CN1034964A - Rare-earth hexaboronide synthesized by melted salt electrolysis technique - Google Patents
Rare-earth hexaboronide synthesized by melted salt electrolysis technique Download PDFInfo
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- CN1034964A CN1034964A CN 88100855 CN88100855A CN1034964A CN 1034964 A CN1034964 A CN 1034964A CN 88100855 CN88100855 CN 88100855 CN 88100855 A CN88100855 A CN 88100855A CN 1034964 A CN1034964 A CN 1034964A
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Abstract
The present invention is a kind of method by rare-earth hexaboronide synthesized by melted salt electrolysis technique or mishmetal hexaboride.This method comprises the preparation of corresponding fused salt, and ionogen accompanying in the cathode product is removed in the casual eccysis of hot water and aqueous hydrochloric acid, and electrolysis temperature can adopt 800 ℃, uses metal or graphite (the most handy metallic copper) to make negative electrode.
With product advantages of good crystallization, purity height that this law makes, product proves single-phase through the gamma ray material phase analysis, and lattice constant is also consistent with literature value.
Description
The invention belongs to the synthetic method of rare-earth hexboride compound or mishmetal hexaboride.
People foretell that very early fused salt electrolysis is synthetic LaB
6Best method.But produce LaB so far
6Be not to adopt fused salt electrolysis process, but adopt boron thermal reduction method, this mainly is because it is believed that fused salt electrolysis is difficult to obtain pure LaB
6
We think that the major cause that fused salt electrolysis always is difficult to obtain single-phase product has 2 points: the one, before the used fused salt of electrolysis contained alkaline-earth metal fluoride, fluoaluminate etc., this makes to separate removes difficulty of electrolytic condenser accompanying in the cathode deposition, simultaneously, alkaline-earth metal ions, the Al in these fused salts
3+, Na
+Deng metal ion under the given electrolytic condition easily and rare earth ion, B
3+Separate out simultaneously, thereby be difficult to obtain single-phase product; The 2nd, the used negative electrode of electrolysis mostly used graphite rod or plumbago crucible in the past, must sneak into the carbon that is difficult to flush away in a large number in the cathode product like this, made the purity drop of product.The interior Tian Jianzhi of Japan reports in the clear 52-78799 of patent, uses La
2(B
4O
7)
3Or AlF
3+ LiF+La
2(B
4O
7)
3Make the fused salt component, under 800 °～1050 ℃ temperature and under nitrogen protection, carry out electrolysis as negative electrode, the LaB that on cathode bar, separates out with graphite rod
6Use HCl+AlCl
3Or H
2SO
4+ Al
2(SO
4)
3After the washing, obtained surpassing the LaB of theoretical amount
6[by 52 gram La
2(B
4O
7)
3Make the LaB of 36 grams
6], as seen its product purity is problematic.And, use Al when using nitrogen protection and washing cathode deposition
2(SO
4)
3And AlCl
3, all make the cost up of product; The fused salt component that it is used must use the temperature up to 1050 ℃ when electrolysis, the heat energy of consumption is too big; Because use graphite rod to make negative electrode, product is difficult to avoid sneaking into carbon, is difficult to obtain monophasic product.
It is easy to the objective of the invention is to seek a kind of technological operation, and production cost is low, can make the molten salt electrolysis method of the rare-earth hexboride compound monophasic, that purity is high.
The present invention adopts I (RE
2O
3+ B
2O
3+ Li
2O) or II (RE
2O
3+ B
2O
3+ Li
2CO
3) or III (RE
2O
3+ B
2O
3+ Li
2CO
3+ LiF) as fused salt component (wherein RE represents rare earth element), in the inherent air of 800 °～850 ℃ temperature ranges, carry out electrolysis, use metal (the most handy copper) rod to make negative electrode, the precipitate of negative electrode uses the hydrochloric acid soln washing of boiling water and 5%, promptly obtains rare-earth hexboride compound monophasic, that purity is high or mishmetal hexaboride.
Use the technology of present method manufacturing rare-earth hexboride compound simple, production cost is low, and product proves single-phase through the X ray material phase analysis, and lattice constant conforms to the report of document [1], the degree of purity of production height.
Example 1
Take by weighing 58.1 gram La
2O
3, 186.0 gram B
2O
3, 186.0 gram Li
2CO
369.8 put into a plumbago crucible after gram LiF mixes; changing diameter 850 ℃ of heating over to after 2 hours is 60mm; in another plumbago crucible of high 95mm; and the diameter that the latter is put into as protective sleeve is 90mm; height is in the steel crucibles of 120mm, this steel crucibles is put into diameter 100mm, in the crucible electrical resistance furnace of high 150mm.Be diameter that the rod iron of 5.4mm inserts the central authorities that the fused electrolyte 5cm degree of depth and suspention are fixed on plumbago crucible under the protection of diamond spar pipe box, be connected as anode with plumbago crucible with another root copper cash.Resistance furnace begins to heat up, and reaches 800 ℃ and keeps constant temperature 1 hour later on.Connect behind negative electrode and the anode at 20A, electrolysis is 8 hours under the 4.5-5.3V.Take out cathode bar and obtain cathode product 60.8 grams, after 50-100 ℃ hot water embathes, embathe with the 5%HCl aqueous solution again, embathe several times repeatedly, obtain purpureal LaB after the washing
6, get 25.6 gram products after the drying.This product proves single-phase LaB through the X ray material phase analysis
6(see figure 1), lattice constant are a
0=4.1658A conforms to the report of document [1].
Example 2
Take by weighing 30 gram Sm
2O
3, 96.5 gram B
2O
3, 96 gram Li
2CO
3Change in the plumbago crucible of diameter 40mm, high 80mm after the step fusion by example 1.As negative electrode, connect negative electrode and anode with diameter 2.3mm copper rod by the step of example 1.Electrolysis is 5 hours under 14A, 3.5-4.0V.Obtain cathode product 37.4 grams at last, embathe several times, obtain the blue SmB of 13.9 grams after washing, the drying through boiling water and aqueous hydrochloric acid
6This product proves single-phase SmB through the X ray material phase analysis
6(see figure 2), lattice constant a
0=4.1301A conforms to the report of document [1].
Example 3
This example is four circulations of continuous charging, prepares NdB respectively
6, NdB
6, (La, Nd) B
6, (La, Nd, Sm) B
6The fused salt of being mentioned in this example consist of 17.8%RE
2O
3+ 59.3%B
2O
3+ 22.9%Li
2O.Electrolysis temperature is 800 ℃, and electrolyzer is diameter 40mm, the plumbago crucible of high 80mm.As negative electrode, it is dark that negative electrode inserts fused salt 6cm with the copper rod of diameter 4mm.Used electric current is 20A, voltage 4.5-6V.Now four circulation institutes are added the fused salt amount and other general datas see Table 1.
Table 1, four circulation general datas
Circulation fused salt RE electrolysis time cathode product product
3 hours 41.0 gram 12.3 grams of 1 214.6 gram Nd
2 hours 30 minutes 32.5 gram 9.5 grams of 2 50.0 gram Nd
1 hour 47 minutes 20.5 gram 6.1 grams of 3 70.0 gram La
1 hour 30 minutes 29.5 gram 6.7 grams of 4 50.0 gram Sm
The product of circulation 1,2 is single-phase NdB by analysis
6, lattice constant a
0=4.1268A conforms to the report of document [1]; Product NdB
6Be blue.The product of circulation 3 is single-phase (La, Nd) B by analysis
6, lattice constant a
0=4.1413A.Product (La, Nd) B
6Be hepatic.The product of circulation 4 is single-phase (La, Nd, Sm) B by analysis
6Be blue [NdB
6, (La, Nd) B
6, (La, Nd, Sm) B
6Material phase analysis see Fig. 3,4 and 5]
Drawings attached 5 width of cloth of the present invention:
Fig. 1: LaB
6The X-ray powder diffraction pattern.
Fig. 2: SmB
6The X-ray powder diffraction pattern.
Fig. 3: LaB
6The X-ray powder diffraction pattern.
Fig. 4: (La, Nd) B
6The X-ray powder diffraction pattern.
Fig. 5: (La, Nd, Sm) B
6The X-ray powder diffraction pattern.
Reference
[1]AIIEN.M.AIPER，“Phase Diagrams：Materials Science and Technology”Vol.6-Ⅳ 1976.
Claims (6)
1, a kind of use rare-earth hexaboronide synthesized by melted salt electrolysis technique is (as LaB
6, SmB
6And NdB
6) or the mishmetal hexaboride [as (La, Nd) B
6, (La, Nd, Sm) B
6] method, it is characterized in that synthetic LaB
6, SmB
6And NdB
6The time, use fused salt component I (RE
2O
3+ B
2O
3+ Li
2O), II (RE
2O+B
2O
3+ Li
2CO
3) or III (RE
2O
3+ B
2O
3+ Li
2CO
3+ LiF), and synthesize (La, Nd) B
6(La, Nd, Sm) B
6The time, preferably use III to make fused salt component (wherein RE represents rare earth element), in the inherent air of 800 °～850 ℃ temperature range, carry out electrolysis then, the cathode deposition after electrolysis is intact promptly obtains rare-earth hexboride compound (as LaB after washing
6, SmB
6And NdB
6) or the mishmetal hexaboride [as (La, Nd) B
6(La, Nd, Sm) B
6].
2, according to the said use rare-earth hexaboronide synthesized by melted salt electrolysis technique of claim 1 (as LaB
6, SmB
6And NdB
6) or the mishmetal hexaboride [as (La, Nd) B
6, (La, Nd, Sm) B
6] method, it is characterized in that being to use in the electrolytic process metal (preferably copper) rod to make negative electrode.
3, according to the said use rare-earth hexaboronide synthesized by melted salt electrolysis technique of claim 2 (as LaB
6, SmB
6, NdB
6) or the mishmetal hexaboride [as (La, Nd) B
6, (La, Nd, Sm) B
6] method, it is characterized in that its cathodic metal rod is to use alundum tube interplanting protection, in order to avoid cathode bar oxidation by air at high temperature.
4, according to the said use rare-earth hexaboronide synthesized by melted salt electrolysis technique of claim 1 (as LaB
6, SmB
6, NdB
6) or the mishmetal hexaboride [as (La, Nd) B
6, (La, Nd, Sm) B
6] method, it is characterized in that material weight in the fused salt component I is than for RE
2O: B
2O
3: Li
2O=17.8: 59.3: 22.9, the weight ratio of II was Sm
2O: B
2O
3: Li
2CO
3=13.5: 43.4: 43.1, the weight ratio of III was La
2O
3: B
2O
3: Li
2CO
3: LiF=11.6: 37.2: 37.2: 14.0.
5, according to the said use rare-earth hexaboronide synthesized by melted salt electrolysis technique of claim 2 (as LaB
6, SmB
6And NdB
6) or the mishmetal hexaboride [as (La, Nd) B
6, (La, Nd, Sm) B
6] method, it is characterized in that using plumbago crucible to make electrolyzer, simultaneously as anode.
6, according to claim 1 and 2 said use rare-earth hexaboronide synthesized by melted salt electrolysis technique (as LaB
6, SmB
6And NdB
6) or the mishmetal hexaboride [as (La, Nd) B
6, (La, Nd, Sm) B
6] method, it is characterized in that using the HCl solution of boiling water and 5% to wash cathode deposition, monophasic to obtain, highly purified electrolysate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100855 CN1011247B (en) | 1988-02-09 | 1988-02-09 | Rare-earth hexaboronide synthesized by melted salt electrolysis technique |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88100855 CN1011247B (en) | 1988-02-09 | 1988-02-09 | Rare-earth hexaboronide synthesized by melted salt electrolysis technique |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1034964A true CN1034964A (en) | 1989-08-23 |
| CN1011247B CN1011247B (en) | 1991-01-16 |
Family
ID=4831532
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88100855 Expired CN1011247B (en) | 1988-02-09 | 1988-02-09 | Rare-earth hexaboronide synthesized by melted salt electrolysis technique |
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|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348483C (en) * | 2006-05-26 | 2007-11-14 | 华南理工大学 | Europium boride nano line, nano tube and its preparing method |
| CN100348484C (en) * | 2006-05-26 | 2007-11-14 | 华南理工大学 | Praseodymium boride nano line, and its preparing method and use |
| CN100360402C (en) * | 2006-06-16 | 2008-01-09 | 北京工业大学 | In-situs synthesis of high-purity nano-crystal LaB6 block material |
| CN102251251A (en) * | 2011-06-24 | 2011-11-23 | 武汉大学 | Method for preparing superfine metal boride |
| CN1479810B (en) * | 2000-11-15 | 2015-05-06 | 剑桥企业有限公司 | Method for producing intermetallic compounds |
| CN107034487A (en) * | 2017-05-02 | 2017-08-11 | 中南大学 | A kind of rare earth molten-salt electrolysis matter and electrolysis method for production |
-
1988
- 1988-02-09 CN CN 88100855 patent/CN1011247B/en not_active Expired
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1479810B (en) * | 2000-11-15 | 2015-05-06 | 剑桥企业有限公司 | Method for producing intermetallic compounds |
| CN100348483C (en) * | 2006-05-26 | 2007-11-14 | 华南理工大学 | Europium boride nano line, nano tube and its preparing method |
| CN100348484C (en) * | 2006-05-26 | 2007-11-14 | 华南理工大学 | Praseodymium boride nano line, and its preparing method and use |
| CN100360402C (en) * | 2006-06-16 | 2008-01-09 | 北京工业大学 | In-situs synthesis of high-purity nano-crystal LaB6 block material |
| CN102251251A (en) * | 2011-06-24 | 2011-11-23 | 武汉大学 | Method for preparing superfine metal boride |
| CN107034487A (en) * | 2017-05-02 | 2017-08-11 | 中南大学 | A kind of rare earth molten-salt electrolysis matter and electrolysis method for production |
| CN107034487B (en) * | 2017-05-02 | 2018-09-14 | 中南大学 | A kind of rare earth molten-salt electrolysis matter and electrolysis method for production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1011247B (en) | 1991-01-16 |
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