CN102127810B - Basic bismuth nitrate nonlinear crystal material and preparation method and application thereof - Google Patents
Basic bismuth nitrate nonlinear crystal material and preparation method and application thereof Download PDFInfo
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- CN102127810B CN102127810B CN 201110004735 CN201110004735A CN102127810B CN 102127810 B CN102127810 B CN 102127810B CN 201110004735 CN201110004735 CN 201110004735 CN 201110004735 A CN201110004735 A CN 201110004735A CN 102127810 B CN102127810 B CN 102127810B
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Abstract
The invention relates to a basic bismuth nitrate nonlinear crystal material and a preparation method and an application thereof. The basic bismuth nitrate nonlinear crystal material belongs to an orthorhombic crystal system, has a chemical formula of Bi2O2(OH)(NO3) and a space group of Cmc21, and has the following cell parameters: a=5.3878(11), b=5.3984(10), c=17.136(2), alpha=beta3=gamma=90 degrees. The basic bismuth nitrate nonlinear crystal material is prepared through reaction between a bismuth salt and deionized water under the heating condition. The prepared crystal is millimeter-sized, transparent, not easy to disintegrate, easy to store, and has stable physical and chemical properties, good frequency-doubling effect and no deliquescence. The preparation method has the characteristics of rapid crystal growth rate, low cost, mild condition and pure product, and is simple to operate.
Description
Technical field
The present invention relates to a kind of novel non-linearity crystalline material.
Background technology
Non-linear optic crystal can be realized the laser frequency conversion, widens laser wavelength range, thereby makes the application of laser more extensive.Nonlinear optical material is in modern times in the science and technology, in particularly some military and civilian high-tech areas, and for example submarine deep water communication, blinding laser weapons; The ocean locating fish, video disc recording, color laser printing; Laser projection tv, photometry calculation and optical-fibre communications etc. all have a series of application.
The growth of non-linear optic crystal, method commonly used has flux method, melting method, hydrothermal method etc.Hydrothermal method be utilize the aqueous solution of HTHP make those under atmospheric condition insoluble or indissoluble substance dissolves; Or the lysate of this material of reaction generation, make the generation convection current separate out the crystalline method through the temperature difference of controlling solution in the autoclave to form hypersaturated state.Crystal is grown under hydrothermal condition has following advantage: 1, the hydro-thermal crystal is under relatively low thermal stress conditions, to grow, so its dislocation desity is far below the crystal of growing in the high-temperature fusant; 2, relatively low temperature is used in the hydro-thermal crystal growth, thereby can obtain the material low temperature isomr that additive method is difficult to obtain; 3, the hydrothermal method crystal growth is in a closed system, to carry out, and can control reaction atmosphere and forms oxidation or reduction reaction conditions, realizes that some thing of the material that additive method is difficult to obtain generates mutually; 4, hydro-thermal reaction system exists the quick convection current of solution and the diffusion of highly effective solute, so hydrothermal crystallization has growth velocity faster.
Bi
2O
2(OH) (NO
3) belonging to rhombic system, mostly existing this crystal is powder, up to now, the report of this crystal double frequency effect of Shang Weiyou and the crystal growth of millimeter level.
Summary of the invention
The purpose of this invention is to provide a kind of non-linear optical crystal material Bi
2O
2(OH) (NO
3).
The technical scheme that the present invention takes is:
A kind of Vikaline (BINO) nonlinear crystalline material, its chemical formula is Bi
2O
2(OH) (NO
3), belonging to rhombic system, spacer is Cmc2
1, unit cell parameters is: a=5.3878 (11) b=5.3984 (10), and c=17.136 (2), α=β=γ=90 °,
Described nonlinear crystalline material, frequency multiplication are 5-10 times of KDP.
The preparation method of described Vikaline nonlinear crystalline material, step is following:
(1) weighing contains the salt of Bi, puts into reaction kettle, adds or do not add mineralizer;
(2) add deionized water, uncomfortable PH or regulate PH with mineral alkali is stirred to till the hydrolysis fully evenly;
(3) reaction kettle is placed in 100 ℃-250 ℃ the baking oven reacting by heating 1-7 days;
(4) after reaction finished, the room temperature cooling was with product washing, oven dry.
The salt of the described Bi of containing is Bi (NO
3)
35H
2O or Bi
2(SO
4)
37H
2O, preferred Bi (NO
3)
35H
2O.
Described deionized water consumption is 1:1 ~ 14:1 with the mass ratio that contains the salt of Bi, (even the compactedness of 25ml still is 10%-100%).
Described mineralizer is boric acid, oxalic acid, KNO
3Or urea, preferred KNO
3, consumption is the 5%-50% that contains the salt quality of Bi.
Described mineral alkali is with NaOH, KOH or ammoniacal liquor.Be adjusted to the PH scope and be PH 8, best PH < 1.
Temperature of reaction is preferred 160 ℃ among the above-mentioned preparation method, step (3), preferred 3 days of reaction times.
The application of described Vikaline nonlinear crystalline material in wavelength conversion device, optical parameter and image intensifer, electrooptical light modulator.
It is fast that preparation method of the present invention has crystalline growth velocity, simple to operate, and cost is low, mild condition, the purified characteristics of product.Made crystalline size is the millimeter level, and is transparent, not easily broken, and physico-chemical property is stable, and deliquescence is not prone to preserve; The nonlinear crystalline material that obtains has good frequency-doubled effect.
Description of drawings
Fig. 1 is the Bi of the present invention's preparation
2O
2(OH) (NO
3) crystalline crystalline structure figure;
Fig. 2 is the Bi of the present invention's preparation
2O
2(OH) (NO
3) the X-ray diffraction in crystals spectrogram;
Fig. 3 is the Bi of the present invention's preparation
2O
2(OH) (NO
3) the crystalline photo.
Embodiment
Embodiment 1:
Weighing Bi (NO
3)
35H
2O 3.2335g puts into the 30ml reaction kettle.Add the 25ml deionized water, promptly the compactedness of still is 70%-80%.On magnetic stirring apparatus, stirred 15-20 minute, till hydrolysis stirs fully.Reaction kettle is placed in 160 ℃ the baking oven reacting by heating 5 days.After reaction finishes,, then the product in the still is transferred in the small beaker of 50ml, supernatant liquid is outwelled, use washed with de-ionized water, till supernatant PH=7 reaction kettle naturally cooling at room temperature.Outwell supernatant, the baking oven of product being put into 50-60 ℃ is dried.
Embodiment 2:
Weighing Bi (NO
3)
35H
2O 3.2316g, H
3BO
30.6280g, put into the 25ml reaction kettle.Add the 20ml deionized water, promptly the compactedness of still is 70%-80%.On magnetic stirring apparatus, stirred 15-20 minute, till hydrolysis stirs fully.Reaction kettle is placed in 160 ℃ the baking oven reacting by heating 3 days.After reaction finishes,, then the product in the still is transferred in the small beaker of 50ml, supernatant liquid is outwelled, use washed with de-ionized water, till supernatant PH=7 reaction kettle naturally cooling at room temperature.Outwell supernatant, the baking oven of product being put into 50-60 ℃ is dried.
Embodiment 3:
Weighing Bi (NO
3)
35H
2O 1.6143g puts into the 25ml reaction kettle.Add the 20ml deionized water, promptly the compactedness of still is 70%-80%.On magnetic stirring apparatus, stirred 15-20 minute, till hydrolysis stirs fully.Reaction kettle is placed in 160 ℃ the baking oven reacting by heating 3 days.After reaction finishes,, then the product in the still is transferred in the small beaker of 50ml, supernatant liquid is outwelled, use washed with de-ionized water, till supernatant PH=7 reaction kettle naturally cooling at room temperature.Outwell supernatant, the baking oven of product being put into 50-60 ℃ is dried.
Embodiment 4:
Weighing Bi (NO
3)
35H
2O 3.2333g, urea 0.2506g puts into the 25ml reaction kettle.Add the 15-20ml deionized water, promptly the compactedness of still is 70%-80%.On magnetic stirring apparatus, stirred 20 minutes, till hydrolysis stirs fully.Reaction kettle is placed in 200 ℃ the baking oven reacting by heating 3 days.After reaction finishes,, then the product in the still is transferred in the small beaker of 50ml, supernatant liquid is outwelled, use washed with de-ionized water, till supernatant PH=7 reaction kettle naturally cooling at room temperature.Outwell supernatant, the baking oven of product being put into 50-60 ℃ is dried.
Embodiment 5:
Weighing Bi (NO
3)
35H
2O 3.2324g, KNO
30.2123g, put into the 25ml reaction kettle.Add the 20ml deionized water, promptly the compactedness of still is 70%-80%.On magnetic stirring apparatus, stirred 15-20 minute, till hydrolysis stirs fully.Reaction kettle is placed in 200 ℃ the baking oven reacting by heating 3 days.After reaction finishes,, then the product in the still is transferred in the small beaker of 50ml, supernatant liquid is outwelled, use washed with de-ionized water, till supernatant PH=7 reaction kettle naturally cooling at room temperature.Outwell supernatant, the baking oven of product being put into 50-60 ℃ is dried.
Embodiment 6:
Weighing Bi (NO
3)
35H
2O 1.6197g, H
2C
2O
40.6317g, put into the 25ml reaction kettle.Add the 20ml deionized water, promptly the compactedness of still is 70%-80%.On magnetic stirring apparatus, stirred 15-20 minute, till hydrolysis stirs fully.Reaction kettle is placed in 200 ℃ the baking oven reacting by heating 2 days.After reaction finishes,, then the product in the still is transferred in the small beaker of 50ml, supernatant liquid is outwelled, use washed with de-ionized water, till supernatant PH=7 reaction kettle naturally cooling at room temperature.Outwell supernatant, the baking oven of product being put into 50-60 ℃ is dried.
Embodiment 7:
Weighing Bi (NO
3)
35H
2O 3.2354g, H
3BO
30.6183g.Put into the 25ml reaction kettle.Add the 20ml deionized water, promptly the compactedness of still is 70%-80%.Add NaOH regulator solution PH=6.On magnetic stirring apparatus, stirred 15-20 minute, till hydrolysis stirs fully.Reaction kettle is placed in 200 ℃ the baking oven reacting by heating 2 days.After reaction finishes,, then the product in the still is transferred in the small beaker of 50ml, supernatant liquid is outwelled, use washed with de-ionized water, till supernatant PH=7 reaction kettle naturally cooling at room temperature.Outwell supernatant, the baking oven of product being put into 50-60 ℃ is dried.
Embodiment 8:
Weighing Bi (NO
3)
35H
2O 3.2354g puts into the 25ml reaction kettle.Add the 15ml deionized water, add ammoniacal liquor regulator solution PH=3.The compactedness that is still is 70%-80%.On magnetic stirring apparatus, stirred 15-20 minute, till hydrolysis stirs fully.Reaction kettle is placed in 100 ℃ the baking oven reacting by heating 1 day.After reaction finishes,, then the product in the still is transferred in the small beaker of 50ml, supernatant liquid is outwelled, use washed with de-ionized water, till supernatant PH=7 reaction kettle naturally cooling at room temperature.Outwell supernatant, the baking oven of product being put into 50-60 ℃ is dried.
Embodiment 9:
Weighing Bi (NO
3)
35H
2O 3.2354g puts into the 25ml reaction kettle.Add the 20ml deionized water, promptly the compactedness of still is 70%-80%.Add KOH regulator solution PH=7.On magnetic stirring apparatus, stirred 15-20 minute, till hydrolysis stirs fully.Reaction kettle is placed in 230 ℃ the baking oven reacting by heating 3 days.After reaction finishes,, then the product in the still is transferred in the small beaker of 50ml, supernatant liquid is outwelled, use washed with de-ionized water, till supernatant PH=7 reaction kettle naturally cooling at room temperature.Outwell supernatant, the baking oven of product being put into 50-60 ℃ is dried.
Embodiment 10:
Weighing Bi (NO
3)
35H
2O 1.6142g puts into the 25ml reaction kettle.Add the 10ml deionized water, promptly the compactedness of still is 30%-40%.On magnetic stirring apparatus, stirred 15-20 minute, till hydrolysis stirs fully.Reaction kettle is placed in 200 ℃ the baking oven reacting by heating 3 days.After reaction finishes,, then the product in the still is transferred in the small beaker of 50ml, supernatant liquid is outwelled, use washed with de-ionized water, till supernatant PH=7 reaction kettle naturally cooling at room temperature.Outwell supernatant, the baking oven of product being put into 50-60 ℃ is dried.
Embodiment 11:
Weighing Bi
2(SO
4)
37H
2O 3.2620g, KNO
30.4258g put into the 25ml reaction kettle.Add the 20ml deionized water, promptly the compactedness of still is 70%-80%.On magnetic stirring apparatus, stirred 15-20 minute, till hydrolysis stirs fully.Reaction kettle is placed in 200 ℃ the baking oven reacting by heating 3 days.After reaction finishes,, then the product in the still is transferred in the small beaker of 50ml, supernatant liquid is outwelled, use washed with de-ionized water, till supernatant PH=7 reaction kettle naturally cooling at room temperature.Outwell supernatant, the baking oven of product being put into 50-60 ℃ is dried.
Performance test:
Fig. 1 is Bi
2O
2(OH) (NO
3) crystalline crystalline structure figure, belonging to rhombic system, spacer is Cmc2
1, unit cell parameters is: a=5.3878 (11) b=5.3984 (10) c=17.136 (2), α=β=γ=90.，
Adopt the D8 type X-ray diffractometer of German BRUKER company that sample is carried out the thing identification of phases.Use CuK α radiation to be gamma ray source;
graphite monochromator; Pipe is pressed 40kv, pipe stream 40-60Ma.The Bi that obtains
2O
2(OH) (NO
3) X-ray diffraction in crystals spectrogram such as Fig. 2.
The frequency-doubled effect test is a standard with KDP, uses YAG Q-switch laser (1046nm) device to carry out powder frequency-doubled effect (SHG) test, and the 5-10 that product frequency multiplication of the present invention is KDP doubly.
The Bi of the present invention's preparation
2O
2(OH) (NO
3) crystalline digital photograph patriot GE-5 digital micrograph takes a picture and to see Fig. 3.
Claims (2)
1. the preparation method of a Vikaline nonlinear crystalline material is characterized in that, step is following:
(1) weighing contains the salt of Bi, puts into reaction kettle, adds or do not add mineralizer; The salt of the described Bi of containing is Bi (NO
3)
35H
2O or Bi
2(SO
4)
37H
2O, described mineralizer are boric acid, oxalic acid, KNO
3Or urea, the salt that wherein ought contain Bi is Bi
2(SO
4)
37H
2Must add mineralizer KNO during O
3, described mineralizer consumption is the 5%-50% that contains the salt quality of Bi;
(2) add deionized water, described deionized water is 1:1～14:1 with the mass ratio that contains the salt of Bi, uncomfortable pH or with mineral alkali NaOH, KOH or ammoniacal liquor be adjusted to pH 8, and be stirred to hydrolysis even fully till;
(3) reaction kettle is placed in 100 ℃-250 ℃ the baking oven reacting by heating 1-7 days;
(4) after reaction finished, the room temperature cooling was shifted out with product, and supernatant liquid is outwelled, and uses washed with de-ionized water, till supernatant PH=7, outwells supernatant, and the baking oven of product being put into 50-60 ℃ is dried.
2. the preparation method of Vikaline nonlinear crystalline material according to claim 1 is characterized in that, temperature of reaction is 160 ℃ in the step (3), and the reaction times is 3 days.
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| CN105056986B (en) * | 2015-08-10 | 2017-04-05 | 南京信息工程大学 | A kind of method and catalyst applications for preparing lamellar hydroxyl bismuth subnitrate photocatalyst |
| CN107899602B (en) * | 2017-11-01 | 2020-09-18 | 河南师范大学 | Preparation method of gray bismuth subnitrate photocatalytic material with visible light response |
| CN110129877B (en) * | 2019-06-12 | 2021-09-10 | 中国科学院新疆理化技术研究所 | Basic zinc borate nonlinear optical crystal and preparation method and application thereof |
Citations (2)
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|---|---|---|---|---|
| CN1528674A (en) * | 2003-09-29 | 2004-09-15 | 中国科学院上海硅酸盐研究所 | Method for preparing topographic controlled bismuth oxide poxder |
| CN1587063A (en) * | 2004-07-22 | 2005-03-02 | 中国地质大学（武汉） | Process for preparing nano alkaline bismuth nitrate by micro emulsion |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3173528B2 (en) * | 1992-06-19 | 2001-06-04 | 東亞合成株式会社 | Method for immobilizing carbonate ion or bicarbonate ion |
| JP3384419B2 (en) * | 1994-06-15 | 2003-03-10 | 東亞合成株式会社 | Hydrogen halide gas adsorbent |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1528674A (en) * | 2003-09-29 | 2004-09-15 | 中国科学院上海硅酸盐研究所 | Method for preparing topographic controlled bismuth oxide poxder |
| CN1587063A (en) * | 2004-07-22 | 2005-03-02 | 中国地质大学（武汉） | Process for preparing nano alkaline bismuth nitrate by micro emulsion |
Non-Patent Citations (5)
| Title |
|---|
| JP特开平6-366A 1994.01.11 |
| JP特开平7-328431A 1995.12.19 |
| N. Henry et al..《[Bi6O4.5(OH)3.5]2(NO3)11: a new anhydrous bismuth basic nitrate. Synthesis and structure determination from twinned crystals》.《Journal of Solid State Chemistry》.2003,第176卷(第1期), * |
| N. Henry et al..《Polycationic disorder in [Bi6O4(OH)4](NO3)6: Structure determination using synchrotron radiation and microcrystal X-ray diffraction》.《Journal of Solid State Chemistry》.2006,第179卷(第10期), * |
| 范力仁 等.《微乳液法制备纳米碱式硝酸铋》.《功能材料》.2004,第35卷 * |
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