CN101892514B - Process for growing sodium nitrate monocrystal by Bridgman method - Google Patents
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- CN101892514B CN101892514B CN2010102316212A CN201010231621A CN101892514B CN 101892514 B CN101892514 B CN 101892514B CN 2010102316212 A CN2010102316212 A CN 2010102316212A CN 201010231621 A CN201010231621 A CN 201010231621A CN 101892514 B CN101892514 B CN 101892514B
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Abstract
The invention relates to a method for growing a sodium nitrate monocrystal with large dimension and high quality by a Bridgman method, belonging to the technical field of crystal growth and comprising the following steps: adopting analytically pure sodium nitrate as a raw material, adopting a monolayer taper base platinum crucible or arc bottom quartz glass crucible for containing materials and utilizing a Bridgman furnace which adopts a silicon carbide rod or silicon-molybdenum rod as a heating element to carry out crystal growth, wherein the growth furnace temperature is 350-380 DEG C, the growth rate is 0.2-1.0mm/h, and the growth interface temperature gradient is 5-15 DEG C/cm. The growth process of the Bridgman method is simple and has the advantages that crystal growth can be carried out according to established conditions, the temperature field is stable, the radial temperature gradient is small, crystal cleavage can be effectively reduced, and sodium nitrate monocrystals with different specifications can be simultaneously grown in the same furnace.
Description
Technical field
The present invention relates to a kind of SODIUMNITRATE crystalline Bridgman-Stockbarge method for growing technology, especially relate to a kind of optical module, belong to the crystal technique field with SODIUMNITRATE crystalline Bridgman-Stockbarge method for growing technology.
Background technology
Sodium nitrate monocrystal (NaNO
3) the genus hexagonal system, spacer R3c, density 2.26g/cm
3, 306.8 ℃ of fusing points are prone to deliquescence, and soluble in water and liquefied ammonia is slightly soluble in ethanol, glycerine and acetone.Uniaxial negative crystal with big degree of birefringence, optical homogeneity is good, and transparency range can be applicable to optoisolator, circulator and various optical polarization prism between 0.2～2 μ m.The degree of birefringence of SODIUMNITRATE is bigger than calcite, helps simplifying device architecture, and with low cost, and transmittance is high, is more suitable for being applied to various polarizers than calcite.
The preparation difficult point of sodium nitrate monocrystal is that (1) raw material is prone to deliquescence, is easy to generate bubble at crystallisation process; (2) there is the paradoxical phase height at 275 ℃, has decomposition point, had relatively high expectations in temperature field and growth technique control at 380 ℃; (3) crystal is easy to crack, is difficult to obtain the complete monocrystalline of large size.At present, the report of the growing technology of relevant sodium nitrate monocrystal also seldom, it is not ideal enough on size, purity and crystallization degree to obtain crystal.
Summary of the invention
The object of the present invention is to provide a kind of technology of Bridgman-Stockbarge method for growing sodium nitrate monocrystal, to overcome the deficiency of prior art.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
A kind of Bridgman-Stockbarge method for growing technology of sodium nitrate monocrystal may further comprise the steps:
1) with raw material SODIUMNITRATE after 100～250 ℃ of roastings dewatered in 2～5 hours, in the crucible of packing into;
2) crucible after will feeding places the decline stove, and the control furnace temperature is 360～380 ℃, when the crucible bottom temperature reaches the SODIUMNITRATE fusing point, and the beginning crystal growth, fall off rate is 0.2～1.0mm/h, the thermograde of solid-liquid interface is 5～15 ℃/cm; After crystal growth finishes, make body of heater naturally cool to room temperature, take out crucible, crystal is peeled off from crucible, promptly obtain colourless sodium nitrate monocrystal.
Said SODIUMNITRATE is analytical pure, its purity >=99.0%.
Preferable, said crucible is an individual layer conical bottom platinum crucible, its wall thickness is 0.10～0.20mm.The preparation method of this platinum crucible is: at first metal platinum is carried out that melting is purified, forged, compressing tablet, use the conical bottom crucible that processes such as spot welding becomes required specification then, the disposable use of this crucible is through refine and can be repeatedly used again.Confirm as required by the shape and the size of predetermined growing crystal with big I for the shape of said individual layer conical bottom platinum crucible.
Preferable, said crucible is a circular arc bedstone English glass pot, its wall thickness is 1～2.5mm.This crucible is selected the crucible material of the silica glass of 500 ℃ of heatproofs as growing crystal, disposable use, not reproducible utilization for use.Confirm as required by the shape and the size of predetermined growing crystal with big I for the shape of said circular arc bedstone English glass pot.
Preferable, described decline stove is a heating element with globars or Si-Mo rod, the growth temperature field of this decline stove is stable, radially the temperature ladder is little for crystal, so the crystalline thermal stresses is little, can reduce crystal cleavage.
Further, in order to improve crystal purity and optical quality, with above-mentioned steps 2) the SODIUMNITRATE crystal that obtains inserts in the crucible repeating step 2 again), carry out secondary or three recrystallizations.
Further, in order fully to eliminate intracrystalline stress, reduce crystal cleavage, with the SODIUMNITRATE crystal that adopts aforesaid method to obtain anneal 10～24 hours under 100～250 ℃ of air atmospheres, the sodium nitrate monocrystal after annealing promptly can be used for mechanical workout.
Aforesaid method provided by the present invention, the sodium nitrate monocrystal of 4～8 different sizes of can a stove growing simultaneously, the sodium nitrate monocrystal (as shown in Figure 2) of the different shapes of promptly can growing simultaneously and size, its purity can reach 99.99%.
The present invention is a raw material with SODIUMNITRATE analytical pure (>=99.0%), is crucible with platinum or silica glass, the growth sodium nitrate monocrystal, and reach high-purity purpose through recrystallization.Simultaneously, it is the reactors of heating element that the present invention adopts globars or Si-Mo rod, and by the growth conditions growth sodium nitrate monocrystal of formulation, warm of its growth is stablized, radially the temperature ladder is little for crystal, so the crystalline thermal stresses is little, can reduce crystal cleavage.In addition, method growth technique of the present invention is simple, the sodium nitrate monocrystal of the many different sizes of can a stove growing simultaneously.Compare with existing growth method, method of the present invention can grow the complete high pure nitric acid sodium monocrystalline of crystalline phase.Therefore sodium nitrate monocrystal can be realized the yield rate height, crystal property is consistent, technology is simple and convenient, cost is low to use the present invention to grow; Be applicable to the sodium nitrate monocrystal of the required various size of growing optics polarizer.
Description of drawings
Fig. 1 is a crucible lowering method crystal growth device structure synoptic diagram;
Among the figure: 1 body of heater, 2 draw pipe down, 3 heating elements, 4 crucibles, 5 raw materials, 6 crystal, 7 thermopairs, 8 lowering means.
The SODIUMNITRATE crystal picture that Fig. 2 makes a living and looks, crystalline size is respectively Ф 25 * 80mm
3, Ф 20 * 150mm
3
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.Should be understood that these embodiment only are used to explain the present invention, and unrestricted scope of the present invention.
Sodium nitrate monocrystal Bridgman-Stockbarge method for growing technology of the present invention comprises: raw materials pretreatment, crucible preparation, growth apparatus, crystal growth, crystal are purified and the crystal aftertreatment.Concrete grammar is following:
One, raw materials pretreatment
Adopting SODIUMNITRATE analytical pure (>=99.0%) is raw material, after 100～250 ℃ of roastings dewatered in 2～5 hours, in loft drier, feeds.
Two, crucible preparation
Select the crucible material of platinum for use as growing crystal; At first metal platinum through melting purify, forge, compressing tablet; Use the individual layer conical bottom crucible that processes such as spot welding become required specification then; Sidewall of crucible thickness is generally 0.10～0.20mm, and the disposable use of crucible is through refine and can be repeatedly used again.
Select the crucible material of the silica glass of 500 ℃ of heatproofs for use, be processed as thickness 1～2.5mm, crucible at the bottom of the circular arc, the disposable use of crucible, not reproducible utilization as growing crystal.
Three, growth apparatus
The liner of crystal growing furnace and lagging material use alumina light-weight brick and aluminum silicate fiber; Heating element is made up of four Si-Mo rods; Adopt platinum-rhodium thermocouple through the accurate controller control of JWT-702 furnace; And monitor crystal growth with platinum rhodium thermocouple, crystalline growth velocity drives VSG by small machine and realizes that adjustable constant rate of speed decline crucible controls.The present invention adopts number of patent application 94114075.X, the growth apparatus described in the publication number CN1125787A, and its structure is shown in accompanying drawing 1.
Four, crystal growth
Raw material after handling is packed in platinum or the quartz glass crucibles, and charging should be fine and close as far as possible, after the charging mouth of pot end sealed.Draw in the following pipe inserting aluminum oxide at the bottom of the crucible down, fill with aluminum oxide powder in the space therebetween.To draw down and manage on the platform of placing lowering means, furnace temperature risen to 350～380 ℃, be incubated 4～6 hours then, and promote gradually again and draw pipe down, the interior raw material of crucible is melted gradually through 5-8 hour.Regulate crucible bottom and thermopair at same level attitude, when thermopair is shown as the SODIUMNITRATE fusing point, opens lowering means and begin crystal growth, fall off rate 0.2～1.0mm/h, the growth interface thermograde is 5～15 ℃/cm.After the distance that descends reached crystal expectation length, powered-down made body of heater naturally cool to room temperature, takes out crucible, and crystal is peeled off from crucible, obtains colourless sodium nitrate monocrystal.
Five, crystal is purified
In order to improve crystal purity and optical quality, the SODIUMNITRATE crystal that a secondary growth obtains is inserted in the platinum crucible again, repeat above-mentioned steps, carry out secondary or three recrystallization growths.
Six, crystal aftertreatment
In order fully to eliminate intracrystalline stress, reduce crystal cleavage, crystal to be annealed 10-24 hour under 100-250 ℃ of air atmosphere, the sodium nitrate monocrystal after annealing promptly can be used for mechanical workout.
With following specific embodiment is that example is further set forth content of the present invention.Related each processing parameter among the embodiment can be replaced by other numerical value in the above-mentioned disclosed processing condition scope, and these all can obtain effect of the present invention equally.
Embodiment 1:
(1) adopting SODIUMNITRATE analytical pure (>=99.0%) is raw material, after 200 ℃ of roastings dewatered in 2 hours, in loft drier, feeds;
(2) adopt size Ф 10 * 100mm
3, the cylindric quartz glass crucibles of wall thickness 1.5mm is packed the raw material compacting in the crucible into; Again crucible is inserted and draw down in the pipe, furnace temperature is risen to 370 ℃, be incubated 4～6 hours then and promote gradually and draw pipe down through 5 hours; When the crucible bottom temperature reaches the SODIUMNITRATE fusing point; Open lowering means and begin crystal growth, fall off rate 0.4mm/h, the growth interface thermograde is 5 ℃/cm;
(3) growth ending, powered-down makes body of heater naturally cool to room temperature, takes out quartz glass crucibles, and crystal is peeled off from crucible, obtains colourless sodium nitrate monocrystal.The present embodiment one stove 4 SODIUMNITRATE crystal of can growing.
Embodiment 2:
(1) adopting SODIUMNITRATE analytical pure (>=99.0%) is raw material, after 200 ℃ of roastings dewatered in 3 hours, in loft drier, feeds;
(2) adopt size Ф 20 * 200mm
3, the cylindric platinum crucible of wall thickness 0.12mm, with Control for Kiln Temperature at 370 ℃, fall off rate 0.4mm/h, the growth interface thermograde is 5 ℃/cm, other processing condition with the operation with embodiment 1.The present embodiment one stove 4 SODIUMNITRATE crystal of can growing.
Embodiment 3:
(1) adopting SODIUMNITRATE analytical pure (>=99.0%) is raw material, after 200 ℃ of roastings dewatered in 2 hours, in loft drier, feeds;
(2) adopt size Ф 25 * 200mm
3, the cylindric platinum crucible of wall thickness 0.14mm, with Control for Kiln Temperature at 370 ℃, fall off rate 0.6mm/h, the growth interface thermograde is 5 ℃/cm, other processing condition with the operation with embodiment 1.The present embodiment one stove 6 SODIUMNITRATE crystal of can growing.
Embodiment 4:
(1) the SODIUMNITRATE crystal (removing the impure part in top) that adopts embodiment 1-3 acquisition is as raw material;
(2) adopt size Ф 25 * 200mm
3, the cylindric platinum crucible of wall thickness 0.14mm grinds above-mentioned crystal block material in the platinum crucible of packing into, with Control for Kiln Temperature at 380 ℃, fall off rate 0.6mm/h, the interface growth thermograde is 10 ℃/cm, other processing condition and operation are with embodiment 1.The present embodiment one stove 8 SODIUMNITRATE crystal of can growing.
Embodiment 5:
(1) the SODIUMNITRATE crystal (removing the impure part in top) that adopts embodiment 4 acquisitions is as raw material;
(2) adopt size Ф 20 * 200mm
3, the cylindric quartz glass crucibles of wall thickness 2mm grinds above-mentioned crystal block material in the quartz glass crucibles of packing into, with Control for Kiln Temperature at 380 ℃, fall off rate 0.6mm/h, the interface growth thermograde is 10 ℃/cm, other processing condition and operation are with embodiment 1.The present embodiment one stove 8 SODIUMNITRATE crystal of can growing.
(3) step 2 acquisition crystal being incubated 24h under 200 ℃ of air atmospheres and making anneal, can obtain transparent, complete, the high pure nitric acid sodium monocrystalline of diameter Ф 25mm, is 99.99% through detecting its purity.
Claims (8)
1. the Bridgman-Stockbarge method for growing technology of a sodium nitrate monocrystal may further comprise the steps:
1) with raw material SODIUMNITRATE in 100～250 ℃ of roastings after 2～5 hours, in the crucible of packing into;
2) crucible after will feeding places the decline stove, and the control furnace temperature is 360～380 ℃, when the crucible bottom temperature reaches the SODIUMNITRATE fusing point, and the beginning crystal growth, fall off rate is 0.2～1.0mm/h, the thermograde of solid-liquid interface is 5～15 ℃/cm; After crystal growth finishes, make body of heater naturally cool to room temperature, take out crucible, crystal is peeled off from crucible, promptly obtain colourless sodium nitrate monocrystal.
2. the Bridgman-Stockbarge method for growing technology of sodium nitrate monocrystal as claimed in claim 1 is characterized in that, the purity of said raw material SODIUMNITRATE >=99.0%.
3. the Bridgman-Stockbarge method for growing technology of sodium nitrate monocrystal as claimed in claim 1 is characterized in that, gained SODIUMNITRATE crystal is inserted in the crucible again, carries out secondary or three recrystallization growths.
4. the Bridgman-Stockbarge method for growing technology of sodium nitrate monocrystal as claimed in claim 3 is characterized in that, with recrystallization gained SODIUMNITRATE crystal anneal 10～24 hours under 100～250 ℃ of air atmospheres.
5. like the Bridgman-Stockbarge method for growing technology of the described sodium nitrate monocrystal of arbitrary claim among the claim 1-4, it is characterized in that said crucible is an individual layer conical bottom platinum crucible, its wall thickness is 0.10～0.20mm.
6. like the Bridgman-Stockbarge method for growing technology of the described sodium nitrate monocrystal of arbitrary claim among the claim 1-4, it is characterized in that said crucible is a circular arc bedstone English glass pot, its wall thickness is 1～2.5mm.
7. like the Bridgman-Stockbarge method for growing technology of the described sodium nitrate monocrystal of arbitrary claim among the claim 1-4, it is characterized in that described decline stove is a heating element with globars or Si-Mo rod.
8. like the Bridgman-Stockbarge method for growing technology of the described sodium nitrate monocrystal of arbitrary claim among the claim 1-4, it is characterized in that, can place many crucibles in the described decline stove.
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| CN105063753A (en) * | 2015-08-28 | 2015-11-18 | 中国科学院上海硅酸盐研究所 | Czochralski method growth process of sodium nitrate monocrystalline |
| CN111155170A (en) * | 2020-01-09 | 2020-05-15 | 陕西华燕航空仪表有限公司 | Preparation method and application of sodium nitrate crystal |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189545A (en) * | 1997-01-30 | 1998-08-05 | 中国科学院上海光学精密机械研究所 | Vertical temperature gradient method for growing lithium aluminate and lithium gallate crystals |
| CN1196405A (en) * | 1997-04-15 | 1998-10-21 | 中国科学院上海光学精密机械研究所 | High temperature phase barium metaborate (alpha-BaB)2O4) Method for growing crystal |
| CN101235542A (en) * | 2007-11-14 | 2008-08-06 | 哈尔滨工业大学 | Polycrystalline synthesis and single-crystal growth method for germanium zinc phosphide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1989158B1 (en) * | 2006-01-31 | 2011-06-01 | Osram Sylvania, Inc. | Rare earth-activated aluminum nitride powders and method of making |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1189545A (en) * | 1997-01-30 | 1998-08-05 | 中国科学院上海光学精密机械研究所 | Vertical temperature gradient method for growing lithium aluminate and lithium gallate crystals |
| CN1196405A (en) * | 1997-04-15 | 1998-10-21 | 中国科学院上海光学精密机械研究所 | High temperature phase barium metaborate (alpha-BaB)2O4) Method for growing crystal |
| CN101235542A (en) * | 2007-11-14 | 2008-08-06 | 哈尔滨工业大学 | Polycrystalline synthesis and single-crystal growth method for germanium zinc phosphide |
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