CN118108726A - K2(HC9N13)·3H2O compound, birefringent crystal, and preparation method and application thereof - Google Patents
K2(HC9N13)·3H2O compound, birefringent crystal, and preparation method and application thereof Download PDFInfo
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- CN118108726A CN118108726A CN202410242326.9A CN202410242326A CN118108726A CN 118108726 A CN118108726 A CN 118108726A CN 202410242326 A CN202410242326 A CN 202410242326A CN 118108726 A CN118108726 A CN 118108726A
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- 239000013078 crystal Substances 0.000 title claims abstract description 61
- 150000001875 compounds Chemical class 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title description 7
- 230000003287 optical effect Effects 0.000 claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 6
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims 1
- 238000004891 communication Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- 230000010287 polarization Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910009372 YVO4 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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Abstract
The invention relates to a K 2(HC9N13)·3H2 O compound and the use of crystal for manufacturing polarized optical device, the crystal belongs to monoclinic system, the space group is P2 1/n, the unit cell parameter is Α=90°, β= 106.046 °, γ=90°, z=4; the invention has the following beneficial effects: has the advantages of simple operation, low cost, less pollution, low toxicity of the used raw materials, short growth period, large double refractive index, stable physical and chemical properties and the like; the crystal can be used for manufacturing a polarized optical device; the polarized optical device manufactured by the birefringent optical crystal plays an important role in modulating polarized light in the fields of optics and communication.
Description
Technical Field
The invention relates to a K 2(HC9N13)·3H2 O compound, a birefringent crystal, a preparation method and application thereof.
Technical Field
Birefringence refers to the phenomenon that when a light wave enters an uneven body, the light wave is decomposed into two linearly polarized lights with different propagation directions and mutually perpendicular polarization directions. The root cause of this phenomenon is the anisotropy of the material. The included angle between the two linearly polarized light beams is related to the incident direction and the polarization state, wherein one light beam always follows the law of refractive index, namely ordinary light (o light), and the refractive index (n o) of the two linearly polarized light beams is irrelevant to the incident direction; the other beam does not follow the ordinary law of refractive index, called extraordinary light (e-light), and its refractive index (n e) is related to the incident direction, and the birefringence is Δn= |n o-ne |, i.e. the difference between the maximum and minimum refractive indices of the two beams. Non-homogeneous bodies such as uniaxial crystals, biaxial crystals, etc. that can produce a birefringence phenomenon are called birefringent crystals.
The birefringent crystal is a very important linear optical material, can be used for manufacturing polarized optical devices, is widely applied to the fields of optics and communication, and is a key material for manufacturing optical elements such as an optical polarizer, a polarization beam splitter, an optical isolator, a circulator, a phase delay device and the like. Currently, commercial birefringent crystals mainly include TiO 2,YVO4、CaCO3、α-BaB2O4 and MgF 2, but they have various drawbacks. For example, although TiO 2 has a large birefringence, it mainly exists in a natural form, is difficult to synthesize artificially, has a narrow light transmission range, and is difficult to apply in an ultraviolet band; while MgF 2 has a wide light transmission range, its birefringence is very small, and is not suitable for manufacturing high-precision polarization optical devices. In view of the difficulty in meeting the demands of the prior commercial birefringent crystals, it is still urgent and necessary to search for novel ultraviolet birefringent optical crystals with excellent comprehensive properties.
Disclosure of Invention
The invention provides a K 2(HC9N13)·3H2 O compound, a birefringent crystal, a preparation method and application thereof. The K 2(HC9N13)·3H2 O birefringent optical crystal has the advantages of large birefringence, stable physical and chemical properties and the like, and can be used for manufacturing polarizing optical devices.
The technical scheme of the invention is as follows:
1. A compound of K 2(HC9N13)·3H2 O, wherein the chemical formula of the K 2(HC9N13)·3H2 O compound is K 2(HC9N13)·3H2 O.
2. The invention provides a K 2(HC9N13)·3H2 O double refraction optical crystal, the chemical formula of the crystal is K 2(HC9N13)·3H2 O, the crystal belongs to monoclinic system, P2 1/n space group, and the unit cell parameter is α＝90°，β＝106.046°，γ＝90°，Z＝4。
The basic structure of the crystal is a two-dimensional layered structure formed by (HC 9N13)- anions connected by hydrogen bonds, the layers are arranged in parallel, and K + and H 2 O molecules are filled between the layers to maintain the balance of the whole three-dimensional structure.
3. The preparation method of the K 2(HC9N13)·3H2 O birefringent optical crystal adopts a simple solution method to prepare the K 2(HC9N13)·3H2 O compound, and specifically comprises the following steps of:
(1) Firstly, placing melamine into a muffle furnace, then heating to 390-410 ℃ at a speed of 10-100 ℃/h, and carrying out heat preservation and sintering for 84-108 hours to obtain (C 6H3N9)n compound;
(2) Fully grinding and uniformly mixing the (C 6H3N9)n compound and potassium thiocyanate) obtained in the step (1) with the mass ratio of 1:1.8-2.2 at room temperature, heating to 450-470 ℃, and sintering at the temperature for 30-60 minutes to obtain a K 3C9N13 compound;
(3) Dissolving the K 3C9N13 compound obtained in the step (2) in deionized water, heating to 90-100 ℃, adding hydrochloric acid until the pH value of the solution is between 3 and 4, cooling to room temperature, and standing for more than 2 days to obtain the K 2(HC9N13)·3H2 O birefringent optical crystal.
Specifically, the step (2) is performed with purification by recrystallization for more than 2 times by using deionized water after heat preservation and sintering.
Specifically, the ratio of the K 3C9N13 compound obtained in the step (2) to deionized water in the step (3) is 407mg: 15-20 ml.
4. Use of a K 2(HC9N13)·3H2 O birefringent optical crystal for the manufacture of a polarizing optical device, said K 2(HC9N13)·3H2 O birefringent optical crystal.
5. A polarizing optic comprising said K 2(HC9N13)·3H2 O birefringent optical crystal. The polarizing optical device may be an optical polarizer, a circulator, an optical isolator, a phase retarder, or the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention obtains the K 2(HC9N13)·3H2 O compound and the birefringent optical crystal, and the crystal has the advantages of large birefringent index, stable physical and chemical properties and the like;
(2) The reagent and the raw materials used in the preparation method have small toxicity to human bodies, short growth period and low cost;
(3) The K 2(HC9N13)·3H2 O double refraction optical crystal can be used for manufacturing a polarized optical device;
(4) The polarized optical device manufactured by the birefringent optical crystal can be applied to the fields of optics and communication, such as an optical polarizer, a circulator, an optical isolator or a phase delay device.
Drawings
FIG. 1 is a photograph of K 2(HC9N13)·3H2 O crystals of the present invention under an optical microscope.
FIG. 2 is a graph of the K 2(HC9N13)·3H2 O polycrystalline powder X-ray diffraction pattern of the present invention with a simulated X-ray diffraction pattern based on the K 2(HC9N13)·3H2 O single crystal structure and a graph of the K 2(HC9N13)·3H2 O polycrystalline powder X-ray diffraction pattern after two weeks of standing in air.
FIG. 3 is a diagram showing the structure of K 2(HC9N13)·3H2 O crystals according to the present invention.
FIG. 4 is a graph of the ultraviolet-visible-near infrared diffuse reflectance spectrum of K 2(HC9N13)·3H2 O crystals. The ultraviolet-visible-near infrared diffuse reflection spectrum shows that the absorption cut-off edge of the crystal is 334nm. Experimental results show that the birefringence of the crystal is about 0.87@546nm.
Fig. 5 is a schematic diagram of the operation of an opto-isolator made with a K 2(HC9N13)·3H2 O crystal.
Detailed Description
The invention is further described below with reference to examples and figures. It will be appreciated by persons skilled in the art that the following examples are not intended to limit the scope of the invention, and that any modifications and variations made on the basis of the present invention are within the scope of the invention.
Examples 1-4 relate to the preparation of K 2(HC9N13)·3H2 O compounds.
Example 1
(1) Firstly, placing melamine into a muffle furnace, then heating to 400 ℃ at a speed of 10-100 ℃/h, and carrying out heat preservation and sintering for 100 hours to obtain (C 6H3N9)n compound;
(2) Fully grinding and uniformly mixing the (C 6H3N9)n compound and potassium thiocyanate) obtained in the step (1) with the mass ratio of 1:2 at room temperature, heating to 460 ℃, preserving heat and sintering for 50 minutes to obtain a K 3C9N13 compound, and recrystallizing with deionized water for 2 times for purification;
(3) Dissolving the K 3C9N13 compound obtained in the step (2) in deionized water, heating to 98 ℃, adding hydrochloric acid until the pH value of the solution is between 3 and 4, cooling to room temperature, and standing for more than 2 days to obtain the K 2(HC9N13)·3H2 O birefringent optical crystal.
Example 2
The solution method is used for preparing K 2(HC9N13)·3H2 O monocrystal, and the specific operation is carried out according to the following steps:
(1) Firstly, placing melamine into a muffle furnace, then heating to 390 ℃ at a speed of 10-100 ℃/h, and carrying out heat preservation and sintering for 84 hours to obtain (C 6H3N9)n compound;
(2) Fully grinding and uniformly mixing the (C 6H3N9)n compound and potassium thiocyanate) obtained in the step (1) with the mass ratio of 1:1.8 at room temperature, heating to 450 ℃, preserving heat and sintering for 30 minutes to obtain a K 3C9N13 compound, and recrystallizing with deionized water for 2 times for purification;
(3) Dissolving the K 3C9N13 compound obtained in the step (2) in deionized water, heating to 90 ℃, adding hydrochloric acid until the pH value of the solution is between 3 and 4, cooling to room temperature, and standing for more than 2 days to obtain the K 2(HC9N13)·3H2 O birefringent optical crystal.
Example 3
The solution method is used for preparing K 2(HC9N13)·3H2 O monocrystal, and the specific operation is carried out according to the following steps:
Firstly, placing melamine into a muffle furnace, then heating to 400 ℃ at a speed of 10-100 ℃/h, and carrying out heat preservation and sintering for 96 hours to obtain (C 6H3N9)n compound;
(2) Fully grinding and uniformly mixing the (C 6H3N9)n compound and potassium thiocyanate) obtained in the step (1) with the mass ratio of 1:2 at room temperature, heating to 460 ℃, preserving heat and sintering for 40 minutes to obtain a K 3C9N13 compound, and recrystallizing with deionized water for 2 times for purification;
(3) Dissolving the K 3C9N13 compound obtained in the step (2) in deionized water, heating to 95 ℃, adding hydrochloric acid until the pH value of the solution is between 3 and 4, cooling to room temperature, and standing for more than 2 days to obtain the K 2(HC9N13)·3H2 O birefringent optical crystal.
Example 4
The solution method is used for preparing K 2(HC9N13)·3H2 O monocrystal, and the specific operation is carried out according to the following steps:
(1) Firstly, placing melamine into a muffle furnace, then heating to 410 ℃ at a speed of 10-100 ℃/h, and carrying out heat preservation and sintering for 108 hours to obtain (C 6H3N9)n compound;
(2) Fully grinding and uniformly mixing the (C 6H3N9)n compound and potassium thiocyanate) obtained in the step (1) with the mass ratio of 1:2.2 at room temperature, heating to 470 ℃, preserving heat and sintering for 60 minutes to obtain a K 3C9N13 compound, and recrystallizing with deionized water for 2 times for purification;
(3) Dissolving the K 3C9N13 compound obtained in the step (2) in deionized water, heating to 100 ℃, adding hydrochloric acid until the pH value of the solution is between 3 and 4, cooling to room temperature, and standing for more than 2 days to obtain the K 2(HC9N13)·3H2 O birefringent optical crystal.
Fig. 1 is a photograph of a crystal under an optical microscope. The crystal obtained in the above example has a chemical formula of K 2(HC9N13)·3H2 O, belongs to monoclinic system, and has a space group of P2 1/n, and a unit cell parameter of α＝90°，β＝106.046°，γ＝90°，Z＝4。
As shown in fig. 2, the X-ray diffraction pattern of the polycrystalline powder obtained by the test was consistent with the pattern obtained by fitting according to the single crystal structure thereof; the crystal has stable physical and chemical properties, and the X-ray diffraction pattern of the K 2(HC9N13)·3H2 O polycrystal powder after being placed in the air for two weeks is consistent with the X-ray diffraction pattern based on the simulation of the monocrystal structure.
As shown in fig. 3, the basic structure of the crystal is a two-dimensional layered structure formed by (HC 9N13)- anions connected by hydrogen bonds), the layers are arranged in parallel, and K + and H 2 O molecules are filled between the layers to maintain the balance of the whole three-dimensional structure.
The birefringence of the K 2(HC9N13)·3H2 O birefringent optical crystal obtained in example 1 was measured using a polarizing microscope, and the birefringence of the crystal was about 0.87@546nm.
The K 2(HC9N13)·3H2 O birefringent crystal obtained in the above example 1 was subjected to ultraviolet-visible-near infrared diffuse reflection spectrum test, and as shown in FIG. 4, the absorption cut-off edge of the crystal was 334nm.
The K 2(HC9N13)·3H2 O crystal prepared by the embodiment can be used for preparing an optical isolator, the principle of which is shown in fig. 5, wherein ①⑤ is a coupler, ②④ is a birefringent crystal, and ③ is an optically active material. Light passing through the birefringent crystal can be decomposed into two linearly polarized light beams with different propagation directions and mutually perpendicular polarization directions.
The above detailed description is only for explaining the technical solution of the present invention in detail, the present invention is not limited to the above examples, and it should be understood that those skilled in the art should all modifications and substitutions based on the above principles and spirit are within the scope of the present invention.
Claims (7)
1. A compound of K 2(HC9N13)·3H2 O, characterized in that: the chemical formula of the K 2(HC9N13)·3H2 O compound is K 2(HC9N13)·3H2 O.
2. A K 2(HC9N13)·3H2 O birefringent optical crystal, characterized in that: the crystal belongs to monoclinic system, P2 1/n space group, and the unit cell parameter isα＝90°，β＝106.046°，γ＝90°，Z＝4。
3. The method for preparing the K 2(HC9N13)·3H2 O birefringent optical crystal according to claim 2, wherein: the method specifically comprises the following steps in sequence:
(1) Firstly, placing melamine into a muffle furnace, then heating to 390-410 ℃ at a speed of 10-100 ℃/h, and carrying out heat preservation and sintering for 84-108 hours to obtain (C 6H3N9)n compound;
(2) Fully grinding and uniformly mixing the (C 6H3N9)n compound and potassium thiocyanate) obtained in the step (1) with the mass ratio of 1:1.8-2.2 at room temperature, heating to 450-470 ℃, and sintering at the temperature for 30-60 minutes to obtain a K 3C9N13 compound;
(3) Dissolving the K 3C9N13 compound obtained in the step (2) in deionized water, heating to 90-100 ℃, adding hydrochloric acid until the pH value of the solution is between 3 and 4, cooling to room temperature, and standing for more than 2 days to obtain the K 2(HC9N13)·3H2 O birefringent optical crystal.
4. A method for preparing a K 2(HC9N13)·3H2 O birefringent optical crystal according to claim 3, wherein: and (3) after heat preservation and sintering, the mixture is recrystallized for more than 2 times by using deionized water for purification.
5. A method for preparing a K 2(HC9N13)·3H2 O birefringent optical crystal according to claim 3, wherein: the ratio of K 3C9N13 compound obtained in step (2) to deionized water in step (3) was 407mg: 15-20 ml.
6. Use of a K 2(HC9N13)·3H2 O birefringent optical crystal according to claim 2, characterized in that: the K 2(HC9N13)·3H2 O double refraction optical crystal is used for manufacturing a polarized optical device.
7. A polarizing optical device comprising the K 2(HC9N13)·3H2 O birefringent optical crystal of claim 2.
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