CN116791203A - Method for preparing electro-optic crystal growth raw material of oxygen titanium rubidium phosphate by wet chemical coprecipitation method - Google Patents
Method for preparing electro-optic crystal growth raw material of oxygen titanium rubidium phosphate by wet chemical coprecipitation method Download PDFInfo
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- 239000013078 crystal Substances 0.000 title claims abstract description 166
- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000002994 raw material Substances 0.000 title claims abstract description 56
- QXSDKTDYKUJBRX-UHFFFAOYSA-K [O-]P([O-])([O-])=O.O.[Ti+4].[Rb+] Chemical compound [O-]P([O-])([O-])=O.O.[Ti+4].[Rb+] QXSDKTDYKUJBRX-UHFFFAOYSA-K 0.000 title claims abstract description 21
- 238000000975 co-precipitation Methods 0.000 title claims abstract description 17
- 239000000126 substance Substances 0.000 title claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 76
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 76
- 239000010452 phosphate Substances 0.000 claims abstract description 76
- 229910052701 rubidium Inorganic materials 0.000 claims abstract description 72
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000000498 ball milling Methods 0.000 claims abstract description 45
- 239000010936 titanium Substances 0.000 claims abstract description 41
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 239000012456 homogeneous solution Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 claims description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 3
- KBAHJOGZLVQNBH-UHFFFAOYSA-K rubidium(1+);phosphate Chemical compound [Rb+].[Rb+].[Rb+].[O-]P([O-])([O-])=O KBAHJOGZLVQNBH-UHFFFAOYSA-K 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 16
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- 238000002360 preparation method Methods 0.000 abstract description 6
- 230000003287 optical effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 28
- 239000000843 powder Substances 0.000 description 12
- 210000003298 dental enamel Anatomy 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- FTBVYZILUXWEJK-UHFFFAOYSA-N [Rb].[Ti] Chemical compound [Rb].[Ti] FTBVYZILUXWEJK-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
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- 239000012535 impurity Substances 0.000 description 3
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- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- VJDVOZLYDLHLSM-UHFFFAOYSA-N diethylazanide;titanium(4+) Chemical compound [Ti+4].CC[N-]CC.CC[N-]CC.CC[N-]CC.CC[N-]CC VJDVOZLYDLHLSM-UHFFFAOYSA-N 0.000 description 1
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Abstract
The application provides a method for preparing a rubidium titanyl phosphate electro-optic crystal growth raw material by a wet chemical coprecipitation method, which uses organic titanium and NH 4 H 2 PO 4 And Rb 2 CO 3 The electro-optic crystal growth material of the oxygen titanium rubidium phosphate is prepared by adopting a wet chemical coprecipitation method and a ball milling method as raw materials. The method for preparing the electro-optic crystal growth raw material of the oxygen titanium rubidium phosphate provided by the application has the advantages of low raw material price, simple operation and low preparation cost; the prepared rubidium titanyl phosphate electro-optic crystal growth raw material has high purity, good uniformity and good repeatability; the prepared rubidium titanyl phosphate electro-optic crystal has good quality, no defects of grain boundary, stripes, scattering particles and the like, and good optical performance.
Description
Technical Field
The application relates to the technical field of crystal growth, in particular to a method for preparing a rubidium titanyl phosphate electro-optic crystal growth raw material by a wet chemical coprecipitation method.
Background
MM' OXO over the last decades 4 (M＝K/Rb/Cs/Tl/Na/NH 4 The M' =ti/Nb/Ta/Sn/Sb/Zr/Al/Cr/Fe/V/Ga, x=p/As/Si/Ge) series of crystals, in which rubidium titanyl phosphate (formula RbTiOPO 4 RTP for short) is a new generation of material for electro-optic devices due to its excellent electro-optic and physical-chemical properties such as high electro-optic coefficient, low half-wave voltage, high threshold value of laser damage resistance (for high power), low electrical conductivity, small insertion loss, small device, strong environmental adaptability, good mechanical and chemical stability, no deliquescence, etc., and is widely used internationally, such as "curiosity", "perseveration" Mars, T iclsat-2 satellite ATLAS laser system, laser interference gravitational wave astronomical station (LIGO), etc.
Rubidium titanyl phosphate crystals are typically grown using a top-seeded high temperature melt process because the crystalline material is a non-uniform molten compound and cannot be grown directly from its high temperature melt, with the aid of a suitable fluxing agent system, rb being currently most commonly used in RTP production 6 P 4 O 13 Cosolvents, wherein [ Rb ]]/[P]The molar ratio was 6/4. The growth method is that NH 4 H 2 PO 4 、Rb 2 CO 3 、TiO 2 Uniformly mixing, placing into a platinum crucible, processing by solid phase synthesis methods such as melting, cooling and the like to obtain a crystal growth raw material, then placing into a seed crystal after high-temperature heat treatment, and carrying out electro-optic crystal growth of the rubidium titanyl phosphate. The raw materials for crystal growth in the method are synthesized by adopting a common solid phase method, the method is simple to operate and easy to prepare, but the obtained long crystal material is insufficient in uniformity and poor in batch consistency, so that defects such as grain boundaries, stripes and scattering particles are easy to occur in the generated crystal, the optical performance is poor, and the practical application of the crystal is influenced.
Disclosure of Invention
The application aims to provide a method for preparing a rubidium titanyl phosphate electro-optic crystal growth raw material by a wet chemical coprecipitation method, so as to improve the purity, uniformity and repeatability of the prepared rubidium titanyl phosphate electro-optic crystal growth raw material. The specific technical scheme is as follows:
the first aspect of the application provides a method for preparing a rubidium titanyl phosphate electro-optic crystal growth raw material, which is prepared by using organic titanium and NH 4 H 2 PO 4 And Rb 2 CO 3 The electro-optic crystal growth material of the oxygen titanium rubidium phosphate is prepared by adopting a wet chemical coprecipitation method and a ball milling method as raw materials.
In some embodiments of the application, the organotitanium and the NH are 4 H 2 PO 4 And the Rb 2 CO 3 The molar ratio of (2.7-32.2): (66.5-76.0): (44.2-48.9).
In some embodiments of the application, the organic titanium is selected from at least one of titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetra-isopropoxide, and titanium tetra (diethylamino).
In some embodiments of the application, a method of preparing a rubidium titanyl phosphate electro-optic crystal growth feedstock comprises the steps of: uniformly mixing the organic titanium and the solvent to obtain a homogeneous solution; NH is subjected to 4 H 2 PO 4 The Rb is 2 CO 3 Dissolving in water to obtain a solution; adding the solution to the homogeneous solution, and stirring to form an opacified coprecipitated compound; drying the emulsion coprecipitated compound and then forming ballsGrinding to obtain the electro-optic crystal growth raw material of the oxygen titanium rubidium phosphate.
In some embodiments of the application, the volume ratio of the organic titanium to the solvent is (3-6): (1.5-4).
In some embodiments of the application, the solvent is selected from at least one of ethanol, isopropanol, and n-butanol.
In some embodiments of the application, the stirring time is from 5 to 8 hours.
In some embodiments of the application, the temperature of the drying is 90-115 ℃ and the time of the drying is 48-72 hours.
In some embodiments of the application, the temperature of the ball milling is 650-750 ℃, the time of the ball milling is 25-60 hours, and the rotating speed of the ball milling is 30-50r/min.
In a second aspect, the application provides a rubidium titanyl phosphate electro-optic crystal growth raw material prepared by the method in the first aspect.
The third aspect of the application provides a method for growing an electro-optic crystal of rubidium titanyl phosphate, comprising the following steps: performing overheat treatment on the electro-optic crystal growth raw material of the rubidium titanyl phosphate in the second aspect of the application to obtain an overheat solution; and cooling the overheated solution to 5-20 ℃ above the saturation point temperature, and then putting seed crystals into the overheated solution to grow the electro-optic crystal of the rubidium titanyl phosphate.
In some embodiments of the application, the temperature of the heat treatment is 900-950 ℃.
In some embodiments of the application, the process of growing an electro-optic crystal of rubidium titanyl phosphate comprises: putting seed crystals into contact with the liquid level; cooling to the saturation point temperature, and cooling at a speed of 0.01-0.3 ℃/h to grow crystals; and after the crystal growth is completed, separating the grown electro-optic crystal of the rubidium titanyl phosphate from the liquid surface, and cooling to room temperature.
The application has the beneficial effects that:
the method for preparing the electro-optic crystal growth raw material of the oxygen titanium rubidium phosphate has the advantages of low raw material price, simple operation and low preparation cost; the prepared rubidium titanyl phosphate electro-optic crystal growth raw material has high purity, good uniformity and good repeatability; the prepared rubidium titanyl phosphate electro-optic crystal has good quality, no defects of grain boundary, stripes, scattering particles and the like, and good optical performance.
Of course, it is not necessary for any one product or method of practicing the application to achieve all of the advantages set forth above at the same time.
Drawings
In order to more clearly illustrate the embodiments of the application or the technical solutions in the prior art, the drawings used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the application, and other embodiments may be obtained according to these drawings to those skilled in the art.
FIG. 1 is an X-ray diffraction chart of the electro-optic crystal product of rubidium titanyl phosphate prepared in example 1;
FIG. 2 is a photograph of a rubidium titanyl phosphate electro-optic crystal product prepared in example 1;
fig. 3 is a photograph of the electro-optic crystal product of rubidium titanyl phosphate prepared in comparative example 1.
Detailed Description
The following description of the embodiments of the present application will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present application, but not all embodiments. All other embodiments obtained by the person skilled in the art based on the present application fall within the scope of protection of the present application.
The first aspect of the application provides a method for preparing a rubidium titanyl phosphate electro-optic crystal growth raw material, which is prepared by using organic titanium and NH 4 H 2 PO 4 And Rb 2 CO 3 The electro-optic crystal growth material of the oxygen titanium rubidium phosphate is prepared by adopting a wet chemical coprecipitation method and a ball milling method as raw materials.
In the application, liquid-phase organic titanium is adopted as Ti source in the aspect of raw material synthesis, the raw material of the Ti source is low in cost, and the raw material is used for replacing solid-phase TiO commonly used in the original molten salt method 2 As a raw material; wet chemical coprecipitation method is adopted to make the initial raw material inThe ions or molecules are horizontally mixed and ball-milled by a ball mill, so that the synthesized growth raw materials are more fully and uniformly mixed, the process is simple, the energy consumption is low, and the cost is low; and decomposing the organic group by adopting a high-temperature calcination method, and finally obtaining the high-purity uniform electro-optic crystal growth raw material of the rubidium titanyl phosphate without introducing other impurity ions.
In general, the starting material is organotitanium, NH 4 H 2 PO 4 、Rb 2 CO 3 All are analytical pure reagents, so that the influence of impurities on the purity of the electro-optic crystal of the oxygen titanium rubidium phosphate can be avoided, and the quality of the electro-optic crystal of the oxygen titanium rubidium phosphate is further improved.
The application aims at the initial raw material NH 4 H 2 PO 4 、Rb 2 CO 3 The particle size of (2) is not particularly limited as long as the object of the present application can be achieved.
In some embodiments of the application, the organotitanium and the NH are 4 H 2 PO 4 And the Rb 2 CO 3 The molar ratio of (2.7-32.2): (66.5-76.0): (44.2-48.9).
The inventors found that rubidium titanyl phosphate (RbTiOPO 4 )、Rb 6 P 4 O 13 The mass ratio of the (cosolvent) is controlled to be (60-85): within the range of 100, high-quality electro-optic crystals of the oxygen titanium rubidium phosphate can be grown; that is to say, for the initial raw material, the organic titanium and NH are controlled 4 H 2 PO 4 、Rb 2 CO 3 、Rb 6 P 4 O 13 The molar ratio of (2.075-2.940): (2.075-2.940): (1.037-1.470): 1. due to Rb 6 P 4 O 13 Is made of NH 4 H 2 PO 4 And Rb 2 CO 3 Obtained by reaction, i.e. controlling the organic titanium, NH 4 H 2 PO 4 And Rb 2 CO 3 The molar ratio of (2.7-32.2): (66.5-76.0): (44.2-48.9).
In some embodiments of the application, the organic titanium is selected from at least one of titanium (IV) tetraethoxide, titanium (IV) tetra-n-propoxide, titanium (IV) tetra-isopropoxide, and titanium (IV) tetra (diethylamino). The application selects the substances as the organic titanium, and can better obtain the high-purity uniform electro-optic crystal growth raw material of the oxygen titanium rubidium phosphate.
The molecular formula of the tetraethoxide titanium (IV) is Ti (OC) 2 H 5 ) 4 Titanium tetra-n-propoxide (IV) has the molecular formula Ti (OC) 3 H 7 ) 4 Titanium (IV) tetraisopropoxide has the molecular formula of Ti (O-iPr) 4 The molecular formula of tetra (diethylamino) titanium (IV) is Ti (NC) 4 H 10 ) 4 。
In some embodiments of the application, a method of preparing a rubidium titanyl phosphate electro-optic crystal growth feedstock comprises the steps of:
(1) Uniformly mixing the organic titanium and the solvent to obtain a homogeneous solution;
(2) NH is subjected to 4 H 2 PO 4 The Rb is 2 CO 3 Dissolving in water to obtain a solution;
(3) Adding the solution to the homogeneous solution, and stirring to form an opacified coprecipitated compound;
(4) And drying and ball-milling the opacified coprecipitation compound to obtain the electro-optic crystal growth raw material of the oxygen titanium rubidium phosphate.
The method for preparing the electro-optic crystal growth raw material of the oxygen titanium rubidium phosphate has simple operation and low preparation cost; the prepared rubidium titanyl phosphate electro-optic crystal growth raw material has high purity, good uniformity and good repeatability.
In the present application, the solution may be added to the homogeneous solution in a slow manner.
In some embodiments of the application, the volume ratio of the organic titanium to the solvent is (3-6): (1.5-4). When the volume ratio of the organic titanium to the solvent is controlled within the above range, the organic titanium can be better dispersed in the solvent.
In some embodiments of the application, the solvent is selected from at least one of ethanol, isopropanol, and n-butanol. The application selects the substances as the solvent for dispersing the organic titanium, so that a more stable opacified coprecipitated compound can be obtained.
In some embodiments of the application, the stirring time is from 5 to 8 hours. When the stirring time is controlled within the above range, a more stable, opacified coprecipitated compound can be obtained.
The stirring method of the present application is not particularly limited as long as the object of the present application can be achieved, and for example, a magnetic stirrer is used for stirring.
In some embodiments of the application, the temperature of the drying is 90-115 ℃ and the time of the drying is 48-72 hours. When the temperature and time of drying are controlled within the above ranges, the solvent can be removed better, the energy consumption is reduced as much as possible, and the quality of the obtained electro-optic crystal growth raw material powder of the rubidium titanyl phosphate is ensured.
The manner and specific operation of the drying method are not particularly limited as long as the object of the present application can be achieved, for example: transferring the emulsion coprecipitation compound to an experimental enamel thick disc covered with a polytetrafluoroethylene film, and placing the experimental enamel thick disc in an oven for drying.
In some embodiments of the application, the temperature of the ball milling is 650-750 ℃, the time of the ball milling is 25-60 hours, and the rotating speed of the ball milling is 30-50r/min. When the temperature, rotation speed and time of the ball milling are controlled within the above ranges, a raw material powder having higher purity and more sufficiently uniform mixing suitable for crystal growth can be obtained.
The second aspect of the application provides a rubidium titanyl phosphate electro-optic crystal growth raw material prepared by the method according to the first aspect of the application.
The electro-optic crystal growth raw material of the rubidium titanyl phosphate provided by the application has high purity, good uniformity and good repeatability; high quality electro-optic crystals of rubidium titanyl phosphate without defects such as grain boundaries, stripes, scattering particles and the like are easy to grow.
The third aspect of the application provides a method for growing an electro-optic crystal of rubidium titanyl phosphate, which comprises the following steps: performing overheat treatment on the electro-optic crystal growth raw material of the rubidium titanyl phosphate in the second aspect of the application to obtain an overheat solution; and cooling the overheated solution to 5-20 ℃ above the saturation point temperature, and then putting seed crystals into the overheated solution to grow the electro-optic crystal of the rubidium titanyl phosphate.
The rubidium titanyl phosphate electro-optic crystal prepared by the method has the advantages of high quality, good repeatability, no defects of grain boundaries, stripes, scattering particles and the like, and good optical performance.
The saturation point temperature refers to the temperature at which the crystal does not melt and does not grow.
The specific operation process of the electro-optic crystal of rubidium titanyl phosphate for the heat treatment is not particularly limited as long as the object of the application can be achieved, for example: charging the rubidium titanyl phosphate electro-optic crystal growth raw material powder into a crucible, transferring to a top seed crystal molten salt furnace, and heating to a specific temperature to enable the molten liquid to be subjected to overheat treatment to obtain overheat solution.
In some embodiments of the application, the temperature of the heat treatment is 900-950 ℃. When the temperature of the heat treatment is controlled within the above range, a more uniform superheated solution can be formed, which is more advantageous for subsequent growth of high quality crystals. The time of the heat treatment is not particularly limited as long as the object of the present application can be achieved.
In some embodiments of the application, the process of growing an electro-optic crystal of rubidium titanyl phosphate comprises: putting seed crystals into contact with the liquid level; cooling to the saturation point temperature, and cooling at a speed of 0.01-0.3 ℃/h to grow crystals; and after the crystal growth is completed, separating the grown electro-optic crystal of the rubidium titanyl phosphate from the liquid surface, and cooling to room temperature. This process ensures that the seed crystal melts slightly without coming out of contact with the liquid surface. When the process of growing the rubidium titanyl phosphate electro-optic crystal is controlled in the mode, various defects and stress can be reduced, and therefore the high-quality crystal is grown.
The room temperature in the present application is the room temperature, generally about 25 ℃.
Examples
Hereinafter, embodiments of the present application will be described in more detail with reference to examples and comparative examples. The various tests and evaluations were carried out according to the following methods. Unless otherwise specified, "parts" and "%" are mass references.
NH used in the following examples and comparative examples 4 H 2 PO 4 、Rb 2 CO 3 、Ti(OC 2 H 5 ) 4 、Ti(OC 3 H 7 ) 4 、Ti(O-iPr) 4 、Ti(NC 4 H 10 ) 4 All are analytically pure reagents.
Testing of X-ray diffraction patterns: testing the prepared rubidium titanyl phosphate electro-optic crystal by adopting an X-ray powder diffractometer (model Bruker D8 Advance) (Cu K alpha), wherein the scanning range is 2 theta: 10 ° -75 °, scan rate: 6 °/min, test temperature: 20.+ -. 5 ℃.
According to the application, whether the electro-optic crystal of the rubidium titanyl phosphate prepared in the embodiment or the comparative example is good in quality or not is determined by naked eye observation, namely, whether crystal defects such as grain boundaries, stripes, scattering particles and the like exist or not.
Example 1
469mL of Ti (OC) was measured separately 2 H 5 ) 4 And 156mL of ethanol, and stirring at room temperature to mix them thoroughly, thereby forming transparent homogeneous solution A. 670.7g NH are weighed respectively 4 H 2 PO 4 、895.0g Rb 2 CO 3 Dissolving with deionized water to form solution B. Ti (OC) used in the above 2 H 5 ) 4 、NH 4 H 2 PO 4 、Rb 2 CO 3 The molar ratio of (2) to (7): 66.5:44.2.
solution B was slowly added to homogenized solution a and stirred with a magnetic stirrer for 6 hours to form a stable, opacified co-precipitated compound.
Transferring the opacified coprecipitation compound to an enamel thick disc covered with a polytetrafluoroethylene film, and then placing the enamel thick disc in an oven, and drying at 90 ℃ for 72 hours; and (3) loading the dried coprecipitate into a ball milling tank of a ball mill, adding grinding balls, sealing the ball milling tank, putting the ball milling tank back into a hearth of the ball mill, starting the ball mill at the rotating speed of 40r/min, gradually heating the hearth with the ball milling tank to 650 ℃ for sintering and ball milling, performing constant-temperature ball milling for 60 hours, closing the ball mill, cooling the hearth to room temperature, taking out the product of the ball milling tank, and obtaining high-purity and fully and uniformly mixed electro-optic crystal growth raw material powder of the titanium rubidium titanyl phosphate.
Charging the above-mentioned electro-optic crystal growth raw material powder of rubidium titanyl phosphate into a crucible, transferring to a top seed crystal molten salt furnace, heating to 900 deg.C to make the molten liquid undergo the process of overheat treatment so as to obtain overheat solution; cooling the overheated solution to 6 ℃ above the saturation point temperature (namely 873 ℃), and putting seed crystals into the overheated solution to enable the seed crystals to contact the liquid level, so that the seed crystals are slightly melted and cannot leave the liquid level; cooling to saturation point temperature (867 deg.c), and cooling at 867-800 deg.c and 0.01-0.3 deg.c/hr to grow crystal. After the completion of the crystal growth for 84 days, the as-formed crystal was separated from the liquid surface and cooled to room temperature, to obtain a conical colorless transparent electro-optic crystal of rubidium titanyl phosphate having a size of 36mm×39mm×34mm and a weight of 97.3g.
Example 2
588mL of Ti (OC) was measured separately 3 H 7 ) 4 And 147mL of isopropanol, and stirring at room temperature to mix thoroughly to form a transparent homogeneous solution A. 604.7g NH was weighed out separately 4 H 2 PO 4 、791.1g Rb 2 CO 3 Dissolving with deionized water to form solution B. Ti (OC) used in the above 3 H 7 ) 4 、NH 4 H 2 PO 4 、Rb 2 CO 3 The molar ratio of (2) is 28.4:72.1:47.0.
solution B was slowly added to homogenized solution a and stirred with a magnetic stirrer for 8 hours to form a stable, opacified co-precipitated compound.
Transferring the opacified coprecipitation compound to an enamel thick disc covered with a polytetrafluoroethylene film, and then placing the enamel thick disc in an oven, and drying at 110 ℃ for 58 hours; and (3) loading the dried coprecipitate into a ball milling tank of a ball mill, adding grinding balls, sealing the ball milling tank, putting the ball milling tank back into a hearth of the ball mill, starting the ball mill at the rotating speed of 40r/min, gradually heating the hearth with the ball milling tank to 670 ℃ for sintering and ball milling, performing constant-temperature ball milling for 50 hours, closing the ball mill, cooling the hearth to room temperature, taking out the product of the ball milling tank, and obtaining high-purity and fully and uniformly mixed electro-optic crystal growth raw material powder of the titanium rubidium titanyl phosphate.
Charging the above-mentioned electro-optic crystal growth raw material powder of rubidium titanyl phosphate into a crucible, transferring to a top seed crystal molten salt furnace, heating to 916 deg.C to make the molten liquid undergo the process of overheat treatment so as to obtain overheat solution; cooling the overheated solution to 6 ℃ above the saturation point temperature (namely 870 ℃), and putting seed crystals into the solution to enable the seed crystals to contact the liquid level, so that the seed crystals are slightly melted and cannot leave the liquid level; cooling to saturation point temperature (i.e. 864 deg.C), and cooling at 0.02-0.25 deg.C/h to grow crystal at 864-800 deg.C. After the 86-day crystal growth was completed, the as-formed crystal was separated from the liquid surface and cooled to room temperature to obtain a conical colorless transparent electro-optic crystal of rubidium titanyl phosphate having a size of 37mm×40mm×35mm and a weight of 103.8g.
Example 3
610mL (Ti (O-iPr) 4 And 244mL of isopropanol, and stirring at room temperature to thoroughly mix them to form a transparent homogeneous solution A. 603.5g NH are weighed respectively 4 H 2 PO 4 、784.9g Rb 2 CO 3 Dissolving with deionized water to form solution B. Ti (O-iPr) used in the above 4 、NH 4 H 2 PO 4 、Rb 2 CO 3 The molar ratio of (2) is 30.3:74.0:48.0.
solution B was slowly added to homogenized solution a and stirred with a magnetic stirrer for 5 hours to form a stable, opacified co-precipitated compound.
Transferring the opacified coprecipitation compound to an enamel thick disc covered with a polytetrafluoroethylene film, and then placing the enamel thick disc in an oven, and drying the enamel thick disc at 115 ℃ for 48 hours; and (3) loading the dried coprecipitate into a ball milling tank of a ball mill, adding grinding balls, sealing the ball milling tank, putting the ball milling tank back into a hearth of the ball mill, starting the ball mill at the rotating speed of 50r/min, gradually heating the hearth with the ball milling tank to 690 ℃ for sintering and ball milling, performing constant-temperature ball milling for 30 hours, closing the ball mill, cooling the hearth to room temperature, taking out the product of the ball milling tank, and obtaining high-purity and fully and uniformly mixed electro-optic crystal growth raw material powder of the titanium rubidium titanyl phosphate.
Charging the above-mentioned electro-optic crystal growth raw material powder of rubidium titanyl phosphate into a crucible, transferring to a top seed crystal molten salt furnace, heating to 930 deg.C to make the molten liquid undergo the process of overheat treatment so as to obtain overheat solution; cooling the overheated solution to 10 ℃ above the saturation point temperature (namely 869 ℃), and putting seed crystals into the overheated solution to enable the seed crystals to contact the liquid level, so that the seed crystals are slightly melted and cannot leave the liquid level; cooling to the saturation point temperature (i.e. 859 ℃), and cooling at the speed of 0.05-0.3 ℃/h in the temperature range of 859-800 ℃ to grow crystals. After the completion of 90 days of crystal growth, the as-formed crystal was separated from the liquid surface and cooled to room temperature, to obtain a conical colorless transparent electro-optic crystal of rubidium titanyl phosphate having a size of 47mm×42mm×37mm and a weight of 157.2g.
Example 4
694mLTi (NC) was measured separately 4 H 10 ) 4 And 278mL of ethanol, and stirring at room temperature to mix them thoroughly, thereby forming a transparent homogeneous solution A. 560.1g NH are weighed respectively 4 H 2 PO 4 、724.4g Rb 2 CO 3 Dissolving with deionized water to form solution B. Ti (NC) 4 H 10 ) 4 、NH 4 H 2 PO 4 、Rb 2 CO 3 The molar ratio of (2): 76.0:48.9.
solution B was slowly added to homogenized solution a and stirred with a magnetic stirrer for 7 hours to form a stable, opacified co-precipitated compound.
Transferring the opacified coprecipitation compound to an enamel thick disc covered with a polytetrafluoroethylene film, and then placing the enamel thick disc in an oven, and drying at 100 ℃ for 55 hours; loading the dried coprecipitate into a ball milling tank of a ball mill, adding grinding balls, sealing the ball milling tank, placing the ball milling tank back into a hearth of the ball mill, starting the ball mill at the rotating speed of 40r/min, gradually heating the hearth with the ball milling tank to 710 ℃, sintering and ball milling the raw materials, performing constant-temperature ball milling for 25 hours, closing the ball mill, cooling the hearth to room temperature, taking out the product of the ball milling tank, and obtaining high-purity and fully and uniformly mixed electro-optic crystal growth raw material powder of the titanium rubidium titanyl phosphate.
Charging the above-mentioned electro-optic crystal growth raw material powder of rubidium titanyl phosphate into a crucible, transferring to a top seed crystal molten salt furnace, heating to 920 deg.C to make the molten liquid undergo the process of overheat treatment so as to obtain overheat solution; cooling the overheated solution to 7 ℃ above the saturation point temperature (namely 876 ℃), and putting seed crystals into the overheated solution to enable the seed crystals to contact the liquid level, so that the seed crystals are slightly melted and cannot leave the liquid level; cooling to saturation point temperature (869 deg.c), and cooling at 869-800 deg.c and 0.01-0.2 deg.c/hr to grow crystal. After the completion of the crystal growth for 95 days, the as-formed crystal was separated from the liquid surface and cooled to room temperature to obtain a conical colorless transparent electro-optic crystal of rubidium titanyl phosphate having a size of 46mm×41mm×36mm and a weight of 150.4g.
Comparative example 1
159.0g of TiO is weighed respectively 2 、670.7g NH 4 H 2 PO 4 、895.0g Rb 2 CO 3 And mixing uniformly to obtain a mixture; tiO employed above 2 、NH 4 H 2 PO 4 、Rb 2 CO 3 The molar ratio of (2) to (7): 66.5:44.2. and adding the mixture into a crucible, putting the crucible into a muffle furnace, slowly heating to melt, keeping the temperature for 3 hours, and cooling to room temperature to obtain the electro-optic crystal growth raw material of the rubidium titanyl phosphate.
The subsequent crystal growth portion was the same as in example 1.
Comparative examples 2 to 8
The procedure of example 1 was repeated except that the preparation parameters were adjusted as shown in Table 1.
TABLE 1 preparation parameters and product conditions for example 1 and comparative examples 1-8
Note that: "-" means no presence of
The electro-optic crystals of rubidium titanyl phosphate prepared in examples 1-4 and comparative examples 1-8 are shown in Table 2 below.
TABLE 2 conditions of electro-optic crystals of rubidium titanyl phosphate prepared in examples 1-4 and comparative examples 1-8
| Crystal body | Size (mm) 3 ) | Quality (g) | Grain boundary | Stripe pattern | Scattering particles |
| Example 1 | 36×39×34 | 97.3 | Without any means for | Without any means for | Without any means for |
| Example 2 | 37×40×35 | 103.8 | Without any means for | Without any means for | Without any means for |
| Example 3 | 47×42×37 | 157.2 | Without any means for | Without any means for | Without any means for |
| Example 4 | 46×41×36 | 150.4 | Without any means for | Without any means for | Without any means for |
| Comparative example 1 | 35×37×32 | 89.6 | Has the following components | Has the following components | Has the following components |
| Comparative example 2 | 41×37×35 | 107.1 | Has the following components | Has the following components | Has the following components |
| Comparative example 3 | 43×38×33 | 134.5 | Without any means for | Has the following components | Has the following components |
| Comparative example 4 | 38×41×36 | 113.3 | Has the following components | Has the following components | Has the following components |
| Comparative example 5 | 45×40×35 | 143.2 | Without any means for | Has the following components | Has the following components |
| Comparative example 6 | 39×36×33 | 93.8 | Has the following components | Has the following components | Without any means for |
| Comparative example 7 | 42×37×32 | 126.9 | Has the following components | Without any means for | Has the following components |
| Comparative example 8 | 34×37×32 | 86.1 | Has the following components | Without any means for | Has the following components |
The X-ray diffraction pattern (XRD) of the rubidium titanyl phosphate electro-optic crystal product obtained in example 1 is shown in FIG. 1, wherein PDF #77-0948 refers to RbTiOPO 4 The standard diffraction PDF card (space group Pna 21) corresponds to the diffraction peak of the pure phase. As can be seen from FIG. 1, the electro-optic crystal of the rubidium titanyl phosphate prepared in example 1 has a single crystal phase, which shows that the electro-optic crystal of the rubidium titanyl phosphate prepared by the preparation method of the application has high crystal phase purity and does not contain impurities.
As shown in FIG. 2, the photograph of the electro-optic crystal product of the rubidium titanyl phosphate obtained in the example 1 shows that the electro-optic crystal of the rubidium titanyl phosphate prepared in the example 1 has good crystal phase quality and no crystal defects such as grain boundaries, stripes, scattering particles and the like.
As shown in FIG. 3, the photograph of the electro-optic crystal product of the rubidium titanyl phosphate obtained in comparative example 1 shows that the electro-optic crystal of the rubidium titanyl phosphate prepared in comparative example 1 has poor crystal phase quality and has crystal defects such as grain boundaries, stripes, scattering particles and the like.
As can be seen from tables 1 and 2 above, the volume ratio of the titanium source, the solvent, the organic titanium and the solvent in examples 1 to 4, the organic titanium, NH 4 H 2 PO 4 And Rb 2 CO 3 The molar ratio of the oxygen titanium rubidium phosphate electro-optic crystal is controlled in the range of the application, and the prepared oxygen titanium rubidium phosphate electro-optic crystal has no crystal defects such as grain boundary, stripes, scattering particles and the like, and the crystal size is favorable for practical use.
Comparative example 1 Using TiO 2 As a titanium source, a method which is obviously different from that in the embodiment 1 is adopted to prepare a raw material for electro-optic crystal growth of the rubidium titanyl phosphate, so that the quality of the finally prepared electro-optic crystal of the rubidium titanyl phosphate is poor, and crystal defects such as grain boundaries, stripes, scattering particles and the like exist.
The ball milling temperatures adopted in comparative example 2, comparative example 7 and comparative example 8 are not controlled within the scope of the application, so that the quality of the prepared rubidium titanyl phosphate electro-optic crystal is poor, and crystal defects such as grain boundaries, scattering particles and the like exist; even streaks exist in the rubidium titanyl phosphate electro-optic crystal prepared in comparative example 2.
The type of the solvent adopted in the comparative example 3 is not controlled in the range of the application, so that the quality of the prepared rubidium titanyl phosphate electro-optic crystal is poor, and crystal defects such as stripes, scattering particles and the like exist.
The volume ratio of the organic titanium and the solvent adopted in the comparative example 4 is not controlled in the range of the application, so that the quality of the prepared rubidium titanyl phosphate electro-optic crystal is poor, and crystal defects such as grain boundaries, stripes, scattering particles and the like exist.
Comparative example 5 organotitanium, NH 4 H 2 PO 4 And Rb 2 CO 3 The molar ratio of the oxygen titanium rubidium phosphate is not controlled in the range of the application, so that the quality of the prepared electro-optic crystal of the oxygen titanium rubidium phosphate is poor, and crystal defects such as stripes, scattering particles and the like exist.
The baking temperature adopted in comparative example 6 is not controlled in the range of the application, so that the quality of the prepared rubidium titanyl phosphate electro-optic crystal is poor, and crystal defects such as grain boundaries, stripes and the like exist.
The foregoing description of the preferred embodiments of the application is not intended to limit the application to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the application are intended to be included within the scope of the application.
Claims (10)
1. A method for preparing a rubidium titanyl phosphate electro-optic crystal growth raw material is characterized in that: with organic titanium, NH 4 H 2 PO 4 And Rb 2 CO 3 The electro-optic crystal growth material of the oxygen titanium rubidium phosphate is prepared by adopting a wet chemical coprecipitation method and a ball milling method as raw materials.
2. The method according to claim 1, characterized in that: the organic titanium and the NH 4 H 2 PO 4 And the Rb 2 CO 3 The molar ratio of (2.7-32.2): (66.5-76.0): (44.2-48.9).
3. The method according to claim 1, characterized in that: the organic titanium is at least one selected from the group consisting of titanium tetraethoxide, titanium tetra-n-propoxide, titanium tetra-isopropoxide and titanium tetra (diethylamino).
4. A method according to any one of claims 1-3, comprising the steps of:
uniformly mixing the organic titanium and the solvent to obtain a homogeneous solution;
NH is subjected to 4 H 2 PO 4 The Rb is 2 CO 3 Dissolving in water to obtain a solution;
adding the solution to the homogeneous solution, and stirring to form an opacified coprecipitated compound;
and drying and ball-milling the opacified coprecipitation compound to obtain the electro-optic crystal growth raw material of the oxygen titanium rubidium phosphate.
5. The method according to claim 4, wherein:
the volume ratio of the organic titanium to the solvent is (3-6): (1.5-4);
preferably, the solvent is selected from at least one of ethanol, isopropanol and n-butanol.
6. The method according to claim 4, wherein:
the stirring time is 5-8 hours.
7. The method according to claim 4, wherein:
the temperature of the drying is 90-115 ℃, and the time of the drying is 48-72 hours;
preferably, the temperature of the ball milling is 650-750 ℃, the time of the ball milling is 25-60 hours, and the rotating speed of the ball milling is 30-50r/min.
8. A rubidium titanyl phosphate electro-optic crystal growth feedstock prepared according to the method of any one of claims 1-7.
9. The method for growing the electro-optic crystal of the rubidium titanyl phosphate is characterized by comprising the following steps of:
performing heat treatment on the electro-optic crystal growth raw material of the titanyl phosphate rubidium in claim 8 to obtain a superheated solution; cooling the overheated solution to 5-20 ℃ above the saturation point temperature, and then putting seed crystals into the overheated solution to grow the electro-optic crystal of the oxygen titanium rubidium phosphate;
preferably, the temperature of the heat treatment is 900-950 ℃.
10. The growth method according to claim 9, wherein the process of growing the electro-optic crystal of rubidium titanyl phosphate comprises: putting seed crystals into contact with the liquid level; cooling to the saturation point temperature, and cooling at a speed of 0.01-0.3 ℃/h to grow crystals; and after the crystal growth is completed, separating the grown electro-optic crystal of the rubidium titanyl phosphate from the liquid surface, and cooling to room temperature.
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