CN114016120A - Preparation method and device of thiourea zinc sulfate crystal - Google Patents
Preparation method and device of thiourea zinc sulfate crystal Download PDFInfo
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- CN114016120A CN114016120A CN202111326615.XA CN202111326615A CN114016120A CN 114016120 A CN114016120 A CN 114016120A CN 202111326615 A CN202111326615 A CN 202111326615A CN 114016120 A CN114016120 A CN 114016120A
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- 239000013078 crystal Substances 0.000 title claims abstract description 195
- MREWRIBFHKNJTG-UHFFFAOYSA-L NC(=S)N.S(=O)(=O)([O-])[O-].[Zn+2] Chemical compound NC(=S)N.S(=O)(=O)([O-])[O-].[Zn+2] MREWRIBFHKNJTG-UHFFFAOYSA-L 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000005303 weighing Methods 0.000 claims abstract description 8
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 239000012153 distilled water Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 12
- 239000003153 chemical reaction reagent Substances 0.000 claims description 9
- 238000013021 overheating Methods 0.000 claims description 9
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 229940076153 heptahydrate zinc sulfate Drugs 0.000 claims description 3
- 229920002545 silicone oil Polymers 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 230000007423 decrease Effects 0.000 claims 1
- 238000000746 purification Methods 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 description 54
- 230000007547 defect Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000002834 transmittance Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- -1 zinc sulfourea sulfate Chemical compound 0.000 description 3
- GLVOVYXPKVSFFY-UHFFFAOYSA-L zinc;thiourea;sulfate Chemical compound [Zn+2].NC(N)=S.NC(N)=S.NC(N)=S.[O-]S([O-])(=O)=O GLVOVYXPKVSFFY-UHFFFAOYSA-L 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 239000002019 doping agent Substances 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002109 crystal growth method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
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- 238000001228 spectrum Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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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
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/08—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by cooling of the solution
-
- 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
- C30B29/54—Organic compounds
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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
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/02—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent
- C30B7/04—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by evaporation of the solvent using aqueous solvents
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/3551—Crystals
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Abstract
The invention relates to the technical field of growth and preparation of novel nonlinear optical crystal materials, in particular to a preparation method and a device of thiourea zinc sulfate crystals. The preparation method comprises the following steps: preparing a growth solution: presetting the saturation point temperature of the solution to be 51 ℃, calculating and weighing thiourea zinc sulfate powder according to the temperature solubility curve of the thiourea zinc sulfate, dissolving the thiourea zinc sulfate powder in distilled water at the temperature higher than the saturation point temperature to obtain a growth solution required by crystal growth, and adjusting the pH value of the growth solution; then purifying the growth solution; preparing supersaturated thiourea zinc sulfate solution, and spontaneously crystallizing by a natural cooling evaporation method to obtain small crystals as seed crystals for crystal growth; fixing a seed crystal on a seed crystal rod, immersing the seed crystal in a growth solution, performing crystal growth according to a theoretically calculated thiourea zinc sulfate crystal growth cooling curve, and growing for a period of time to obtain a thiourea zinc sulfate crystal; the prepared crystal has larger size and better optical quality.
Description
Technical Field
The invention relates to the technical field of growth and preparation of novel nonlinear optical crystal materials, in particular to a preparation method and a device of thiourea zinc sulfate crystals.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The trithiourea sulfate zinc is abbreviated as thiourea zinc sulfate ([ Zn (NH)2)2)3SO4]) The metal organic complex nonlinear optical crystal is a functional material with excellent performance, has larger nonlinear optical coefficient, strong laser damage resistance, wide transmission waveband, small angle sensitivity and very good mechanical strength, and has huge application potential in the photoelectric field.
The growth preparation of thiourea zinc sulfate crystal materials has a plurality of problems which are not solved all the time: the growth habit and regularity are not clear enough; the crystal growth method is sensitive to the growth environment, and the size and the quality of the crystal obtained under different growth conditions are greatly different; the traditional crystal growth process is difficult to prepare high-quality crystals, and the like; these become bottlenecks and obstacles for research and application of the crystal, and limit the application of the crystal as a laser frequency doubling material to practical devices.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method and a device of thiourea zinc sulfate crystals, the preparation method can improve the transparency and transmittance of the crystals, solve the problems of unstable growth, quality defects and the like of the trithiourea sulfate zinc crystals, and the prepared crystals have larger size and better optical quality, and the light transmittance of the crystals can reach 76% after characterization test, thereby being beneficial to the application of the crystals as nonlinear optical materials in laser devices and providing guarantee for the optical application of the crystals.
In order to achieve the above object, the technical solution of the present invention is as follows:
in a first aspect of the invention, a preparation method of thiourea zinc sulfate crystals is provided, and the preparation method comprises the following steps:
preparing a growth solution: presetting the saturation point temperature of the growth solution, calculating and weighing thiourea zinc sulfate powder according to the temperature solubility curve of thiourea zinc sulfate, dissolving the thiourea zinc sulfate powder in distilled water at the temperature higher than the saturation point temperature to obtain a growth solution required by crystal growth, and adjusting the pH value of the growth solution; then purifying the growth solution;
preparing supersaturated thiourea zinc sulfate solution, and spontaneously crystallizing by a natural cooling evaporation method to obtain small crystals as seed crystals for crystal growth;
fixing a seed crystal on a seed crystal rod, immersing the seed crystal in a growth solution, performing crystal growth according to a theoretically calculated thiourea zinc sulfate crystal growth cooling curve, and growing for a period of time to obtain a thiourea zinc sulfate crystal;
in one or more embodiments, the thiourea zinc sulfate crystal growth cooling curve is Δ T ═ 0.07T2+1.39T +6.95)/(1.15T + 50.15); the growth of the high-quality crystal is a process with constant growth speed and a gradual change process of the crystal from small to large; at the beginning, because the seed crystal is very small, the cooling speed is more accurately controlled, so that defects are prevented from being generated in the crystal or mixed crystals are prevented from being generated in the solution; therefore, in order to determine an accurate cooling program, a clear guidance is provided for the crystal growth experiment of the thiourea zinc sulfate, and the cooling amount and the cooling curve are calculated in a systematic and detailed manner before the experiment to obtain the crystal growth cooling curve of the thiourea zinc sulfate.
In a second aspect of the present invention, there is provided a thiourea zinc sulfate crystal growth apparatus, comprising:
the growth bottle is internally provided with a seed rod, and the seed rod is used for the growth of crystals; the seed crystal rod is connected with a crystal conversion motor above the growth bottle; the growth bottle is positioned in a water bath which is used for keeping the growth bottle at a constant temperature.
The preparation method of the thiourea zinc sulfate crystal of the first aspect of the invention can use the thiourea zinc sulfate crystal growth device of the second aspect for growth, and can also use a crystal growth device known in the prior art for growth.
The specific embodiment of the invention has the following beneficial effects:
the crystal growth solution prepared in the preparation method of the thiourea zinc sulfate crystal can improve the transparency and transmittance of the crystal and solve the problems of unstable growth, quality defect and the like of the trithiourea sulfate zinc crystal;
according to the preparation method of the thiourea zinc sulfate crystal, the cooling amount and the cooling curve are systematically calculated in detail, crystal growth is carried out according to the theoretically calculated thiourea zinc sulfate crystal growth cooling curve, the cooling speed is accurately controlled, and defects generated by the crystal or mixed crystals generated in solution are avoided;
according to the preparation method of the thiourea zinc sulfate crystal, after the crystal growth is finished, the crystal is slowly lifted to leave the growth liquid level, and the crystal is taken out of the growth bottle when the temperature of the growth solution is naturally reduced to room temperature, so that the defects that the crystal cracks and the like due to too large temperature difference inside and outside the bottle can be prevented;
according to the invention, a normal-temperature water solution method is used for growing crystals, the size of the prepared thiourea zinc sulfate crystals reaches 4.3cm multiplied by 1.5cm multiplied by 0.9cm, the crystals have regular appearance and good transparency; the size of the growing thiourea zinc sulfate crystal is greatly improved, the transparency and the optical quality of the thiourea zinc sulfate crystal are obviously improved through optimization of doping conditions, and the improvement of the size and the quality of the crystal provides guarantee for nonlinear optical application of the crystal.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a photograph of a crystal of zinc thiourea sulfate prepared in example 1 of the present invention;
FIG. 2 is a transmission curve diagram of thiourea zinc sulfate crystals prepared in example 1 of the present invention;
FIG. 3 is a structural diagram of a thiourea zinc sulfate crystal growth device.
In FIG. 3, 1, a crystal rotating motor, 2, a silicon oil sealing device, 3, a water bath thermometer, 4, a seed crystal rod, 5, a thermal resistor, 6, a growth bottle, 7, a stirring device, 8, a heater, 9, a grown crystal, 10 and a water bath.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In one embodiment of the invention, the preparation method of the zinc sulfate thiourea crystal comprises the following steps:
preparing a growth solution: presetting the saturation point temperature of the growth solution, calculating and weighing thiourea zinc sulfate powder according to the temperature solubility curve of thiourea zinc sulfate, dissolving the thiourea zinc sulfate powder in distilled water at the temperature higher than the saturation point temperature to obtain a growth solution required by crystal growth, and adjusting the pH value of the growth solution; then purifying the growth solution;
preparing supersaturated thiourea zinc sulfate solution, and spontaneously crystallizing by a natural cooling evaporation method to obtain small crystals as seed crystals for crystal growth;
and fixing a seed crystal on a seed crystal rod, immersing the seed crystal in a growth solution, performing crystal growth according to a theoretically calculated thiourea zinc sulfate crystal growth cooling curve, and growing for a period of time to obtain the thiourea zinc sulfate crystal.
In one or more embodiments, the thiourea zinc sulfate powder is obtained by accurately calculating and weighing a high-purity heptahydrate zinc sulfate reagent and a high-purity thiourea reagent according to a molar ratio, dissolving and mixing, fully reacting, spontaneously crystallizing, filtering and drying;
preferably, the molar ratio of the zinc sulfate heptahydrate reagent to the thiourea reagent is 1: 3;
preferably, after thiourea zinc sulfate powder is obtained, the powder is recrystallized for 3 times, so that the impurity content in the raw material is reduced;
in one or more embodiments, adjusting the pH of the growth solution is performed by: adding a sulfuric acid solution as an acid regulator and a doping agent, fully and uniformly mixing, and regulating the pH value of the growth solution to 4.2;
in one or more embodiments, the specific steps of purifying the growth solution are: filtering and overheating the solution, raising the temperature of the solution to 4-6 ℃ higher than the saturation point, preferably 5 ℃, keeping the temperature, cleaning a suction filtration device, drying, and quickly finishing the whole step, wherein microporous qualitative filter paper is adopted for filtration;
and (3) after the filtration is finished, carrying out overheating treatment on the solution, wherein the overheating temperature of the solution is 4-6 ℃ higher than the saturation point temperature, preferably 5 ℃, and the treatment time is 24-26 hours, preferably 24 hours.
Preferably, the accurate saturation point of the growth solution is measured by a concentration vortex method, and the temperature accuracy of the solution saturation point measured by the method can reach about 0.1 ℃; the saturation point of the obtained growth solution is 51 ℃, namely the saturation point temperature of the growth solution is preset to be 51 ℃;
preferably, the volume ratio of the growth solution in the growth bottle is 75%;
the whole process of crystal growth is carried out in solution, the quality of the solution determines the stability of crystal growth and the quality of grown crystal, and the solution treatment aims at improving the purity of the solution and reducing the pollution of harmful impurities.
In one or more embodiments, the thiourea zinc sulfate crystal growth cooling curve is Δ T ═ 0.07T2+1.39T +6.95)/(1.15T + 50.15); the growth of a good quality crystal is a growthThe process of constant speed and the gradual change process of the crystal from small to large are carried out simultaneously; at the beginning, because the seed crystal is very small, the cooling speed is more accurately controlled, so that defects are prevented from being generated in the crystal or mixed crystals are prevented from being generated in the solution; therefore, in order to determine an accurate cooling program, a clear guidance is provided for a crystal growth experiment of the thiourea zinc sulfate, and the cooling amount and a cooling curve are calculated in a systematic and detailed manner before the experiment to obtain the crystal growth cooling curve of the thiourea zinc sulfate;
in one or more embodiments, the crystal growth time is 30-40 days, preferably 36 days;
in one or more embodiments, after the crystal growth is completed, the crystal is slowly lifted away from the growth liquid level, and the crystal is taken out from the growth bottle when the temperature of the growth solution is naturally cooled to room temperature, so as to prevent the crystal from generating defects such as cracks and the like due to too large temperature difference between the inside and the outside of the bottle.
In one embodiment of the present invention, there is provided a thiourea zinc sulfate crystal growth apparatus, including:
the growth bottle is internally provided with a seed rod, and the seed rod is used for the growth of crystals; the seed crystal rod is connected with a crystal conversion motor above the growth bottle; the growth bottle is positioned in a water bath which is used for keeping the growth bottle at a constant temperature.
In one or more embodiments, a water bath thermometer, a thermal resistor, a stirring device and a heater are arranged in the water bath;
in one or more embodiments, a silicone oil sealing device is arranged between the crystal rotating motor and the growth bottle.
The preparation method of the thiourea zinc sulfate crystal can use the thiourea zinc sulfate crystal growth device for growth, and can also use a crystal growth device known in the prior art for growth.
The invention will be further explained and illustrated with reference to specific examples.
Example 1
The utility model provides a thiourea zinc sulfate crystal growth device, growth device includes: a seed crystal rod 4 is arranged in the growth bottle 6, and the seed crystal rod is used for the growth of crystals; the seed crystal rod 4 is connected with the crystal conversion motor 1 above the growth bottle; the growth flask is located in a water bath 10 for maintaining the growth flask at a constant temperature.
A water bath thermometer 3, a thermal resistor 5, a stirring device 7 and a heater 8 are arranged in the water bath 10; and a silicone oil sealing device 2 is arranged between the crystal conversion motor 1 and the growth bottle 6.
Example 2
Adopting a normal-temperature water solution method to grow and prepare thiourea zinc sulfate crystals:
(1) synthesizing thiourea zinc sulfate raw material: accurately calculating and weighing a high-purity heptahydrate zinc sulfate reagent and a high-purity thiourea reagent according to a molar ratio of 1:3, respectively dissolving the reagents in a certain amount of distilled water, and obtaining a raw material after uniformly mixing, fully reacting, spontaneously crystallizing, filtering and drying. The raw material is recrystallized for three times, so that the impurity content in the raw material is reduced.
(2) Preparing a crystal growth solution: presetting the saturation point temperature of the solution to be 51 ℃, preparing 600mL of the solution by adopting an 800mL growth bottle, calculating and weighing raw materials according to the temperature solubility curve of the zinc sulfourea sulfate, and dissolving the raw materials in distilled water at the temperature higher than the saturation point to obtain the growth solution required by crystal growth. Adding 2mL of sulfuric acid solution serving as an acid regulator and a doping agent, fully and uniformly mixing, and regulating the pH value of the growth solution to 4.2;
the treatment of the growth solution is then carried out to improve the purity of the solution and reduce the contamination by harmful impurities: filtering and overheating the solution, raising the temperature of the solution to 5 ℃ higher than the saturation point, keeping the temperature constant, cleaning a suction filtration device, drying, wherein microporous qualitative filter paper is adopted for filtering, and the whole step is rapidly completed; and (3) after the filtration is finished, carrying out overheating treatment on the solution, wherein the overheating temperature of the solution is higher than the saturation point temperature by 5 ℃ generally, and the treatment time is 24 hours.
(3) And (3) carrying out crystal growth: firstly, adopting a natural cooling evaporation self-crystallization method to obtain thiourea zinc sulfate seed crystals, specifically, preparing 300mL of saturated solution, standing the saturated solution in an evaporation dish, slowly and naturally evaporating the solvent, and gradually precipitating and growing small crystals after 7 days to obtain seed crystals with different sizes;
fixing seed crystals on seed crystal rods, placing the seed crystals into a growth bottle, and fixing the upper parts of the seed crystals and the crystal rods; the cooling speed is accurately controlled so as to prevent the crystal from generating defects or the solution from generating mixed crystals; according to the crystal growth cooling curve delta T (0.07T) of thiourea zinc sulfate2+1.39T +6.95)/(1.15T +50.15) to grow crystal at reduced temperature, and according to the growth cooling curve, the initial cooling rate of thiourea zinc sulfate crystal growth is slow, and the cooling rate is gradually increased along with the growth, and the growth period is 36 days;
after the crystal growth is finished, stopping crystal rotation, slowly lifting the grown crystal until the crystal leaves the growth liquid level, and taking the crystal out of the growth bottle when the temperature of the growth solution is naturally reduced to room temperature so as to prevent the crystal from generating cracks and other defects caused by too large temperature difference between the inside and the outside of the growth bottle.
And (4) carrying out appearance observation analysis and various analysis tests on the crystal after the crystal is taken out.
FIG. 2 is a crystal of zinc sulfate thiosemicarbazide prepared in example 1, and it can be seen that the size reaches 4.3 cm. times.1.5 cm. times.0.9 cm, the crystal has a regular shape, and the transparency is good; the phase structure of the crystal is tested by an EMPYREAN X-ray diffractometer of Dutch Pasnake company, and the characterization result shows that the XRD diffraction spectrum of the crystal sample prepared by the method is consistent with the standard powder diffraction pattern of the zinc thiourea sulfate, no impurity peak appears, and the prepared crystal is really the zinc thiourea sulfate crystal;
the light transmittance of the crystal was measured by an ultraviolet-visible spectrophotometer (UV-Vis), and fig. 3 is a graph showing the transmittance of the crystal of zinc sulfourea sulfate prepared in example 1. The characterization result shows that the transmittance of the crystal sample prepared by the method reaches 70% at the 400-800nm wave band and 76% at the 800-1100nm wave band, and the transmittance can meet the transmission condition of optical application. The size of the growing thiourea zinc sulfate crystal is greatly improved through the design and the transformation of equipment and a process flow, the transparency and the optical quality of the thiourea zinc sulfate crystal are obviously improved through the optimization of doping conditions, and the improvement of the size and the quality of the crystal provides guarantee for the nonlinear optical application of the crystal.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the thiourea zinc sulfate crystal is characterized by comprising the following steps:
preparing a growth solution: presetting the saturation point temperature of the growth solution, calculating and weighing thiourea zinc sulfate powder according to the temperature solubility curve of thiourea zinc sulfate, dissolving the thiourea zinc sulfate powder in distilled water at the temperature higher than the saturation point temperature to obtain a growth solution required by crystal growth, and adjusting the pH value of the growth solution; then purifying the growth solution;
preparing a growth seed crystal: preparing supersaturated thiourea zinc sulfate solution, and spontaneously crystallizing by a natural cooling evaporation method to obtain small crystals as seed crystals for crystal growth;
crystal growth: and fixing a seed crystal on a seed crystal rod, immersing the seed crystal in a growth solution, performing crystal growth according to a theoretically calculated thiourea zinc sulfate crystal growth cooling curve, and growing for a period of time to obtain the thiourea zinc sulfate crystal.
2. The preparation method of the thiourea zinc sulfate crystal of claim 1, wherein the thiourea zinc sulfate powder is obtained by precisely calculating and weighing a high-purity heptahydrate zinc sulfate reagent and a high-purity thiourea reagent according to a molar ratio, dissolving and mixing, fully reacting, spontaneously crystallizing, filtering and drying.
3. The preparation method of the thiourea zinc sulfate crystal of claim 2, wherein the thiourea zinc sulfate powder is obtained and then recrystallized for 3 times.
4. The method for preparing thiourea zinc sulfate crystals as claimed in claim 1, wherein the operation of adjusting the pH of the growth solution is: adding sulfuric acid solution, mixing, and adjusting pH of the growth solution to 4.2.
5. The preparation method of thiourea zinc sulfate crystals as claimed in claim 1, wherein the purification treatment of the growth solution comprises the following steps: filtering and overheating the solution, raising the temperature of the solution to be 4-6 ℃ higher than the saturation point, keeping the temperature, preferably raising the temperature of the solution to be 5 ℃ higher than the saturation point, keeping the temperature, cleaning a suction filtration device, drying, and filtering by adopting microporous qualitative filter paper, wherein the whole step is quickly finished;
after the filtration is finished, the solution is subjected to overheating treatment, wherein the overheating temperature of the solution is 4-6 ℃ higher than the saturation point temperature, preferably 5 ℃, and the treatment time is 24-6 ℃, preferably 24 hours.
6. The method for preparing thiourea zinc sulfate crystal of claim 1, wherein the accurate saturation point of the growth solution is measured by concentration vortex method, and the saturation point temperature of the obtained growth solution is 51 ℃;
preferably, the volume ratio of the growth solution in the growth flask is 75%.
7. The method for preparing the thiourea zinc sulfate crystal of claim 1, wherein the growth cooling curve of the thiourea zinc sulfate crystal is Δ T ═ (0.07T)2+1.39t+6.95)/(1.15T+50.15)；
Preferably, the crystal growth time is 30-40 days, preferably 36 days.
8. The method for preparing thiourea zinc sulfate crystals as claimed in claim 1, wherein after the crystals are grown, the crystals are slowly lifted away from the growth liquid level, and the crystals are taken out from the growth bottle when the temperature of the growth solution naturally decreases to room temperature.
9. The utility model provides a thiourea zinc sulfate crystal growth device which characterized in that, growth device includes:
the growth bottle is internally provided with a seed rod, and the seed rod is used for the growth of crystals; the seed crystal rod is connected with a crystal conversion motor above the growth bottle; the growth bottle is positioned in a water bath which is used for keeping the growth bottle at a constant temperature.
10. The thiourea zinc sulfate crystal growing apparatus of claim 9, wherein a water bath thermometer, a thermal resistor, a stirring device and a heater are disposed in the water bath;
and a silicone oil sealing device is arranged between the crystal conversion motor and the growth bottle.
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| CN115233285A (en) * | 2022-07-20 | 2022-10-25 | 江西新余新材料科技研究院 | Crystal growth apparatus and method, and TGS-based crystal |
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