CN118996606A - Preparation method of precious-grade beryllium aluminate crystal - Google Patents
Preparation method of precious-grade beryllium aluminate crystal Download PDFInfo
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- CN118996606A CN118996606A CN202411483460.4A CN202411483460A CN118996606A CN 118996606 A CN118996606 A CN 118996606A CN 202411483460 A CN202411483460 A CN 202411483460A CN 118996606 A CN118996606 A CN 118996606A
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- 239000013078 crystal Substances 0.000 title claims abstract description 119
- 229910052790 beryllium Inorganic materials 0.000 title claims abstract description 63
- -1 beryllium aluminate Chemical class 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 26
- 239000000155 melt Substances 0.000 claims abstract description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 3
- 238000005086 pumping Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 claims description 4
- 230000000737 periodic effect Effects 0.000 claims description 4
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical compound C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- ZBUQRSWEONVBES-UHFFFAOYSA-L beryllium carbonate Chemical compound [Be+2].[O-]C([O-])=O ZBUQRSWEONVBES-UHFFFAOYSA-L 0.000 claims description 2
- 229910000023 beryllium carbonate Inorganic materials 0.000 claims description 2
- WPJWIROQQFWMMK-UHFFFAOYSA-L beryllium dihydroxide Chemical compound [Be+2].[OH-].[OH-] WPJWIROQQFWMMK-UHFFFAOYSA-L 0.000 claims description 2
- 229910001865 beryllium hydroxide Inorganic materials 0.000 claims description 2
- 238000010583 slow cooling Methods 0.000 claims description 2
- 230000007423 decrease Effects 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 12
- 230000031700 light absorption Effects 0.000 abstract description 3
- 230000007547 defect Effects 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 3
- 239000010431 corundum Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 2
- 239000010437 gem Substances 0.000 description 2
- 229910001751 gemstone Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- JNDMLEXHDPKVFC-UHFFFAOYSA-N aluminum;oxygen(2-);yttrium(3+) Chemical compound [O-2].[O-2].[O-2].[Al+3].[Y+3] JNDMLEXHDPKVFC-UHFFFAOYSA-N 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910019901 yttrium aluminum garnet Inorganic materials 0.000 description 1
Classifications
-
- 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
- C30B15/00—Single-crystal growth by pulling from a melt, e.g. Czochralski method
-
- 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
- C30B27/00—Single-crystal growth under a protective fluid
- C30B27/02—Single-crystal growth under a protective fluid by pulling from a melt
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/16—Oxides
- C30B29/22—Complex oxides
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention relates to a preparation method of a precious-grade beryllium aluminate crystal, which comprises the following steps: (S1) feeding an aluminum source and a beryllium source into a crucible, heating to 1800-1850 ℃ for reaction to generate beryllium aluminate, continuously heating to 50-100 ℃ and preserving heat for 1-2 hours to form beryllium aluminate crystal phase, and continuously heating to 2100-2200 ℃ to form beryllium aluminate melt; (S2) pumping vacuum of crystal growth pulling equipment, then filling argon, downwards moving the beryllium aluminate seed crystal above the liquid level of the beryllium aluminate melt, downwards moving the seed crystal below the liquid level of the melt, rotating and upwards pulling the seed crystal, simultaneously applying periodically alternating ultrasonic environment to the environment, starting crystal growth, and maintaining the temperature until the crystal growth is finished; and (S3) after the crystal growth is finished, pulling the crystal away from the melt, and slowly cooling to room temperature to obtain the precious stone-grade beryllium aluminate crystal. The beryllium aluminate crystal prepared by the invention has good optical performance, low weak light absorption coefficient and good optical uniformity.
Description
Technical Field
The invention belongs to the technical field of optical crystal manufacturing, and particularly relates to a preparation method of a precious-grade beryllium aluminate crystal.
Background
Beryllium aluminate (BeAl 2O4) is a terminal phonon laser matrix crystal material with excellent performance, has a tunable range of 650-800nm, can be used for red light lasers, has physical and chemical properties exceeding those of laser quality crystals such as yttrium aluminum garnet, and can be widely applied to the fields of laser precision machining, spectrum analysis, pulse lasers and the like. However, in the growth process of the beryllium aluminate crystal, because the viscosity of the beryllium aluminate melt is high, beAl 2O4 is an anisotropic crystal, and the process conditions are harsh; and the components are easily segregated to cause melt aging, and the obtained large-size crystals are easily subjected to defects such as cracking, micropores and the like to cause the optical properties to be reduced, so that the application thereof has been limited although the optical properties are very outstanding.
CN101407402a discloses a beryllium aluminate crystal matrix discoloration maintaining and preparation method thereof, which is doped with Cr, fe, ti or Ni elements by vertical static temperature gradient method. But the crystal quality is not good enough, the temperature gradient is difficult to regulate and control, and defects easily occur in the crystal growth process. CN1824847a discloses a method for preparing Cr doped beryllium aluminate, beO and Al 2O3、Cr2O3 are used as raw materials, through periodic variable-speed rotation movement of a crucible, the rotation speed is gradually increased from 0 and gradually reduced to 0, and periodic change of the rotation speed of the crucible can reduce the phenomenon of component segregation, but the defects of stripes, color bands, wrappage and the like can be generated in the crystal growth process, and the physicochemical properties of the beryllium aluminate crystal are also affected.
Therefore, development of a preparation method of precious-grade beryllium aluminate is needed, the preparation method is simple in process, and the obtained beryllium aluminate crystal is good in optical performance, free of defects or few in defects, reaches the precious stone grade, and can be applied to the fields of laser processing of high-precision tips, laser pulsers and the like.
Disclosure of Invention
In order to overcome the defect that the product prepared by the beryllium aluminate crystal preparation process in the prior art is not excellent enough in performance, particularly in laser performance, the high-requirement fields such as laser precision manufacturing and laser pulse cannot be met. The invention provides a preparation method of a precious stone-grade beryllium aluminate crystal, which is prepared by an upward pulling method, and an externally-applied ultrasonic environment with periodical change is applied in an initial crystal growth stage of seed crystals, so that defects generated by crystal growth can be well inhibited, and a large-size precious stone-grade beryllium aluminate crystal with few defects can be obtained. Specifically, the invention achieves the above object by the following technical scheme:
the preparation method of the precious-grade beryllium aluminate crystal comprises the following steps:
(S1) feeding an aluminum source and a beryllium source into a crucible, heating to 1800-1850 ℃ to react for 15-20h to generate beryllium aluminate, continuously heating to 50-100 ℃ and preserving heat for 1-2h to form a beryllium aluminate polycrystalline phase, and continuously heating to 2100-2200 ℃ to form a beryllium aluminate melt;
(S2) pumping vacuum of crystal growth pulling equipment, then filling argon, downwards moving beryllium aluminate seed crystal above the liquid level of the beryllium aluminate melt in the step (S1) and keeping the temperature for a period of time, starting to downwards move the seed crystal, enabling the seed crystal to downwards move below the liquid level of the melt and keep for a period of time, starting to rotate and upwards pull the seed crystal, simultaneously applying an ultrasonic environment with the ultrasonic frequency ranging from 50kHz to 60kHz to 100 kHz to 150kHz to periodically and alternately change, starting to grow crystals in each period of 10 to 20 minutes, and removing the ultrasonic environment until the crystal diameter reaches the requirement, and keeping the temperature until the crystal growth is finished;
And (S3) after the crystal growth is finished, pulling the crystal away from the melt, and slowly cooling to room temperature to obtain the precious stone-grade beryllium aluminate crystal.
The crystal growth by the upward pulling method plays a critical role in the initial crystal growth stage of adding seed crystals, and defects such as white color bands and the like can be caused by improper treatment, and the seed crystals must be rebeeded. And even if the seeding is smooth, similar defects can also appear in the crystal growth process, and the crystal growth cannot be smoothly carried out, so that the preparation of large-size crystals is affected. Ultrasonic technology has been used and studied in crystal growth to control crystal growth and morphology by utilizing the physical effects of ultrasonic wave such as pressure change, laminar flow and the like formed in a melt. The inventor has unexpectedly found that, in the initial crystal growth stage of adding seed crystal, the ultrasonic environment with periodically changed environment is given, and the sinusoidal function curve is changed regularly within the time period of 10-20min from 50kHz-120kHz, so that the defect generation can be effectively inhibited, and the preparation of the precious stone-grade beryllium aluminate crystal with large size defect and less defects is facilitated.
Further, in the step (S1), the aluminum source is at least one of aluminum oxide and aluminum hydroxide, the beryllium source is at least one of beryllium oxide, beryllium hydroxide and beryllium carbonate, and the purity of the raw material is more than or equal to 99.9%, preferably more than or equal to 99.99%. The invention adopts high-purity aluminum oxide and beryllium oxide as raw materials, reduces the existence of impurities, and particularly reduces nonferrous metals such as Fe, cu and the like. Aluminum source and beryllium source were as per Al: be molar ratio 2-2.1:1, preferably Al: be molar ratio 2:1, feeding; ensures the raw materials to fully react.
Further, in the step (S2), the crystal growth pulling apparatus is evacuated and then filled with argon gas under a pressure of 1X 10 -3 Pa to 5X 10 -3 Pa, and the argon gas is filled with argon gas of 0.8-1 atm.
Further, in step (S2), the beryllium aluminate seed crystal is moved down to 5-15mm, preferably 8-12mm, above the level of the beryllium aluminate melt in step (S1); the constant temperature is maintained for 0.5-1h at the constant temperature of the environment temperature, so as to preheat the seed crystal and prevent the seed crystal from bursting, cracking and the like when the seed crystal contacts the melt due to overlarge temperature difference between the seed crystal and the melt.
Further, in step (S2), the beryllium aluminate seed crystal is oriented to <001>, <010>, or <100>.
Further, in the step (S2), the seed crystal is lowered to 2-3 mm below the liquid level of the melt and kept for 5-10min, so that the contact part of the seed crystal and the melt is melted.
Further, in the step (S2), an ultrasonic environment with periodically alternating ultrasonic frequencies ranging from 50kHz to 60kHz to 120 kHz is applied to the environment, and each period is 10 to 20 minutes, namely the ultrasonic frequency is gradually increased from a low frequency section (50 kHz to 60 kHz) to a high frequency section (120 kHz to 150 kHz) and then is reduced from the high frequency section to the low frequency section, so that a complete period is calculated. Each cycle time is 10-20min.
Preferably, the periodic variation of the ultrasound frequency is performed according to a sinusoidal function curve.
Further, in the step (S2), the reaching of the crystal diameter to the requirement means that the crystal diameter reaches 30 to 50mm. And rotating and lifting the seed crystal upwards at a lifting speed of 1-2mm/h and a rotating speed of 10-20 rpm.
Further, in the step (S3), slow cooling is program cooling, and the temperature is reduced to 1100-1300 ℃ at a cooling rate of 10-15 ℃/h; and then cooling to 700-900 ℃ at a cooling rate of 20-35 ℃/h, and finally cooling to room temperature at a cooling rate of 40-50 ℃/h to obtain the precious stone-grade beryllium aluminate crystal with large size and few defects.
The slow cooling program cooling mode is adopted, so that color center defects and stress generated in the crystal growth process can be eliminated, and the obtained large-size crystal has fewer defects and is more stable. When cooling is started, the cooling rate is lower and is 10-15 ℃/h, then the cooling rate is gradually increased to 20-35 ℃/h, crystal cracking can be effectively prevented, then the cooling rate can be increased to 40-50 ℃/h after the crystal is stable, and the temperature is reduced to room temperature, so that large-size beryllium aluminate crystals can be obtained.
The preparation method is simple, can be completed by only matching a conventional ultrasonic device in the existing crystal growth device of the Czochralski method, and does not need complex and expensive equipment.
Drawings
FIG. 1 is a schematic diagram of an apparatus for growing crystals by the Czochralski method of the present invention;
in the figure: 1-furnace wall, 2-water cooling inlet, 3-water cooling outlet, 4-gasket, 5-corundum cup, 6-heat preservation sand, 7-crucible, 8-growth raw material, 9-heat preservation cover, 10-intermediate frequency coil, 11-ultrasonic wave generating end, 12-lifting rod, 13-electronic scale, 14-seed crystal and 15-growth crystal.
FIG. 2 is a plot of ultrasound frequency versus time period for the applied ultrasound environment of example 1;
FIG. 3 is a photograph of large-size precious stone grade beryllium aluminate crystals prepared in example 1.
Detailed Description
The materials and equipment used in the examples of the present invention were all from commercial routine purchasing routes.
Al 2O3 was purchased from Zhongtianli New Material Co., ltd, purity 99.99%; beO was purchased from Shanghai Pacific technologies Co., ltd. With a purity of 99.99%.
Example 1
(S1) Al 2O3 and BeO are fed into a corundum crucible according to a molar ratio of 1:1, the temperature is raised to 1800 ℃ for reaction for 15 hours to generate beryllium aluminate, the temperature is continuously raised to 1850 ℃ and kept for 2 hours to form a beryllium aluminate polycrystalline phase, and the temperature is continuously raised to 2100 ℃ to form a beryllium aluminate melt;
(S2) downwards moving the beryllium aluminate seed crystal with the orientation of <001> to the position 8mm above the liquid level of the beryllium aluminate melt in the step (S1), keeping the temperature for 1h, preheating the seed crystal, and preventing the situation that the seed crystal and the melt are unfavorable for crystal growth such as cracking caused by overlarge temperature difference. After preheating, the seed crystal is lowered to 2mm below the liquid level of the melt, the contact part of the seed crystal and the melt is melted, an ultrasonic environment with the ultrasonic frequency ranging from 60kHz to 120kHz periodically changing according to 10min (namely the ultrasonic frequency is raised from 60kHz to 120kHz and then lowered back to 60kHz for 10 min) is applied to the environment, the relationship between the ultrasonic frequency and the time period is shown in figure 2, and the ultrasonic frequency change is a sine function curve. Simultaneously, the seed crystal is lifted upwards, the lifting speed is 2mm/h, the rotating speed is 15rpm, the crystal starts to grow until the diameter of the crystal reaches 35mm, the ultrasonic environment is removed, and the temperature is maintained until the crystal growth is finished;
(S3) after the crystal growth is finished, pulling the beryllium aluminate crystal away from the melt, and setting a program cooling, specifically, cooling to 1300 ℃ at a cooling rate of 10 ℃/h; and then cooling to 900 ℃ at a cooling rate of 20 ℃/h, and finally cooling to room temperature at a cooling rate of 40 ℃/h to obtain the large-size precious stone-grade beryllium aluminate crystal, wherein the size is 520mm in length and 35mm in diameter. The interior of the crystal blank is irradiated by 20mWHe-Ne laser, and no scattering particles are visible to naked eyes.
FIG. 3 is a photograph of a large-sized precious-stone-grade beryllium aluminate crystal prepared in this example.
Example 2
Other conditions are the same as in example 1 except that in step (S2), the applied ultrasonic environment is such that the ultrasonic frequency of 60kHz to 150kHz is changed periodically for 15 minutes.
Example 3
Other conditions are the same as in example 1 except that in step (S2), the applied ultrasonic environment is such that the ultrasonic frequency of 50kHz to 100kHz is changed periodically for 20 minutes.
Example 4
Other conditions are the same as in example 1 except that in step (S3), the temperature is lowered to room temperature at a temperature lowering rate of 20 ℃/h, i.e., no program cooling is provided.
Comparative example 1
Other conditions are the same as in example 1 except that in step (S2), the ultrasonic environment is not applied.
Comparative example 2
The other conditions were the same as in example 1 except that in step (S2), the applied ultrasonic frequency was constant at 60kHz.
Comparative example 3
The other conditions were the same as in example 1 except that in step (S2), the applied ultrasonic frequency was constant at 120kHz.
The beryllium aluminate crystals prepared in the above examples and comparative examples were subjected to optical property test, and the results are shown in table 1 below.
The weak light absorption coefficient test wavelength was 1064nm.
Optical uniformity was performed on a ZYGO laser digital interferometer.
Table 1 optical performance test
。
As can be seen from the data in Table 1, the large-size beryllium aluminate prepared by the upward pulling method under the periodically-changed ultrasonic environment has few crystal defects, and the weak light absorption coefficient and the optical uniformity are very excellent, so that the requirements of high-end laser equipment application can be met. Although the application of an ultrasonic environment can also improve the optical uniformity of the crystal to some extent, it is still not yet satisfactory, and the inventors have unexpectedly found that a periodically changing ultrasonic frequency environment can greatly improve the optical uniformity of the crystal.
Claims (10)
1. The preparation method of the precious-grade beryllium aluminate crystal is characterized by comprising the following steps of:
(S1) feeding an aluminum source and a beryllium source into a crucible, heating to 1800-1850 ℃ for reaction to generate beryllium aluminate, continuously heating to 50-100 ℃ and preserving heat for 1-2 hours to form beryllium aluminate crystal phase, and continuously heating to 2100-2200 ℃ to form beryllium aluminate melt;
(S2) pumping vacuum of crystal growth pulling equipment, then filling argon, downwards moving beryllium aluminate seed crystal above the liquid level of the beryllium aluminate melt in the step (S1) and keeping the temperature for a period of time, starting to downwards move the seed crystal, enabling the seed crystal to downwards move below the liquid level of the melt and keep for a period of time, starting to rotate and upwards pull the seed crystal, simultaneously applying an ultrasonic environment with the ultrasonic frequency ranging from 50kHz to 60kHz to 100 kHz to 150kHz to periodically and alternately change, starting to grow crystals in each period of 10 to 20 minutes, and removing the ultrasonic environment until the crystal diameter reaches the requirement, and keeping the temperature until the crystal growth is finished;
And (S3) after the crystal growth is finished, pulling the crystal away from the melt, and slowly cooling to room temperature to obtain the precious stone-grade beryllium aluminate crystal.
2. The preparation method according to claim 1, wherein in the step (S1), the aluminum source is at least one selected from aluminum oxide and aluminum hydroxide, and the beryllium source is at least one selected from beryllium oxide, beryllium hydroxide and beryllium carbonate, and the purity of the raw material is not less than 99.9%.
3. The method according to claim 1, wherein in step (S1), the aluminum source and the beryllium source are prepared according to Al: feeding the materials according to the molar ratio of Be of 2-2.1:1; the reaction time is 15-20h.
4. The method according to claim 1, wherein in the step (S2), the crystal growth pulling apparatus is evacuated and then filled with argon gas at a pressure of 1X 10 -3 Pa to 5X 10 -3 Pa, and the filling with argon gas is 0.8 to 1 atm.
5. The method of claim 1, wherein in step (S2), the beryllium aluminate seed crystal is moved down to 5-15mm above the level of the beryllium aluminate melt in step (S1); the constant temperature is maintained for a period of time at the constant temperature of 0.5-1h under the ambient temperature.
6. The method of claim 1, wherein in step (S2), the beryllium aluminate seed is oriented as <001>, <010>, or <100>.
7. The method according to claim 1, wherein in the step (S2), the seed crystal is lowered to 2 to 3mm below the melt level and held for 5 to 10 minutes, and the contact portion of the seed crystal and the melt is melted.
8. The method according to claim 1, wherein in the step (S2), the periodically alternating ultrasonic environment means that the ultrasonic frequency gradually increases from the low frequency band to the high frequency band and then decreases from the high frequency band to the low frequency band, so as to calculate a complete cycle; each cycle time is 10-20min; the periodic variation of the ultrasonic frequency is performed according to a sine function curve; the low frequency band is 50-60kHz and the high frequency band is 120-150kHz.
9. The method according to claim 1, wherein in the step (S2), the achievement of the crystal diameter is a requirement that the crystal diameter is 30 to 50mm; and rotating and lifting the seed crystal upwards at a lifting speed of 1-2mm/h and a rotating speed of 10-20 rpm.
10. The preparation method according to claim 1, wherein in the step (S3), slow cooling is programmed cooling, and the cooling rate is 10-15 ℃/h to 1100-1300 ℃; then cooling to 700-900 ℃ at a cooling rate of 20-35 ℃/h, and finally cooling to room temperature at a cooling rate of 40-50 ℃/h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4809283A (en) * | 1988-02-26 | 1989-02-28 | Allied-Signal Inc. | Method of manufacturing chromium-doped beryllium aluminate laser rod and lasers incorporating the rods therein |
| CN1195717A (en) * | 1997-04-08 | 1998-10-14 | 中国科学院上海光学精密机械研究所 | Method and device for growing diamond of aureoviridae family |
| CN1824847A (en) * | 2005-02-23 | 2006-08-30 | 上海中晶企业发展有限公司 | Process and device for overcoming melt ageing, in crystal growth |
| RU2471896C1 (en) * | 2011-10-26 | 2013-01-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Южно-Уральский государственный университет" (национальный исследовательский университет) (ФГБОУ ВПО "ЮУрГУ" (НИУ)) | Method of growing bulk monocrystals of alexandrite |
| CN108060456A (en) * | 2017-12-12 | 2018-05-22 | 中国科学院上海光学精密机械研究所 | The Bridgman-Stockbarger method of beryllium aluminate crystal |
-
2024
- 2024-10-23 CN CN202411483460.4A patent/CN118996606B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4809283A (en) * | 1988-02-26 | 1989-02-28 | Allied-Signal Inc. | Method of manufacturing chromium-doped beryllium aluminate laser rod and lasers incorporating the rods therein |
| CN1195717A (en) * | 1997-04-08 | 1998-10-14 | 中国科学院上海光学精密机械研究所 | Method and device for growing diamond of aureoviridae family |
| CN1824847A (en) * | 2005-02-23 | 2006-08-30 | 上海中晶企业发展有限公司 | Process and device for overcoming melt ageing, in crystal growth |
| RU2471896C1 (en) * | 2011-10-26 | 2013-01-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Южно-Уральский государственный университет" (национальный исследовательский университет) (ФГБОУ ВПО "ЮУрГУ" (НИУ)) | Method of growing bulk monocrystals of alexandrite |
| CN108060456A (en) * | 2017-12-12 | 2018-05-22 | 中国科学院上海光学精密机械研究所 | The Bridgman-Stockbarger method of beryllium aluminate crystal |
Non-Patent Citations (1)
| Title |
|---|
| 王鸿雁等: "大尺寸优质Cr3+∶BeAl2O4晶体生长与性能研究", 人工晶体学报, vol. 53, no. 06, 15 June 2024 (2024-06-15), pages 947 - 953 * |
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