CN100402424C - Synthesis method of nano hexaboride - Google Patents
Synthesis method of nano hexaboride Download PDFInfo
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- CN100402424C CN100402424C CNB2006100534979A CN200610053497A CN100402424C CN 100402424 C CN100402424 C CN 100402424C CN B2006100534979 A CNB2006100534979 A CN B2006100534979A CN 200610053497 A CN200610053497 A CN 200610053497A CN 100402424 C CN100402424 C CN 100402424C
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- hexaboride
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Abstract
The invention discloses a synthesizing method of nanometer hexaboride (RB6), which comprises the following steps: adopting chloride of random one or two combinations of 57-71 rare earth metal elements, metal Y, alkaline earth Ba, Sr and Ca as raw material; making NaBH4 or KBH4 as reducer; reacting under low-temperature condition at 500-600 deg.c; washing; filtering; drying to obtain high-purity RB6 nanometer crystal powder.
Description
Technical field
The invention belongs to field of material synthesis technology, particularly a kind of nano hexaboride (RB
6) synthetic method of material.
Background technology
Has CaB
6One class boride of type cubic crystal structure has the characteristics of high-melting-point, high strength and high chemical stability, they also have many special functional, as: low electronic work function,, neutron uptake factor that emissive power strong and high stronger etc. than strong, the anti-ion bombardment ability of constant, the anti-poisoning capability of resistance, these high-performances make it be widely used in defense and commercial industry, also have broad application prospects in high-tech areas such as military project, aerospace.Best example is lanthanum hexaborane (LaB
6), it has been widely used in electron microscope, the energy spectrometer as cathode assembly.Utilize LaB
6Conduction, thermal conductivity good and stable chemical properties and higher hardness, LaB
6Be used to prepare a kind of novel all solid state iron ion sensitive electrode, have long service life, good stability can be used in high acidity media environment.Organic electroluminescent LED (OLED:Organic Light-Emitting Diode) becomes third generation technique of display, is the focus technology of research and development in the world.Adopt the organic electroluminescent LED of LaB6 preparation to have very thick that transmitance height, negative electrode can do, can solve the problem of cathode leg preferably.Therefore, LaB
6The transparent cathode film be prepared as high purity LaB
6Powder provides huge application market.RB
6High rigidity that compound has and abundant colors also make it become the important materials of top coat and decoration.
At present, be used for suitability for industrialized production RB
6The synthetic method of powder has: boron thermal reduction method, carbothermic method, fused salt electrolysis process and pure element chemical synthesis.The pure element chemical synthesis is to be mixed in proportion with metal R and simple substance B, is heated to prepared in reaction RB between 1300 ℃～2000 ℃
6Powder.Because the easy oxidation of metal R, simple substance B costs an arm and a leg, and scaling loss is serious, and manipulation require carries out in vacuum or inert atmosphere, and this method is to the equipment requirements height, and technique controlling difficulty is big.Boron thermal reduction method is that pyroreaction is synthesized RB with after the oxide compound of R or muriate and the mixing of boron powder
6Powder is because raw material is the high-purity boron powder that adopts, so the production cost height.The carbothermic reduction ratio juris is to add B and C or B in the oxide compound of R
4C is pressed into base with mixture then, heats in vacuum or hydrogen under 1500 ℃～1800 ℃, obtains RB
6Because raw material adopts high-purity B powder or B
4C, thus the production cost height, and the energy consumption height.Also there is the energy consumption height in electrolytic process, problems such as production cost height.Someone once reported with La
2O
3And B
2O
3Being raw material, is that the self-spreading metallurgical legal system of reductive agent is equipped with LaB with the Mg powder
6The method of powder also needs to be higher than 700 ℃ of temperature of reaction, because self-propagating reaction is to take place under the air atmosphere that opens wide, is easy to generate impurity in the product, need ooze out for a long time with hydrochloric acid and clean repeatedly.In addition, the powder diameter that traditional method obtains is difficult to control, is difficult for obtaining nanometer powder.
Summary of the invention
The present invention is exactly cost height, the energy consumption height that exists at traditional method for preparing hexaboride, and shortcomings such as complex process provide that a kind of temperature of reaction and cost are low, the cycle is short, the manageable hexaboride synthetic method of size of microcrystal.
The present invention is a raw material with the muriate of R, with NaBH
4Or KBH
4Be reductive agent, under 500～600 ℃ cold condition, react,, obtain high-purity RB at last through washing, filtration, drying
6The nanocrystal powder.Concrete steps are:
(1) presses reaction formula RCl
3+ 6NaBH
4=RB
6+ 3NaCl+12H
2+ 3Na or
RCl
3+ 6KBH
4=RB
6+ 3KCl+12H
2+ 3K or
RCl
2+ 6NaBH
4=RB
6+ 2NaCl+12H
2+ 4Na or
RCl
2+6KBH
4＝RB
6+2KCl+12H
2+4K
Molar ratio ingredient, the reactant that takes by weighing is carried out thorough mixing;
(2) said mixture is added in the reaction vessel, places autoclave to seal reactor again;
(3) autoclave is heated to 500～600 ℃, is incubated 3～10 hours, react fully and carry out, be cooled to room temperature afterwards;
(4) in vacuum drying oven, carry out drying with product collection and after cleaning, filtering, can obtain nanometer boride RB
6
Described RB
6The CaB that has for rare earth metal or alkaline-earth metal and boron formation
6One class boride of type crystal structure, R are represented in the periodic table of elements from 57 to No. 71 thulium (La～Lu), metal Y, alkaline-earth metal Ba, any or wherein any two kinds combination among Sr and the Ca.
Described reaction container materials is Ceramic Tube Type reaction crucibles such as quartz or aluminum oxide, and purpose is to prevent the reaction between the reactant and stainless steel autoclave when high-temperature.When temperature of reaction is lower than 500 ℃, reactant directly can be put into stainless steel autoclave.
Clean in the described step (4) is with the cleaning that hockets of deionized water or distilled water, dehydrated alcohol.In order to reduce the impurity in the final product, improve nano hexaboride purity, clean with dilute hydrochloric acid and water again.
The shape facility of the nano hexaboride that obtains by the control to pre-reaction material, reaction times, temperature of reaction is nanometer or micron-sized sphere, polyhedron, laminar, needle-like, piped crystal powder.
Synthetic method of the present invention has following advantage:
(1) muriate with R is a raw material, with NaBH
4Or KBH
4Be reductive agent, provide B by reductive agent simultaneously, can reduce production costs greatly;
(2) compare with traditional synthetic method, greatly reduced temperature of reaction, therefore cut down the consumption of energy;
(3) all operations can carry out in air atmosphere, can air in the sealed high pressure reflection still, also can use shielding gas such as nitrogen, argon gas, and simple to operate, low to the processing condition requirement, realize suitability for industrialized production easily;
(4) can be by the control of reaction conditions being obtained the nanometer six boron compound powder of different shape, its shape facility is nanometer or micron-sized sphere, polyhedron, laminar, needle-like, piped crystal powder.
Description of drawings
Fig. 1 is the x-ray diffraction experiment and the simulation collection of illustrative plates of one embodiment of the invention product.
Embodiment
Embodiment 1:
The analytically pure raw material of batching scale in proportion, LaCl
3(2.326g) and NaBH
4(2.1527g), put into the silica tube reaction vessel behind the thorough mixing.Seal after the silica tube reaction vessel put into the stainless steel autoclave; Autoclave is heated to 550 ℃, is incubated 6 hours and reacts fully and carry out, be cooled to room temperature afterwards; Behind product collection, use distilled water successively, 5% hydrochloric acid and distilled water clean, and obtain product after will filtering then and carry out drying in vacuum drying oven, can obtain nanometer boride LaB
6
As seen from Figure 1, resulting product is LaB
6
Embodiment 2:
The analytically pure raw material of batching scale in proportion, CeCl
3(2.1854g) and NaBH
4(2.0126g), put into the silica tube reaction vessel behind the thorough mixing.Seal after the silica tube reaction vessel put into the stainless steel autoclave; Autoclave is heated to 600 ℃, is incubated 3 hours and reacts fully and carry out, be cooled to room temperature afterwards; Behind product collection, use distilled water successively, 5% hydrochloric acid and distilled water clean, and obtain product after will filtering then and carry out drying in vacuum drying oven, can obtain nanometer boride CeB
6
Embodiment 3:
The analytically pure raw material of batching scale in proportion, CaCl
2(1.2011g) and KBH
4(3.5024g), seal after putting into the stainless steel autoclave behind the thorough mixing; Autoclave is heated to 500 ℃, is incubated 10 hours and reacts fully and carry out, be cooled to room temperature afterwards; Behind product collection, use distilled water successively, 5% hydrochloric acid and distilled water clean, and obtain product after will filtering then and carry out drying in vacuum drying oven, can obtain nanometer boride CaB
6
Embodiment 4:
The analytically pure raw material of batching scale in proportion, SrCl
2(2.2374g) and NaBH
4(3.2052g), seal after putting into the stainless steel autoclave behind the thorough mixing; Autoclave is heated to 550 ℃, is incubated 5 hours and reacts fully and carry out, be cooled to room temperature afterwards; Behind product collection, use distilled water successively, 5% hydrochloric acid and distilled water clean, and obtain product after will filtering then and carry out drying in vacuum drying oven, can obtain nanometer boride SrB
6
Embodiment 5:
The analytically pure raw material of batching scale in proportion, CeCl
3(1.6190g), LaCl
3(3.4770g) and NaBH
4(4.5970g), seal after putting into the stainless steel autoclave behind the thorough mixing; Autoclave is heated to 560 ℃, is incubated 8 hours and reacts fully and carry out, be cooled to room temperature afterwards; Behind product collection, use distilled water successively, 5% hydrochloric acid and distilled water clean, and obtain product after will filtering then and carry out drying in vacuum drying oven, can obtain nanometer boride Ce
0.3La
0.7B
6
Embodiment 6:
The analytically pure raw material of batching scale in proportion, YCl
3(1.0558g), GdCl
3(1.5227g) and KBH
4(3.500g), seal after putting into the stainless steel autoclave behind the thorough mixing; Autoclave is heated to 540 ℃, is incubated 10 hours and reacts fully and carry out, be cooled to room temperature afterwards; Behind product collection, use distilled water successively, 5% hydrochloric acid and distilled water clean, and obtain product after will filtering then and carry out drying in vacuum drying oven, can obtain nanometer boride Y
0.5Gd
0.5B
6
Claims (4)
1. the synthetic method of a nano hexaboride is characterized in that this synthetic method is a raw material with the muriate of R, with NaBH
4Or KBH
4Be reductive agent, under 500～600 ℃ cold condition, react,, obtain high-purity RB through washing, filtration, drying
6The nanocrystal powder, wherein R represents in the periodic table of elements from 57 to No. 71 thulium, metal Y, alkaline-earth metal Ba, any or wherein any two kinds combination among Sr and the Ca, concrete steps are:
(1) presses reaction formula RCl
3+ 6NaBH
4=RB
6+ 3NaCl+12H
2+ 3Na or
RCl
3+ 6KBH
4=RB
6+ 3KCl+12H
2+ 3K or
RCl
2+ 6NaBH
4=RB
6+ 2NaCl+12H
2+ 4Na or
RCl
2+6KBH
4＝RB
6+2KCl+12H
2+4K
Molar ratio ingredient, the reactant that takes by weighing is carried out thorough mixing;
(2) said mixture is added in the reaction vessel, places autoclave to seal reactor again;
(3) autoclave is heated to 500～600 ℃, is incubated 3～10 hours, react fully and carry out, be cooled to room temperature afterwards;
(4) in vacuum drying oven, carry out drying with product collection and after cleaning, filtering, can obtain nanometer boride RB
6
2. the synthetic method of a kind of nano hexaboride as claimed in claim 1 is characterized in that described RB
6The CaB that has for rare earth metal or alkaline-earth metal and boron formation
6One class boride of type crystal structure.
3. the synthetic method of a kind of nano hexaboride as claimed in claim 1 is characterized in that described reaction container materials is the Ceramic Tube Type reaction crucible.
4. the synthetic method of a kind of nano hexaboride as claimed in claim 1, it is characterized in that cleaning in the described step (4) is with cleanings that hocket of deionized water, distilled water, dehydrated alcohol, usefulness dilute hydrochloric acid and water cleaning again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100534979A CN100402424C (en) | 2006-09-21 | 2006-09-21 | Synthesis method of nano hexaboride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100534979A CN100402424C (en) | 2006-09-21 | 2006-09-21 | Synthesis method of nano hexaboride |
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|---|---|
| CN1923686A CN1923686A (en) | 2007-03-07 |
| CN100402424C true CN100402424C (en) | 2008-07-16 |
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| CNB2006100534979A Expired - Fee Related CN100402424C (en) | 2006-09-21 | 2006-09-21 | Synthesis method of nano hexaboride |
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Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050457B (en) * | 2009-10-29 | 2012-05-30 | 苏玉长 | Synthesis method of nano rare-earth tetraboride and applications thereof |
| CN101837987B (en) * | 2010-05-21 | 2012-11-14 | 山东大学 | Method for synthetizing synthetic metal boride nano-powder by iodine assisting magnesium co-reduction solid-phase reaction |
| CN101948117B (en) * | 2010-10-11 | 2013-01-30 | 山东大学 | Method for preparing nano superfine rare-earth hexaboride powder |
| CN103101922A (en) * | 2013-01-24 | 2013-05-15 | 浙江大学 | Preparation method of transition metal nano-boride |
| CN103848431A (en) * | 2013-12-10 | 2014-06-11 | 内蒙古师范大学 | Solid-phase reaction preparation method of crystal grain controllable LaB6 nanocrystal |
| CN105271281B (en) * | 2015-06-18 | 2017-08-25 | 贵州理工学院 | The preparation method of rare earth and alkaline earth hexaboride nano wire, nanometer rods and nanotube |
| CN104961137B (en) * | 2015-06-19 | 2018-03-06 | 内蒙古师范大学 | A kind of preparation method of nano alkaline-earth metal boride |
| CN105502428B (en) * | 2015-12-04 | 2016-11-30 | 湖南师范大学 | A kind of preparation method of lanthanum hexaboride quasi-one dimensional nanostructure array material |
| CN110844916A (en) * | 2019-11-27 | 2020-02-28 | 成都理工大学 | CaB6Preparation method of nanosheet |
| CN112898025A (en) * | 2021-02-02 | 2021-06-04 | 中冶节能环保有限责任公司 | Method for preparing vanadium boride ultrafine powder by carbon-thermal boron-thermal method |
| CN114538458B (en) * | 2022-01-28 | 2023-04-07 | 合肥工业大学 | Method for preparing high-purity barium hexaboride |
| CN114933311B (en) * | 2022-06-02 | 2023-08-25 | 安阳工学院 | Method for refining hexaboride powder |
| CN115180632B (en) * | 2022-07-15 | 2023-11-14 | 贵州交通职业技术学院 | Controllable preparation method and application of morphology of rare earth hexaboride nano powder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1252775A (en) * | 1997-04-18 | 2000-05-10 | 美国博拉克有限公司 | Method for producing calcium borate |
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2006
- 2006-09-21 CN CNB2006100534979A patent/CN100402424C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1252775A (en) * | 1997-04-18 | 2000-05-10 | 美国博拉克有限公司 | Method for producing calcium borate |
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| CN1923686A (en) | 2007-03-07 |
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Granted publication date: 20080716 Termination date: 20110921 |