-doped boride in embodiment 1 of the invention 0.6 Eu 0.4 B 6 A spectrum absorption contrast diagram of the nano powder and the commercially available lanthanum hexaboride nano powder;
FIG. 5 is a particle size distribution diagram of the rare earth boride, the rare earth nano heat insulating powder and the commercially available multi-rare earth co-doped boride in example 1;
FIG. 6 is a graph showing the optical transmittance of the rare earth nano heat insulating film in example 1.
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 adopts the combination of the microwave solid phase method and the freeze-drying method, the microwave solid phase method is called as an internal heating mode, does not depend on the promotion of temperature gradient, can uniformly penetrate into the sample in a very short time, and can ensure that reactant molecules can obtain the energy required by reaction and accelerated diffusion under the low-heat condition; the freeze drying mode only causes weak bond agglomeration, can prevent hard agglomeration from forming in the powder, and the combination of the two can obtain the high-transparency rare earth nanometer heat-insulating powder under the conditions of low temperature, low energy consumption and low cost.
The present invention will be described in detail with reference to the following examples and accompanying drawings.
Example 1
Multiple rare earth co-doped boride with the chemical formula of La 0.6 Eu 0.4 B 6 。
The preparation method of the multi-rare earth co-doped boride comprises the following steps: drying the rare earth source in an oven at 180 ℃ for 3h, and drying the boron source at 190 ℃ for 60min. Mixing the dried rare earth source, the dried boron source and the auxiliary agent, ball-milling for 2h, placing the mixed raw materials in a microwave experimental furnace, heating to 700 ℃, preserving heat for 6h, and cooling to room temperature along with the furnace. And repeatedly leaching the synthesized powder with dilute hydrochloric acid at 90 ℃, washing with distilled water, performing suction filtration, and performing vacuum drying to obtain the multi-rare-earth co-doped boride powder. Wherein the contents of the rare earth source, the boron source and the auxiliary agent are as follows:
301 parts by weight of a rare earth source;
324 parts by weight of a boron source;
195 parts by weight of an auxiliary agent;
wherein, the rare earth source is a mixture of lanthanum chloride and europium chloride, and the ratio of La: the Eu molar ratio is 3:2; boron source is potassium borohydride, assistant is magnesium powder, and the obtained multiple rare earth co-doped boride is La 0.6 Eu 0.4 B 6 The average particle diameter of the powder was 60nm. La prepared by multi-rare earth co-doped boride preparation method 0.6 Eu 0.4 B 6 And the XRD of the commercial lanthanum hexaboride is shown in figure 3. As can be seen from FIG. 3, the decrease in interplanar spacing results in a shift of the diffraction peak to a large angle according to the Bragg equation, as shown in the figure, the diffraction peak (211) of the homemade multi-rare earth co-doped boride shifts to a large angle compared to lanthanum hexaboride, indicating that Eu is successfully doped into LaB 6 In (1).
Contains the multi-rare earth co-doped boride La 0.6 Eu 0.4 B 6 The high-permeability rare earth nanometer heat-insulating powder comprises the following components in percentage by weight:
100 parts by weight of ethanol;
La 0.6 Eu 0.4 B 6 10 parts of powder;
0.5 part by weight of polyvinylpyrrolidone.
The preparation method of the high-permeability rare earth nanometer heat-insulating powder comprises the following steps: mixing the La 0.6 Eu 0.4 B 6 And fully mixing the powder with polyvinylpyrrolidone in ethanol, adding the mixed solution into a sand mill, grinding and dispersing for 0.5h at the speed of 2200r/min, taking out, and performing ultrasonic dispersion for 2min to obtain the nano rare earth transparent heat insulation slurry with the particle size of 30nm. And then, filling the transparent heat insulation slurry of the nano rare earth into a self-sealing bag, pre-freezing for 2h at the temperature of minus 40 ℃, drying for the first time, keeping for 3h at the temperature of minus 40 ℃, keeping for 12h at the temperature of minus 20 ℃, drying for the second time, keeping for 5h at the temperature of 35 ℃, and finally obtaining the loose and uniform high-transparency rare earth nano heat insulation powder.
Preparing the commercially available lanthanum hexaboride into nano lanthanum hexaboride with the central particle size of 30nm by the steps of preparing the nano heat insulation powder and preparing the nano lanthanum hexaboride and the self-made La 0.6 Eu 0.4 B 6 The spectrum absorption contrast diagram of the prepared nano heat-insulating powder is shown in figure 4, and as can be seen from figure 4, the spectrum absorption of the rare earth europium-doped lanthanum hexaboride is obviously red-shifted compared with the spectrum absorption of the commercially available lanthanum hexaboride. The particle sizes of the multi-rare earth co-doped boride and rare earth nano heat insulation powder prepared in the embodiment and the commercially available rare earth boride are compared, and a particle size distribution diagram determined by a particle size analyzer is shown in fig. 5. As can be seen from figure 5, the central particle size of the sieved commercial rare earth boride is 5 microns, the central particle size of the self-made multi-rare earth co-doped boride is 60nm which is far smaller than that of the commercial rare earth boride, and the central particle size of the rare earth nano heat insulation powder is only 30nm.
Mixing the high-transparency rare earth nanometer heat-insulating powder with commercially available EVA master batches, performing tape casting to form a film, preparing laminated glass, and testing to obtain: the visible light transmittance is 80%, the infrared ray rejection rate is 91%, the ultraviolet rejection rate is 95.1%, and the temperature drop range of a heat insulation instrument is 12 ℃. The optical transmittance test chart is shown in fig. 5.
Example 2
Multiple rare earth co-doped boride of the formula Gd 0.7 Ce 0.3 B 6 。
The preparation method of the multi-rare earth co-doped boride comprises the following steps: drying the rare earth source mixture in an oven at 150 ℃ for 2h, and drying the boron source at 200 ℃ for 80min. Mixing the dried rare earth source, the dried boron source and the auxiliary agent, ball-milling for 2h, placing the mixed raw materials in a microwave experimental furnace, heating to 600 ℃, preserving heat for 8h, and cooling to room temperature along with the furnace. And repeatedly leaching the synthesized powder with dilute hydrochloric acid at 80 ℃, washing with distilled water, performing suction filtration, and performing vacuum drying to obtain the multi-rare-earth co-doped boride powder. Wherein the contents of the rare earth source, the boron source and the auxiliary agent are as follows:
172 parts by weight of a rare earth oxide mixture;
143 parts by weight of a boron source;
135 parts of an auxiliary agent;
wherein, the rare earth source is a mixture of cerium oxide and gadolinium oxide, ce: the Gd molar ratio is 3:7; the boron source is sodium borohydride, the auxiliary agent is aluminum powder, and the multi-rare earth co-doped boride is Gd 0.7 Ce 0.3 B 6 . The average particle diameter of the powder was 70nm.
Gd containing the multi-rare earth co-doped boride 0.7 Ce 0.3 B 6 The high-permeability rare earth nanometer heat insulation powder comprises the following components in percentage by weight:
100 parts of mixed solution of tert-butyl alcohol and deionized water;
Gd 0.7 Ce 0.3 B 6 30 parts of powder;
polyvinylpyrrolidone and sodium dodecyl sulfate 1.5 weight parts;
wherein the mixing weight ratio of the tert-butyl alcohol to the deionized water is 1:2, the weight ratio of the polyvinylpyrrolidone to the sodium dodecyl sulfate is 4:7.
The preparation method of the high-permeability rare earth nanometer heat-insulating powder comprises the following steps: mixing the above Gd 0.7 Ce 0.3 B 6 And fully mixing the powder with polyvinylpyrrolidone and sodium dodecyl sulfate in a mixed solution of tert-butyl alcohol and deionized water, adding the mixed solution into a sand mill, grinding and dispersing at the speed of 2400r/min for 1h, taking out, and performing ultrasonic dispersion for 15min to obtain the nano rare earth transparent heat insulation slurry with the particle size of 30nm. And then, filling the transparent heat insulation slurry of the nano rare earth into a self-sealing bag, pre-freezing for 2h at the temperature of minus 40 ℃, drying for the first time, keeping for 5h at the temperature of minus 40 ℃, keeping for 10h at the temperature of minus 20 ℃, drying for the second time, keeping for 7h at the temperature of 35 ℃, and finally obtaining the loose and uniform high-transparency rare earth nano heat insulation powder.
Mixing the high-transparency rare earth nanometer heat-insulating powder with commercially available EVA master batches, performing tape casting to form a film, preparing laminated glass, and testing to obtain: the visible light transmittance is 86%, the infrared ray blocking rate is 94%, the ultraviolet blocking rate is 97.2%, and the temperature drop range of a heat insulation instrument is 13 ℃.
Example 3
A multi-rare earth co-doped boride of the formula La 0.9 Gd 0.1 B 6 。
The preparation method of the multi-rare earth co-doped boride comprises the following steps: drying the rare earth source in an oven at 180 ℃ for 3h, and drying the boron source at 190 ℃ for 60min. Mixing the dried rare earth source, the dried boron source and the auxiliary agent, ball-milling for 2h, placing the mixed raw materials in a microwave experimental furnace, heating to 800 ℃, preserving heat for 8h, and cooling to room temperature along with the furnace. And repeatedly leaching the synthesized powder with dilute hydrochloric acid at 90 ℃, washing with distilled water, performing suction filtration, and performing vacuum drying to obtain the multi-rare-earth co-doped boride powder. Wherein the contents of the rare earth source, the boron source and the auxiliary agent are as follows:
458 parts by weight of a rare earth source;
485 parts by weight of a boron source;
234 parts of an auxiliary agent;
wherein, the rare earth source is lanthanum carbonate, gadolinium carbonate mixture, la: the Gd molar ratio is 9:1, the boron source is potassium borohydride, the auxiliary agent is metal potassium, and the rare earth boride is La 0.9 Gd 0.1 B 6 The average particle diameter of the powder was 75nm.
Contains the multi-rare earth co-doped boride La 0.9 Gd 0.1 B 6 The high-permeability rare earth nanometer heat insulation powder comprises the following components in percentage by weight:
100 parts by weight of ethyl acetate;
La 0.9 Gd 0.1 B 6 20 parts of powder;
0.8 part by weight of polyethylene glycol and silane coupling agent KH 550;
wherein the mixing weight ratio of the polyethylene glycol and the silane coupling agent KH550 is 1:2.
The preparation method of the high-permeability rare earth nanometer heat-insulating powder comprises the following steps: mixing the La 0.9 Gd 0.1 B 6 And (3) fully mixing the powder with polyethylene glycol and a silane coupling agent KH550 in ethyl acetate, adding the mixed solution into a sand mill, grinding and dispersing for 2h at the speed of 2600r/min, taking out, and performing ultrasonic dispersion for 30min to obtain the nano rare earth transparent heat insulation slurry with the particle size of 30nm. And then, filling the transparent heat insulation slurry of the nano rare earth into a self-sealing bag, pre-freezing for 2h at the temperature of minus 40 ℃, drying for the first time, keeping for 7h at the temperature of minus 40 ℃, keeping for 18h at the temperature of minus 20 ℃, drying for the second time, keeping for 10h at the temperature of 35 ℃, and finally obtaining the loose and uniform high-transparency rare earth nano heat insulation powder.
Mixing the high-transparency rare earth nano heat-insulating powder with a commercially available water-based coating, uniformly stirring to prepare a transparent heat-insulating coating, coating the rare earth nano heat-insulating coating on transparent glass, and testing to obtain the following components: the visible light transmittance is 87%, the infrared ray rejection rate is 93.2%, the ultraviolet rejection rate is 95.8%, and the temperature drop amplitude of a heat insulation instrument is 12 ℃.
Example 4
A multi-rare earth co-doped boride of the formula Eu 0.5 Yb 0.5 B 6 。
The preparation method of the multi-rare earth co-doped boride comprises the following steps: drying the rare earth source for 4h at 300 ℃ in an oven, and drying the boron source for 90min at 160 ℃. Mixing the dried rare earth source, the dried boron source and the auxiliary agent, ball-milling for 3h, placing the mixed raw materials in a microwave experimental furnace, heating to 900 ℃, preserving heat for 10h, and cooling to room temperature along with the furnace. And repeatedly leaching the synthesized powder with dilute hydrochloric acid at 60 ℃, washing with distilled water, performing suction filtration, and performing vacuum drying to obtain the multi-rare-earth co-doped boride powder. Wherein the contents of the rare earth source, the boron source and the auxiliary agent are as follows:
366 parts by weight of a rare earth source;
358 parts by weight of a boron source;
216 parts of an auxiliary agent;
wherein, the rare earth source is a mixture of europium chloride and ytterbium chloride, and the ratio of Eu: the Yb molar ratio is 1:1; the boron source is potassium borohydride, the auxiliary agent is magnesium powder, and the rare earth boride is Eu 0.5 Yb 0.5 B 6 . The average particle diameter of the powder was 85nm.
Contains the multi-rare earth co-doped boride Eu 0.5 Yb 0.5 B 6 The high-permeability rare earth nanometer heat insulation powder comprises the following components in percentage by weight:
100 parts by weight of cyclohexane;
Eu 0.5 Yb 0.5 B 6 5 parts of powder;
polyvinyl alcohol, sodium dodecyl benzene sulfonate 1 weight part;
wherein the mixing weight ratio of the polyvinyl alcohol and the sodium dodecyl benzene sulfonate is 2:3.
Method for preparing high-permeability rare earth nano heat-insulating powderThe method comprises the following steps: the above Eu is added 0.5 Yb 0.5 B 6 And fully mixing the powder with polyvinyl alcohol and sodium dodecyl benzene sulfonate in cyclohexane, adding the mixed solution into a sand mill, grinding and dispersing for 3 hours at the speed of 2800r/min, taking out, and then ultrasonically dispersing for 20 minutes to obtain the nano rare earth transparent heat insulation slurry with the particle size of 30nm. And then, filling the transparent heat insulation slurry of the nano rare earth into a self-sealing bag, pre-freezing for 2h at the temperature of minus 40 ℃, drying for the first time, keeping for 9h at the temperature of minus 40 ℃, keeping for the second time for 20h at the temperature of minus 20 ℃, and drying for the second time, keeping for 8h at the temperature of 35 ℃, thus finally obtaining the loose and uniform high-transparency rare earth nano heat insulation powder.
Converging the high-permeability rare earth nanometer heat-insulating powder, commercial PVB resin and a plasticizer to form a film and prepare laminated glass, and testing to obtain the following components: the visible light transmittance is 85.3%, the infrared ray rejection rate is 90.7%, the ultraviolet rejection rate is 96.2%, and the temperature drop range of a heat insulation instrument is 11 ℃.
It should be noted that in the above examples 1-4, the commercially available EVA master batches were made by Korean LG chemistry, model number EA28150, and have a VA content of 28wt%; PVB resin powder is produced by Jilin Jinuo resin science and technology Limited; the water-based paint is produced by Tianjin Mei Guang science and technology limited company; the particle size was determined by a malvern laser particle sizer.
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 (9)
1. The preparation method of the multi-rare earth co-doped boride is characterized by comprising the following steps: the chemical formula of the multi-rare earth co-doped boride is R x R’ 1-x B 6 Wherein: r, R' is different rare earth elements, B is boron element, 0<x<1；
R, R' is selected from one of praseodymium, dysprosium, lanthanum, cerium, rubidium, ytterbium, europium, gadolinium or yttrium, the method for codoping boride with multiple rare earth comprises the steps of drying a rare earth source containing two rare earth elements and a boron source, mixing the dried rare earth source and boron source with an auxiliary agent, performing ball milling, and performing microwave radiation treatment on the mixture;
the microwave radiation treatment is carried out in a microwave experimental oven;
also comprises the steps of purifying and purifying the powder treated by microwave radiation, and obtaining the multi-rare earth co-doped boride powder after vacuum drying,
the rare earth source is one or more of rare earth carbonate, rare earth chloride and rare earth oxide;
and/or the rare earth elements in the rare earth source are two of praseodymium, dysprosium, lanthanum, cerium, rubidium, ytterbium, europium, gadolinium or yttrium;
and/or the boron source is one or more than two of boron powder, potassium borohydride, sodium borohydride and boric acid;
and/or the auxiliary agent is one or more than two of magnesium powder, aluminum powder, iron powder, metallic sodium and metallic potassium,
a rare earth source: a boron source: the molar ratio of the auxiliary agent is 1: (3-10): (5-9),
the microwave radiation treatment temperature is 500-1000 deg.C, and the heat preservation time is 4-10h.
2. The method for preparing a multiple rare earth co-doped boride according to claim 1, characterized in that: the purification method comprises acid leaching and distilled water washing and suction filtration.
3. The method for preparing a multiple rare earth co-doped boride according to claim 2, characterized in that: the temperature of acid leaching is 40-100 ℃, and the acid used for acid leaching is dilute hydrochloric acid.
4. A method for preparing a nano heat insulating powder containing multiple rare earth co-doped borides prepared by the method of any one of claims 1-3, characterized by: the nano heat insulating powder also comprises a dispersing agent and a dispersing medium; the content of the dispersing medium is 100 parts by weight, the content of the multi-rare earth co-doped boride is 5-30 parts by weight, and the content of the dispersing agent is 0.05-1.5 parts by weight;
the dispersing agent is one or more than two of polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, tetrapropylammonium bromide, hexadecyl trimethyl ammonium bromide, ethylenediamine, sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium lignosulfonate, polyether modified silicone oil, modified acrylate copolymer, silane coupling agent KH550, silane coupling agent KH560, silane coupling agent KH570 and silane coupling agent KH 792;
and/or the dispersion medium is one or more than two of deionized water, ethanol, tertiary butanol, acetone, diisobutyl ketone, methyl isobutyl ketone, ethyl acetate, propylene glycol methyl ether acetate, cyclohexane and toluene,
the preparation method of the nanometer heat-insulating powder comprises the following steps:
(1) Fully mixing the multi-rare earth co-doped boride and a dispersing agent in a dispersion medium to obtain a dispersion liquid;
(2) Preparing uniformly dispersed high-permeability rare earth nanometer heat insulation slurry after sanding the dispersion liquid;
(3) And (4) carrying out freeze-drying treatment on the heat insulation slurry to obtain the high-permeability rare earth nano heat insulation powder.
5. The method for preparing nano heat-insulating powder according to claim 4, wherein the method comprises the following steps:
in the step (2), the dispersion liquid is sheared and dispersed in a sand mill at a high speed for 0.5 to 24 hours, and then the obtained slurry is uniformly mixed and subjected to ultrasonic treatment for 2 to 60 minutes to obtain the uniformly dispersed high-transparency rare earth nanometer heat insulation slurry.
6. The method for preparing nano heat insulating powder according to claim 5, wherein the method comprises the following steps: in the step (2), the shearing and dispersing speed of the dispersion liquid in the sand mill is 2000-4000r/min.
7. The method for preparing nano heat-insulating powder according to claim 4, wherein the method comprises the following steps: in the step (3), the freeze-drying treatment method comprises the following steps: and (3) putting the heat insulation slurry into a collection container, pre-freezing at (-50) - (-30) DEG C for 1-3h, drying at (-50) - (-30) DEG C for 2-10h for the first time, then keeping at (-30) - (-10) DEG C for 5-25h, drying at 25-45 ℃ for the second time for 2-10h, and finally obtaining the loose and uniform high-permeability rare earth nanometer heat insulation powder.
8. The method for preparing nano heat insulating powder according to claim 7, wherein the method comprises the following steps: in the step (3), the freeze-drying treatment method comprises the following steps: placing the heat insulation slurry into a collecting container, pre-freezing at-40 deg.C for 2h, primary drying at-40 deg.C, maintaining at-20 deg.C for 5-25h, and secondary drying at 35 deg.C for 2-10h.
9. The application of the nanometer heat-insulating powder prepared by the preparation method of any one of claims 4 to 8 in the production of glue films, cloth, coatings and film pasting.
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