CN108193268B - Crystal material and preparation method and application thereof - Google Patents

Crystal material and preparation method and application thereof Download PDF

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CN108193268B
CN108193268B CN201711351658.7A CN201711351658A CN108193268B CN 108193268 B CN108193268 B CN 108193268B CN 201711351658 A CN201711351658 A CN 201711351658A CN 108193268 B CN108193268 B CN 108193268B
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crystalline material
hpo
crystal material
reaction kettle
drying
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CN108193268A (en
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张志杰
徐志魁
钟明峰
吴文刚
黄晓盈
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South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution

Abstract

The invention discloses a crystal material with a chemical formula of Mg11(HPO3)8(OH)6The reflectivity of ultraviolet visible near-infrared band of 0.2-2.5 mu m is more than 88%, and the emissivity of the ultraviolet visible near-infrared band of 2.5-25 mu m is more than 0.90. The invention also discloses a preparation method of the crystal material, which comprises the following steps: based on tetrahydrate magnesium acetate and phosphorous acid raw materials, cyclohexylamine template is added at the same time, and Mg is prepared by hydrothermal synthesis11(HPO3)8(OH)6A crystalline powder. The crystal material can well combine the comprehensive performance of reflection and radiation, the actual cooling effect is 2-10 ℃ better than that of the common heat reflection material titanium dioxide in the market, and the crystal material can be well applied to the field of heat reflection infrared radiation.

Description

Crystal material and preparation method and application thereof
Technical Field
The invention relates to a crystal material, in particular to a material with high ultraviolet-visible near-infrared reflectivity and medium-far infrared emissivity and a preparation method thereof.
Background
Global warming is a serious environmental problem that is not underestimated. There is no doubt that the increasing energy consumption which brings about huge greenhouse gases is the main cause. The energy usage of China increased from 0.59 million tons of standard coal equivalent in 1980 to 29.2 million tons in 2009. In 2011, the building energy consumption accounts for 27.5 percent of the total energy consumption, and the proportion is increased to 35 percent by 2020. Passive cooling or cooling without any power input may have a significant impact on global energy consumption.
The passive cooling or cooling material has high reflectivity in an ultraviolet-visible-near infrared region in solar energy, and can penetrate the self energy through an atmospheric infrared window in a 8-13 um wave band in an infrared radiation mode as far as possible to be efficiently emitted to the outer layer of the atmosphere, so that the purposes of comprehensive cooling or cooling are achieved by combining reflection and emission.
In the daytime passive cooling study, Aaskath P.Raman introduced a seven-layer HfO2And SiO2Integrated photonic solar reflectors and thermal emitters are formed which reflect 97% of incident sunlight while emitting strongly selectively in an atmospheric transparent window. The company Eden Redehaeli uses five layers of a-quartz, SiC, MgF2，TiO2And Ag, etc. have designed passive cooling devices. The test device has low absorptivity in the solar spectrum and high emissivity in the atmospheric window. In summary, most of the current day passive heat dissipation area research is focused on the design of the device, i.e. the combination of the reflective layer and the emissive layer. Most of them are complex in structure and depend on preparation technology.
Disclosure of Invention
In order to overcome the above disadvantages and shortcomings of the prior art, the present invention provides a crystal material, which has a reflectivity of ultraviolet-visible near-infrared band of 0.2-2.5 μm of above 88%, and an emissivity of mid-infrared band of 2.5-25 μm of above 0.90.
The invention also aims to provide a preparation method of the crystal material, which has simple process.
It is a further object of the present invention to provide the use of the crystalline material described above.
The purpose of the invention is realized by the following technical scheme:
a crystalline material having the formula Mg11(HPO3)8(OH)6。
The reflectivity of the crystal material in the ultraviolet visible near-infrared band of 0.2-2.5 mu m is more than 88%, and the emissivity of the crystal material in the middle and far-infrared band of 2.5-25 mu m is more than 0.90.
A method of preparing a crystalline material comprising the steps of:
(1) weighing magnesium acetate tetrahydrate and phosphorous acid according to a molar ratio of 1: 0.5-1.5, adding deionized water for dissolving, and stirring for 15-30 minutes to obtain a solution;
(2) adding a cyclohexylamine template into the solution obtained in the step (1), and continuously stirring for 0.5-1.5 hours to obtain an emulsion; the volume ratio of the cyclohexylamine template to the emulsion is 1: 4.8-1: 12;
(3) reacting the mixed solution obtained in the step (2) in a high-pressure reaction kettle at the reaction temperature of 140-180 ℃;
(4) after reacting for 2000 minutes, cooling the obtained solution, performing suction filtration, drying the obtained solid, and grinding to obtain a powdery crystal material with a chemical formula of Mg11(HPO3)8(OH)6。
The preparation method of the crystal material comprises the following steps of (1) stirring: the magnetic stirring mode is adopted, and the rotating speed is 200-400 r/min.
The preparation method of the crystal material comprises the step (3) of reacting the mixed solution in a high-pressure reaction kettle, and specifically comprises the following steps:
and adding the stirred emulsion into a composite high-pressure reaction kettle, and placing the composite high-pressure reaction kettle in a drying box for reaction.
The preparation method of the crystal material comprises the step (4) of drying, and specifically comprises the following steps: drying at 80-110 ℃.
The crystal material is applied as a heat reflection infrared radiation material.
Use of said crystalline material with Mg11(HPO3)8(OH)6The heat reflection infrared radiation coating is made for the pigment and filler.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the crystal material has high ultraviolet-visible near-infrared high reflectivity and medium-far infrared high emissivity, the ultraviolet-visible near-infrared band reflectivity of 0.2-2.5 mu m can reach more than 88%, and the medium-far infrared band emissivity of 2.5-25 mu m can reach more than 0.90.
(2) The preparation method of the crystal material has simple preparation process, and the prepared material has excellent performance,
(3) The crystal material can well combine the comprehensive performance of reflection and radiation, the actual cooling effect is 2-10 ℃ better than that of the common heat reflection material titanium dioxide in the market, and the crystal material can be well applied to the field of heat reflection infrared radiation.
Drawings
FIG. 1 is Mg prepared in example 1 of the present invention11(HPO3)8(OH)6Fine XRD pattern of (1).
Fig. 2a is a micrograph of hair on the body surface of silver ants in a desert.
FIG. 2b is Mg prepared according to example 1 of the present invention11(HPO3)8(OH)6The surface scanning electron microscope image of (2).
FIG. 3 is Mg prepared in example 1 of the present invention11(HPO3)8(OH)6The cooling effect is compared with that of the most common heat reflecting material titanium dioxide on the market.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
Weighing 2.144g of magnesium acetate tetrahydrate and 1.64g of phosphorous acid solid powder according to a molar ratio of 0.5:1, pouring the powder into a beaker, dissolving the powder with deionized water, adding a magnetic stirrer, stirring, adjusting the rotating speed to 400r/min, adding 5ml of cyclohexylamine after 15 min, covering a preservative film, and stirring for 15 min to obtain uniform emulsion, wherein the volume ratio of the cyclohexylamine to the emulsion is 1: 12; and (3) putting the uniform emulsion into a reaction kettle, putting the reaction kettle into an oven, setting the temperature of the oven at 140 ℃, and reacting for 2000 minutes. And taking out after the reaction is completed, washing and filtering, drying the sample on the filter paper for 5 hours at 80 ℃, and grinding to obtain the sample with uniform particle size.
The test result of the emissivity of the 2.5-25 mu m middle and far infrared bands of the sample is 0.914, and the reflectivity of the ultraviolet visible near infrared bands of 0.2-2.5 mu m is 0.87.
Fig. 1 is a fine XRD simulation result pattern of the sample prepared in this example. With Co in ICSD database11(HPO3)8(OH)6Based on the modeling of the crystal structure (ICSD #72431), the original Co is usedThe son is replaced by Mg atom, the error Rwp between the simulation value and the experimental value is 8.98 percent by a Rietveld fine-trimming method, and the result reliability is high. The refined XRD shows that the synthesized substance is a new synthesized crystal material with the chemical formula of Mg11(HPO3)8(OH)6。
Fig. 2a is a surface profile of the sample prepared in this example. It was found that its surface topography was similar to the body surface of a desert ant (demonstrated to have both high reflectance of visible light and high emissivity of infrared light) (fig. 2b), which is also Mg11(HPO3)8(OH)6Has good heat reflection and radiation effects.
FIG. 3 shows Mg prepared in this example11(HPO3)8(OH)6The cooling effect is compared with that of the most common heat reflecting material titanium dioxide on the market. With Mg11(HPO3)8(OH)6After the coating is prepared for the pigment and filler, the test shows that the coating is compared with the most common titanium dioxide coating of the heat reflection material on the market for a cooling experiment, and the cooling effect of the coating is 2-10 ℃ better than that of the titanium dioxide when the sunlight is sufficient.
Example 2
Weighing 4.289g of magnesium acetate tetrahydrate and 1.64g of phosphorous acid solid powder according to a molar ratio of 1:1, pouring the powder into a beaker, dissolving the powder with deionized water, adding a magnetic stirrer, stirring, adjusting the rotating speed to 300 r/min, adding 12.5ml of cyclohexylamine after 15 min, covering a preservative film, and stirring for 15 min to obtain uniform emulsion, wherein the volume ratio of the cyclohexylamine to the emulsion is 1: 4.8; and (3) putting the uniform emulsion into a reaction kettle, putting the reaction kettle into an oven, setting the temperature of the oven at 160 ℃, and reacting for 2000 minutes. And taking out after the reaction is completed, washing and filtering, drying the sample on the filter paper for 3 hours at 100 ℃, and grinding to obtain the sample with uniform particle size.
The test result of the emissivity of the 2.5-25 mu m middle and far infrared band of the sample is 0.928, and the reflectivity of the ultraviolet visible near infrared band of 0.2-2.5 mu m is 0.88.
Mg prepared in this example11(HPO3)8(OH)6The test results are similar to those of example 1 and are not described herein again.
Example 3
Weighing 8.578g of magnesium acetate tetrahydrate and 1.64g of phosphorous acid solid powder according to a molar ratio of 2:1, pouring the powder into a beaker, dissolving the powder with deionized water, adding a magnetic stirrer, stirring, adjusting the rotating speed to 200 r/min, adding 10ml of cyclohexylamine after 20 min, covering a preservative film, and stirring for 20 min to obtain uniform emulsion, wherein the volume ratio of the cyclohexylamine to the emulsion is 1: 6; and (3) putting the uniform emulsion into a reaction kettle, putting the reaction kettle into an oven, setting the temperature of the oven at 180 ℃, and reacting for 2000 minutes. And taking out after the reaction is completed, washing and filtering, drying the sample on the filter paper for 2 hours at 110 ℃, and grinding to obtain the sample with uniform particle size.
The test result of the emissivity of the 2.5-25 mu m middle and far infrared band of the sample is 0.933, and the reflectivity of the ultraviolet visible near infrared band of 0.2-2.5 mu m is 0.89.
Mg prepared in this example11(HPO3)8(OH)6The test results are similar to those of example 1 and are not described herein again.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. A crystalline material characterized by the formula Mg11(HPO3)8(OH)6。
2. The crystalline material according to claim 1, wherein the reflectance of the ultraviolet-visible near-infrared band of 0.2 to 2.5 μm is 88% or more, and the reflectance of the mid-infrared band of 2.5 to 25 μm is 0.90 or more.
3. A method for preparing a crystalline material, comprising the steps of:
(1) according to the molar ratio of 1: weighing magnesium acetate tetrahydrate and phosphorous acid at 0.5-1.5, adding deionized water for dissolving, and stirring for 15-30 minutes to obtain a solution;
(2) adding a cyclohexylamine template into the solution obtained in the step (1), and continuously stirring for 0.5-1.5 hours to obtain an emulsion; the volume ratio of the cyclohexylamine template to the emulsion is 1: 4.8-1: 12;
(3) reacting the mixed solution obtained in the step (2) in a high-pressure reaction kettle at the reaction temperature of 140-180 ℃;
(4) after reacting for 2000 minutes, cooling the obtained solution, performing suction filtration, drying the obtained solid, and grinding to obtain a powdery crystal material with a chemical formula of Mg11(HPO3)8(OH)6。
4. The method for preparing a crystalline material according to claim 3, wherein the stirring in step (1) is specifically: the magnetic stirring mode is adopted, and the rotating speed is 200-400 r/min.
5. The method for preparing a crystalline material according to claim 3, wherein the mixed solution in the step (3) is reacted in a high-pressure reaction kettle, specifically:
and adding the stirred emulsion into a composite high-pressure reaction kettle, and placing the composite high-pressure reaction kettle in a drying box for reaction.
6. The method for preparing a crystalline material according to claim 3, wherein the drying of step (4) is specifically: drying at 80-110 ℃.
7. Use of the crystalline material of claim 1 as a heat-reflecting infrared radiation material.
8. Use of a crystalline material according to claim 7, characterised in that Mg is used as Mg11(HPO3)8(OH)6The heat reflection infrared radiation coating is made for the pigment and filler.
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Citations (2)

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CN104692353A (en) * 2015-01-30 2015-06-10 南京理工大学 Porous near-infrared reflective heat insulation material and preparation method thereof
CN107215894A (en) * 2017-06-09 2017-09-29 北京华腾新材料股份有限公司 A kind of heat-insulated granules of pigments of bismoclite near-infrared high reflection and preparation method

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US8636068B2 (en) * 2008-07-28 2014-01-28 Baker Hughes Incorporated Method of reducing corrosion in cement

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104692353A (en) * 2015-01-30 2015-06-10 南京理工大学 Porous near-infrared reflective heat insulation material and preparation method thereof
CN107215894A (en) * 2017-06-09 2017-09-29 北京华腾新材料股份有限公司 A kind of heat-insulated granules of pigments of bismoclite near-infrared high reflection and preparation method

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Synthesis and structures of two isostructural phosphite, Fe11(HPO3)8(OH)6 and Mn11(HPO3)8(OH)6;M. P. Attfield, et al.;《Acta Crystallographica Section C》;19940730;981-984 *

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