CN1974400A - Prepn and use of potassium fluorocarbonate - Google Patents
Prepn and use of potassium fluorocarbonate Download PDFInfo
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- CN1974400A CN1974400A CN 200610165039 CN200610165039A CN1974400A CN 1974400 A CN1974400 A CN 1974400A CN 200610165039 CN200610165039 CN 200610165039 CN 200610165039 A CN200610165039 A CN 200610165039A CN 1974400 A CN1974400 A CN 1974400A
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- potassium
- fluorocarbonate
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Abstract
The present invention discloses the preparation process and use of potassium fluorocarbonate. The preparation process includes the following steps: setting the mixture of potassium fluoride and alkali metal carbonate in the molar ratio of 1-1.5 into one reaction container, setting the reaction container in sealed environment filled with CO2 at 1.2-1.4 atm. and heating the reaction container to 500-800 deg.c, maintaining for 10-24 hr and cooling naturally to obtain the product potassium fluorocarbonate. The present invention synthesizes potassium fluorocarbonate with potassium fluoride and alkali metal carbonate, and has low cost, high product purity and other advantages.
Description
Technical field
The present invention relates to a kind of preparation method and its usage of potassium fluorocarbonate, particularly a kind of employing alkaline metal fluoride cpd, alkaline earth metal carbonate carry out the synthetic fluoro carbonate KCaCO of chemical reaction
3F and KSrCO
3Method of F and uses thereof.
Background technology
It is a kind of important non-linear optical effect that frequency of light wave transforms, and it is that the frequency multiplication light wave of 2 ω is called frequency-doubled effect that the fundamental light wave that for example a branch of frequency is ω produces a branch of frequency after by a non-linear optic crystal.The polarizability difference of carbanion in the fluoro carbonate and fluorion is very big, and wherein the polarizability of carbanion is very big and present anisotropy, for example α in lime carbonate
//=3.18 * 10
-24Cm
3α
=3.18 * 10
-24Cm
3, consult document 1:Kinase, W.; Tanaka, M.; Nomura, H.J.Phys.Coc.Japan 47 (1979) 1375; And the polarizability of fluorion is very weak and be isotropic (α=0.86 * 10
-24Cm
3), consult document 2:Jaswal, S.S.; Sharma, T.P.J.Phys.Chem.Solid.34 (1973) 509.Carbanion and fluorion polarizability have so big difference, may produce very strong frequency-doubled effect in suitable structure.
KCaCO has been reported at international powder diffraction data center (ICDD) in 1992
3F (card 44-0085) and KSrCO
3The powder diffraction data of F (card 44-0084).Both belong to hexagonal system.KCaCO
3The unit cell parameters a=b=5.101 of F, c=4.4551 .KSrCO
3The unit cell parameters a=b=5.2524 of F, c=4.6858 .People such as Chen Xiaolong have utilized X-ray powder diffraction data parsing KCaCO
3The crystalline structure of F, the spacer that obtains this compound is P 6m2.Consult document 3:Chen X.L., He Meng, Xu Y.P., Li H.Q, Tu Q.Y., Acta Cryst.E60 (2004) i50, this crystalline structure was further verified by refine according to the neutron diffraction data afterwards, consult document 4:Sun Y.P., Huang Q.Z., Wu L., He Ming, Chen X.L., J.Alloy.Comp.417 (2006) 13.The series compound K that comprises carbanion and fluorion equally
4RE
2(CO
3)
3F
4(Eu Gd) is observed very strong frequency doubling property, consults document 5:N.Mercier for RE=Nd, Sm, M.Leblanc, and J.Durand, Eur.J.SolidState Inorg.Chem.34 (1997) 241, and we infer KCaCO
3F and KSrCO
3These two compounds of F also may have non-linear optical property preferably.
Because different fluoro carbonate chemical property differences, the synthetic way also is not quite similar.With the fluoro carbonate of present discovery, the overwhelming majority is synthesized with hydrothermal method.But hydrothermal method synthetic sample productive rate is low, the equipment complexity, and the severe reaction conditions that needs is consulted document 6:Mercier, N., LeBlanc, M., European J.Solid State Inorg.Chem.31 (1994) 423.Adopt solid phase synthesis comparatively speaking the productive rate height, equipment is simple, operation is simple and easy.Synthetic such fluoro carbonate has adopted carbon-dioxide flow to take offence and has used the way of solid phase synthesis under the atmosphere in document 3 and the document 4, though the relative hydrothermal method of reaction conditions is synthetic fairly simple, and can suppress the decomposition of carbonate in reaction process, but this method has caused the bottom raw material reaction incomplete on the one hand, cause the waste of carbonic acid gas on the one hand, be unfavorable for environmental protection.
Summary of the invention
The object of the present invention is to provide a kind of with low cost, equipment simple, be easy to promote, reaction product purity height, the raw material reaction purposes of the prepared potassium fluorocarbonate of the preparation method of potassium fluorocarbonate and this method completely.
For achieving the above object, technical solution of the present invention is:
A kind of preparation method of potassium fluorocarbonate, this method may further comprise the steps: at first with Potassium monofluoride and alkaline earth metal carbonate by 1: 1-1.5: 1 mixed in molar ratio is put into reaction vessel after evenly, then this reaction vessel is placed the closed environment that is full of 1.2-1.4 atmospheric pressure carbon dioxide, and the temperature of reaction vessel risen to 500-800 ℃, be incubated and make its naturally cooling promptly obtain the potassium fluorocarbonate product after 10-24 hour.
Further, described alkaline earth metal carbonate is lime carbonate or Strontium carbonate powder, and corresponding described potassium fluorocarbonate is fluorine lime carbonate potassium or fluorine Strontium carbonate powder potassium.
Further, described Potassium monofluoride and alkaline earth metal carbonate purity are not less than 99.9%.
Further, before described Potassium monofluoride and alkaline earth metal carbonate mix in agate mortar grind into powder.
Further, described reaction vessel is platinum crucible or iridium crucible or yttrium crucible or tungsten crucible or iron crucible.
Adopt the prepared potassium fluorocarbonate of above-mentioned preparation method, described potassium fluorocarbonate is used to make frequency of light wave conversion crystal.
Further, described frequency of light wave conversion crystal can a branch of at least incident light wave sees through and a branch of at least frequency of generation is 1/2nd or 1/3rd a output light-wave of described incident light wave frequency.
Further, described frequency of light wave conversion crystal can see through and a branch of at least output light-wave of generation by a branch of at least incident light wave, and this output light-wave comprises that wavelength is that 1/2nd light wave of described incident light wave frequency and wavelength are 1/3rd light wave of described incident light wave frequency.
Compared with prior art, the present invention adopts Potassium monofluoride and alkaline earth metal carbonate to synthesize the fluoro carbonate method, and with low cost, equipment is simple, be easy to promote, and reaction product purity height, raw material reaction are complete.In addition, potassium fluorocarbonate powdered sample provided by the invention is through the frequency multiplication test, with non-linear optic crystal KDP (KH
2PO
4) compare KCaCO
3The Clock Multiplier Factor of F is about 5 times of Clock Multiplier Factor of KDP, KSrCO
3The Clock Multiplier Factor of F is about 13.4 times of Clock Multiplier Factor of KDP, is applied to the nonlinear optics purposes and has the high characteristics of shg efficiency.
Description of drawings
Fig. 1 is the KCaCO that adopts the inventive method preparation
3The X ray diffracting spectrum of F powder;
Fig. 2 is the KSrCO that adopts the inventive method preparation
3The X ray diffracting spectrum of F powder.
Embodiment
Embodiment 1
Take by weighing 0.15mol purity and be 99.9% Potassium monofluoride and 0.1mol purity and be 99.9% lime carbonate and in agate mortar, grind after mix, with the powder diameter 90mm that packs into, high 180mm, in the iron crucible of thick 10mm, with pack into vacuum electromagnetic induction furnace and connect pumped vacuum systems and be evacuated to 10 of crucible
-4Behind the Pa, charge into carbon dioxide atmosphere again.At pressure carbon dioxide is under 1.2 atmospheric pressure, rises to 500 ℃ with 8 ℃/minute speed from room temperature, is incubated 10 hours, powered-down, furnace cooling, the synthetic target product KCaCO that obtains white
3The F powder.
Embodiment 2
Taking by weighing 0.15mol purity and be 99.9% Potassium monofluoride and 0.1mol purity and be 99.9% Strontium carbonate powder grinds in agate mortar and mixes, with the powder diameter 90mm that packs into, high 180mm is in the thick 10mm platinum crucible, with pack into vacuum electromagnetic induction furnace and connect pumped vacuum systems and be evacuated to 10 of crucible
-4Behind the Pa, charge into carbon dioxide atmosphere again.At pressure carbon dioxide is under 1.4 atmospheric pressure, rises to 500 ℃ with 8 ℃/minute speed from room temperature, is incubated 20 hours, powered-down, furnace cooling, the synthetic target product KSrCO that obtains white
3The powder of F.
Embodiment 3
Taking by weighing 0.12mol purity and be 99.9% Potassium monofluoride and 0.1mol purity and be 99.9% lime carbonate grinds in agate mortar and mixes, with the powder diameter 90mm that packs into, high 180mm, in the tungsten crucible of thick 10mm, with pack into vacuum electromagnetic induction furnace and connect pumped vacuum systems and be evacuated to 10 of crucible
-4Behind the Pa, charge into carbon dioxide atmosphere again.At pressure carbon dioxide is under 1.3 atmospheric pressure, rises to 800 ℃ with 8 ℃/minute speed from room temperature, is incubated 20 hours, powered-down, furnace cooling, the synthetic target product KCaCO that obtains white
3The powder of F.
Embodiment 4
Taking by weighing 0.1mol purity and be 99.9% Potassium monofluoride and 0.1mol purity and be 99.9% Strontium carbonate powder grinds in agate mortar and mixes, with the powder diameter 90mm that packs into, high 180mm is in the iron crucible of thick 10mm, with pack into vacuum electromagnetic induction furnace and connect pumped vacuum systems and be evacuated to 10 of crucible
-4Behind the Pa, charge into carbon dioxide atmosphere again.At pressure carbon dioxide is under 1.4 atmospheric pressure, rises to 700 ℃ with 8 ℃/minute speed from room temperature, is incubated 24 hours, powered-down, furnace cooling, the synthetic target product KSrCO that obtains white
3The powder of F.
Figure 1 shows that the KCaCO that adopts the inventive method preparation
3The X ray diffracting spectrum of F powder Figure 2 shows that the KSrCO that adopts the inventive method preparation
3The X ray diffracting spectrum of F powder, as can be seen from the figure, the product that adopts the inventive method to obtain is single-phase potassium fluorocarbonate, various impurity such as oxide-free.
Between two sheet glass, the thick 1mm of sample strip measures and uses optical maser wavelength 1064nm, pulse width 10ps, laser intensity I=22.3mJ/cm with embodiment 1 and 3 resulting fluorine lime carbonate potassium specimen holders
2After the selected condition, above-mentioned laser beam is divided into two portions, the second harmonic signal of a part of excited sample, another part excite the second harmonic signal of reference substance, the KH of reference substance with the sample same particle sizes
2PO
4(KDP) compressing tablet will be compared with the signal that partly receives by reference substance KDP by the signal that fluorine lime carbonate sample partly receives, and just can obtain the Clock Multiplier Factor of fluorine lime carbonate with respect to KDP, be 5 times of KDP.
Between two sheet glass, the thick 1mm of sample strip measures and uses optical maser wavelength 1064nm, pulse width 10ps, laser intensity I=22.3mJ/cm with embodiment 2 and 4 resulting fluorine Strontium carbonate powder potassium specimen holders
2After the selected condition, above-mentioned laser beam is divided into two portions, the second harmonic signal of a part of excited sample, another part excite the second harmonic signal of reference substance, the KH of reference substance with the sample same particle sizes
2PO
4(KDP) compressing tablet will be compared with the signal that partly receives by reference substance KDP by the signal that fluorine Strontium carbonate powder sample partly receives, and just can obtain the Clock Multiplier Factor of fluorine Strontium carbonate powder with respect to KDP, be 13.4 times of KDP.
Because above-mentioned character, fluorine Strontium carbonate powder potassium, fluorine lime carbonate potassium can be used for frequency of light wave conversion, promptly fluorine Strontium carbonate powder potassium, fluorine lime carbonate potassium can a branch of at least incident light wave see through and a branch of at least frequency of generation be described incident light wave frequency 1/2nd or (with) 1/3rd output light-wave.
Above embodiment shows, is raw material with Potassium monofluoride and lime carbonate or Strontium carbonate powder, all can effectively synthesize corresponding potassium fluorocarbonate.Be noted that the above embodiments just illustrate the present invention with concrete example, and should not be limitation of the present invention.Simultaneously, those of ordinary skill in the art knows, on design of the present invention basis, to various modifications and variations that the present invention carried out all within the protection domain of this patent.Those of ordinary skill in the art may obtain fluorine lime carbonate potassium and fluorine Strontium carbonate powder potassium sample, and is applied in other the nonlinear optics application, and these all do not exceed design of the present invention and scope.
Claims (8)
1, a kind of preparation method of potassium fluorocarbonate, it is characterized in that, this method may further comprise the steps: at first with Potassium monofluoride and alkaline earth metal carbonate by 1: 1-1.5: 1 mixed in molar ratio is put into reaction vessel after evenly, then this reaction vessel is placed the closed environment that is full of carbon dioxide atmosphere, the pressure of carbon dioxide atmosphere is 1.2-1.4 normal atmosphere, and the temperature of reaction vessel risen to 500-800 ℃, be incubated and make its naturally cooling promptly obtain the potassium fluorocarbonate product after 10-24 hour.
2, the preparation method of a kind of potassium fluorocarbonate as claimed in claim 1 is characterized in that, described alkaline earth metal carbonate is lime carbonate or Strontium carbonate powder, and corresponding described potassium fluorocarbonate is fluorine lime carbonate potassium or fluorine Strontium carbonate powder potassium.
3, the preparation method of a kind of potassium fluorocarbonate as claimed in claim 1 is characterized in that, described Potassium monofluoride and alkaline earth metal carbonate purity are not less than 99.9%.
4, the preparation method of a kind of potassium fluorocarbonate as claimed in claim 1 is characterized in that, before described Potassium monofluoride and alkaline earth metal carbonate mix in agate mortar grind into powder.
5, the preparation method of a kind of potassium fluorocarbonate as claimed in claim 1 is characterized in that, described reaction vessel is platinum crucible or iridium crucible or yttrium crucible or tungsten crucible or iron crucible.
6, adopt aforesaid right to require the prepared potassium fluorocarbonate of 1 to 5 arbitrary preparation method, it is characterized in that, described potassium fluorocarbonate is used to make frequency of light wave conversion crystal.
As potassium fluorocarbonate as described in the claim 6, it is characterized in that 7, described frequency of light wave conversion crystal can a branch of at least incident light wave sees through and a branch of at least frequency of generation is 1/2nd or 1/3rd a output light-wave of described incident light wave frequency.
8, as potassium fluorocarbonate as described in the claim 7, it is characterized in that, described frequency of light wave conversion crystal can see through and a branch of at least output light-wave of generation by a branch of at least incident light wave, and this output light-wave comprises that wavelength is that 1/2nd light wave of described incident light wave frequency and wavelength are 1/3rd light wave of described incident light wave frequency.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103031602A (en) * | 2011-09-29 | 2013-04-10 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal potassium calcium carbonate fluoride |
| CN103031604A (en) * | 2011-09-29 | 2013-04-10 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal rubidium calcium fluorine carbonate |
| CN103031600A (en) * | 2011-09-29 | 2013-04-10 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal cesium barium carbonate fluoride |
| CN103031603A (en) * | 2011-09-29 | 2013-04-10 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal caesium calcium fluorine carbonate |
| CN103031601A (en) * | 2011-09-29 | 2013-04-10 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal rubidium strontium carbonate fluoride |
| CN103031605A (en) * | 2011-09-29 | 2013-04-10 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal potassium strontium fluorine carbonate |
| CN107195901A (en) * | 2017-05-27 | 2017-09-22 | 中国科学院物理研究所 | Perfluorocarbon acid salt material and preparation method thereof, anode pole piece and battery |
| CN118256995A (en) * | 2023-12-25 | 2024-06-28 | 桂林百锐光电技术有限公司 | Fluorocarbonate nonlinear optical crystal and growth method |
-
2006
- 2006-12-12 CN CN 200610165039 patent/CN1974400A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103031602A (en) * | 2011-09-29 | 2013-04-10 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal potassium calcium carbonate fluoride |
| CN103031604A (en) * | 2011-09-29 | 2013-04-10 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal rubidium calcium fluorine carbonate |
| CN103031600A (en) * | 2011-09-29 | 2013-04-10 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal cesium barium carbonate fluoride |
| CN103031603A (en) * | 2011-09-29 | 2013-04-10 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal caesium calcium fluorine carbonate |
| CN103031601A (en) * | 2011-09-29 | 2013-04-10 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal rubidium strontium carbonate fluoride |
| CN103031605A (en) * | 2011-09-29 | 2013-04-10 | 中国科学院福建物质结构研究所 | Nonlinear optical crystal potassium strontium fluorine carbonate |
| CN107195901A (en) * | 2017-05-27 | 2017-09-22 | 中国科学院物理研究所 | Perfluorocarbon acid salt material and preparation method thereof, anode pole piece and battery |
| CN118256995A (en) * | 2023-12-25 | 2024-06-28 | 桂林百锐光电技术有限公司 | Fluorocarbonate nonlinear optical crystal and growth method |
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