CN101891216A - Preparation method of high purity CeB6 nano powder - Google Patents
Preparation method of high purity CeB6 nano powder Download PDFInfo
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- CN101891216A CN101891216A CN 201010233471 CN201010233471A CN101891216A CN 101891216 A CN101891216 A CN 101891216A CN 201010233471 CN201010233471 CN 201010233471 CN 201010233471 A CN201010233471 A CN 201010233471A CN 101891216 A CN101891216 A CN 101891216A
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Abstract
The invention relates to a preparation method of high purity CeB6 nano powder, including the following steps: (1) CeO2, B2O3 and magnesium powder are mixed, high energy ball grinding is carried out, and then blank is obtained by pressing; (2) the blank is placed into an automatic spreading reaction furnace, heating in air atmosphere is carried out to initiate automatic spreading reaction, intermediate product is leached out in a hermetically sealed high pressure autoclave, so as to obtain leachate, filtering is carried out to obtain residue, and washing and drying are carried out to obtain the high purity CeB6 nanopowder. The invention has available raw material, simple operation and low requirement on technological condition; and the obtained CeB6 powder has the advantages of high purity, small granularity and high powder activity.
Description
Technical field
The present invention relates to the preparation method of boride powder, particularly a kind of high-purity CeB
6The preparation method of nano powder.
Background technology
CeB
6Constructional feature with typical rare earth metal hexaboride, belong to cubic structure, have that work function is low, chemical stability good, fusing point is high, hardness is big, strong, the anti-ion bombardment ability of anti-poisoning capability goes advantages such as strong, it is the ideal hot cathode material, extensively be used in high brightness point-like electron source equipment, as Electronic Speculum and high current density electron source application apparatuss such as SEM, TEM, in equipment such as microwave tube, plasma source, planography, electron beam welding machine, free electron laser.For example, CeB
6Has the LaB of ratio as hot cathode material
6More superior performance, the one, anti-Prevent Carbon Contamination ability is strong; The 2nd, rate of evaporation is low, and the rate of evaporation below 1800K compares LaB
6Low 40%; The 3rd, resistivity compares LaB
6Height is more suitable for making heater cathode, compares CeB with tungsten
6The emissive power height, long service life, very likely replacement still has widely used direet-heating type tungsten cathode at present in equipment such as electron beam welding machine, therefore, CeB
6Have a good application prospect.Therefore, in recent years along with development of science and technology, CeB
6Use more and more widely.
At present, CeB
6The preparation method of powder mainly contains fused salt electrolysis process, boron thermal reduction method, norbide method and chemical Vapor deposition process etc., and above method all exists the energy consumption height, and shortcomings such as complex process are also far apart from industrial production.For example, boron thermal reduction method is with CeO
2After the mixing of boron powder, at the synthetic CeB of the pyroreaction more than 1400 ℃
6Powder, because raw material is the high purity boron powder that adopts, thus the production cost height, and the processing requirement harshness, restive.Also there is the energy consumption height in electrolytic process, cost height, the shortcoming that output is little.
Summary of the invention
The objective of the invention is at existing CeB
6Shortcoming on the powder preparation method provides a kind of high-purity CeB
6The preparation method of nano powder is by CeB low-cost, that technology simple, the method that is fit to suitability for industrialized production is prepared the purity height, granularity is little, powder activity is high
6Nano powder.
Method of the present invention is carried out according to the following steps:
1, with CeO
2, B
2O
3Mix with the magnesium powder, blending ratio is pressed mass ratio for being CeO
2: B
2O
3: Mg=100: 110～130: 160～185, to carry out high-energy ball milling then and handle, ball milling to granularity is less than or equal to 0.5 micron, is pressed into blank then, and pressing pressure is 40～70MPa;
2, blank is placed in the self-propagating reaction stove, in air atmosphere, add the thermal initiation self-propagating reaction, obtain CeB
6The intermediate product of disperse in the MgO matrix; Dilute sulphuric acid with mass concentration 40～60% is a leaching agent, in enclosed autoclave intermediate product is leached, and extraction temperature is 50～80 ℃, and extraction time 24～40h obtains to leach product and filters; Obtain filter residue, through washing and the high-purity CeB of dry acquisition
6Nano powder.
Above-mentioned self-propagating reaction is divided into direct initiation and constant temperature detonates two kinds; Direct initiation is a direct heating blank under air atmosphere, and till self-propagating reaction took place, can form dazzling flame this moment, and have a large amount of cigarettes to volatilize, and the temperature of reaction system raises rapidly; Constant temperature detonates and is meant under air atmosphere, the heating blank, and temperature is controlled between 680～900 ℃, and till self-propagating reaction took place, can form dazzling flame this moment, and have a large amount of cigarettes to volatilize, and the temperature of reaction system raises rapidly.
The add-on of dilute sulphuric acid and intermediate product is according to reaction theory requirement excess sulfuric acid 15～25% proportionings when leaching intermediate product in the aforesaid method; The chemical equation of reaction institute foundation is MgO+2H
+=Mg
2++ H
2O.
Washing and drying are that the filter residue that will remove leach liquor is washed with water to washing lotion for neutrality in the aforesaid method, dry under vacuum condition then, and bake out temperature is 80～150 ℃, and the time is 24h at least.
High-purity CeB that aforesaid method obtains
6Nano powder purity is greater than 99.5%, and granularity is at 50～400nm.
Adopt the dynamic circulation washing when washing with water in the aforesaid method, promptly in the washing process in the rinse bath washing lotion keep constant water level, how many fresh waters have how many washing lotions to discharge just has replenish, washing is to neutral.
Principle of the present invention is: at first through overheated method synthesis phase, be about to the processing of reaction mixture high-energy ball milling, briquetting, adopt from spreading pattern to react, obtain containing the CeB of MgO by product
6Primary products.The effect of high-energy ball milling is: make powder stand repeatedly distortion, cold welding, fragmentation in the high-energy ball milling process, thereby reach the level of atomic level alloying between element.At the ball milling initial stage, crimp repeatedly through fragmentation, seam, extruding again, forms lamellated composite particles.Composite particles produces newborn atomic plane under the continuous effect of ball milling mechanical force, the continuous refinement of laminate structure.In mechanical milling process, the formation of laminate structure, the reducing of lamellar spacing shortened solid-state interatomic the evolving path, makes that alloying process quickens between element, and the powder grain degree obviously diminishes.A large amount of collision phenomenons occurs between ball-powder ball in the mechanical milling process simultaneously, and serious viscous deformation takes place under impact effect captive powder, makes powder be subjected to " miniature " forging effect of two collision balls.The carrying out that high density of defects that ball milling produces and nano-interface can promote self-propagating reaction greatly guaranteed the transformation efficiency and the product yield that react.The reaction mass of the high reactivity attitude that obtains after handling through high-energy ball milling simultaneously has higher self-propagating reaction speed and thermograde, has therefore guaranteed the nanocrystalline size and the particle development degree of reaction product.
Because self-propagating reaction is to take place under the air atmosphere that opens wide, and the self-propagating reaction temperature is very high, Mg gasifies in a large number in reaction process, can cause a large amount of volatilization losses of Mg, and Mg will be not enough like this.In order to remedy the volatilization loss of Mg, when batching, can increase the proportioning of Mg in right amount, to guarantee CeO in the reaction system
2And B
2O
3Thoroughly reduced.This section operation is to carry out under the air atmosphere that opens wide, and is therefore simple to operate, do not have potential safety hazard, is well suited for suitability for industrialized production.But in order to remedy the volatilization loss of Mg in the reaction process, suitably increase the proportioning of Mg during batching, magnesium common excessive 5～20%.
With the dilute sulphuric acid is leaching agent, and acid is theoretical excessive 20%, and products of combustion is directly leached without fragmentation, leaches in airtight autoclave, has guaranteed CeB
6Purity and leaching efficiency.Because actual is that Mg at first reduces CeO from the process that spreads
2Generate Ce and MgO in advance, then Mg reduction B
2O
3Generate B and later stage MgO, the synthetic REB that generates of Ce that reduction generates and B
6, and MgO can become crystal seed and is wrapped in CeB in advance
6In; Actual leaching process also will thoroughly be removed by CeB except the MgO reaction in acid and later stage
6The MgO of parcel, and acid wants and be wrapped in CeB
6In the reaction of MgO, must be through diffusing into CeB
6Inside, with the MgO reaction, the acidleach product leaves CeB through diffusing step more then
6Thereby, remove REB
6In the MgO that is wrapped, wherein diffusing step is the controlled step of whole acidleach process.Because the acidleach process is to carry out in airtight autoclave, the leach liquor less turbulence is greatly improved, and wherein the diffusion mass transfer process is also greatly strengthened, thereby has guaranteed by CeB
6The thorough removal of the MgO of parcel has guaranteed CeB
6The high purity of product.In order to prevent removing fully of by product such as MgO in the elementary product, leaching operation must guarantee certain acidity and certain excessive acid degree, is to guarantee washing effect, must adopt the dynamic circulation washing.Because products of combustion directly leaches without fragmentation, therefore avoided the secondary pollution that brings because of broken.
Advantage of the present invention is: with CeO
2And B
2O
3Being raw material, is that reductive agent greatly reduces production cost with the Mg powder; Adopt the self-propagating reaction pattern, made full use of the reaction heat that reacts self, reduced energy consumption; All operations all carries out in air atmosphere, and is simple to operate, low to the processing condition requirement, for suitability for industrialized production is laid a good foundation; Products of combustion directly leaches without fragmentation, has avoided the secondary pollution that brings because of broken; Since adopted the high-energy ball milling processing, from epidemic techniques and airtight high pressure leaching-out technique, so the CeB of gained
6Powder has the purity height, and granularity is little, the powder activity advantages of higher.
Description of drawings
Fig. 1 is the high-purity CeB in the embodiment of the invention 1
6The nano powder XRD figure.
Embodiment
The CeO that adopts in the embodiment of the invention
2, B
2O
3With the magnesium powder be technical grade product, raw material granularity is all less than 0.5mm.
The self-propagating reaction stove that adopts in the embodiment of the invention is the disclosed self-propagating reaction stove of patent " ZL200510047308.2 ", and this Reaktionsofen is made of reaction vessel, well heater, sight glass, transformer, function recording instrument, thermopair, gas valve.
The model of the high energy ball mill that adopts when high-energy ball milling is handled in the embodiment of the invention is Pulveristte 4, and rotational speed of ball-mill is 250～400rpm.
The time of self-propagating reaction is 5～90s in the embodiment of the invention.
Drying time is 24h at least in the embodiment of the invention.
Embodiment 1
Get CeO
2, B
2O
3And the Mg powder is by 100: 120: 162 mass percents batching, and promptly the Mg powder is excessive 5%, the high-energy ball milling batch mixing, raw material is milled to 0.5 micron, be pressed into cylindric block blank, pressing sample pressure is 40MPa, and blank is placed the self-propagating reaction stove, thermostatically heating blank (constant temperature detonates) under air atmosphere, temperature is controlled at 900 ℃, till self-propagating reaction causes, stops heating, naturally cool to room temperature, collect intermediate product; Dilute sulphuric acid with 40% is a leaching agent, by the theoretical consumption that needs acid amount excessive 15%, intermediate product is directly leached without fragmentation, leach in airtight autoclave, extraction temperature is 50 ℃, extraction time 40h, filter and obtain filter residue, circulation is dynamically washed to neutral, vacuum drying filtration product in vacuum drying oven, oven temperature is controlled at 80 ℃, promptly gets CeB
6Nano powder; Wherein, CeB
6Purity 99.5%, granularity is 400nm.
CeB
6The XRD figure of nano powder is single CeB as shown in Figure 1 as we know from the figure
6Phase.
Embodiment 2
Get CeO
2, B
2O
3And the Mg powder is by 100: 110: 170 mass percents batching, and promptly the Mg powder is excessive 10%, the high-energy ball milling batch mixing, raw material is milled to 0.4 micron, be pressed into cylindric block blank, pressing sample pressure is 50MPa, is placed in the self-propagating reaction stove suppressing blank, thermostatically heating blank (constant temperature detonates) under air atmosphere, temperature is controlled at 700 ℃, till self-propagating reaction causes, stops heating, naturally cool to room temperature, collect intermediate product; Dilute sulphuric acid with 50% is a leaching agent, by the theoretical consumption that needs acid amount excessive 20%, intermediate product is directly leached without fragmentation, leach in airtight autoclave, extraction temperature is 80 ℃, extraction time 24h, filter and obtain filter residue, dynamic washing and filtering product to the washings that circulates is neutrality, vacuum drying filtration product in vacuum drying oven, oven temperature is controlled at about 100 ℃, promptly gets CeB
6Nano powder.CeB wherein
6Purity 99.8%, granularity is 150nm.
Embodiment 3
Get CeO
2, B
2O
3, Mg is by 100: 130: 185 mass percents batching, the Mg powder is excessive 20%, the high-energy ball milling batch mixing, raw material is milled to 0.2 micron, be pressed into block blank, pressing sample pressure is 70MPa, is placed in the self-propagating reaction stove suppressing blank, under air atmosphere, heat blank, be direct initiation, till self-propagating reaction causes, stop heating, naturally cool to room temperature, collect intermediate product; Dilute sulphuric acid with 60% is a leaching agent, by the theoretical consumption that needs acid amount excessive 25%, intermediate product is directly leached without fragmentation, leach in airtight autoclave, extraction temperature is 70 ℃, extraction time 30h, filter and obtain filter residue, circulation dynamically washing is dried filtration product to neutral in loft drier, oven temperature is controlled at about 150 ℃, promptly gets CaB
6Ultrafine powder.CeB wherein
6Purity 99.9%, granularity is 50nm.
Claims (5)
1. high-purity CeB
6The preparation method of nano powder is characterized in that carrying out according to the following steps:
(1) with CeO
2, B
2O
3Mix with the magnesium powder, blending ratio is pressed mass ratio for being CeO
2: B
2O
3: Mg=100: 110～130: 160～185, to carry out high-energy ball milling then and handle, ball milling to granularity is less than or equal to 0.5 micron, is pressed into blank then, and pressing pressure is 40～70MPa;
(2) blank is placed in the self-propagating reaction stove, in air atmosphere, add the thermal initiation self-propagating reaction, obtain CeB
6The intermediate product of disperse in the MgO matrix; Dilute sulphuric acid with mass concentration 40～60% is a leaching agent, in enclosed autoclave intermediate product is leached, and extraction temperature is 50～80 ℃, and extraction time 24～40h obtains to leach product and filters; Obtain filter residue, through washing and the high-purity CeB of dry acquisition
6Nano powder.
2. a kind of high-purity CeB according to claim 1
6The preparation method of nano powder is characterized in that described self-propagating reaction is divided into direct initiation and constant temperature detonates two kinds; Direct initiation is a direct heating blank under air atmosphere, till self-propagating reaction takes place; Constant temperature detonates and is meant under air atmosphere, the heating blank, and temperature is controlled between 680～900 ℃, till self-propagating reaction takes place.
3. a kind of high-purity CeB according to claim 1
6The preparation method of nano powder, the add-on of dilute sulphuric acid and intermediate product is according to reaction theory requirement excess sulfuric acid 15～25% proportionings when it is characterized in that described leaching intermediate product; The chemical equation of reaction institute foundation is MgO+2H
+=Mg
2++ H
2O.
4. a kind of high-purity CeB according to claim 1
6The preparation method of nano powder is characterized in that described washing and drying are that the filter residue that will remove leach liquor is washed with water to washing lotion for neutrality, dries under vacuum condition then, and bake out temperature is 80～150 ℃, and the time is 24h at least.
5. a kind of high-purity CeB according to claim 1
6The preparation method of nano powder is characterized in that described high-purity CeB
6Nano powder purity is greater than 99.5%, and granularity is at 50～400nm.
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Cited By (5)
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| RU2540277C1 (en) * | 2013-09-27 | 2015-02-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Кабардино-Балкарский государственный университет им. Х.М. Бербекова (КГБУ) | Electrolytic method of obtaining nanosized cerium hexaboride powder |
| US20200062655A1 (en) * | 2018-08-21 | 2020-02-27 | Korea Institute Of Science And Technology | Method of preparing cerium boride powder |
| WO2020168883A1 (en) * | 2019-02-21 | 2020-08-27 | 刘丽 | Method for preparing metal powder material |
| CN112811457A (en) * | 2021-03-03 | 2021-05-18 | 甘肃农业大学 | Preparation method of loose porous nano cerium oxide |
| CN114933311A (en) * | 2022-06-02 | 2022-08-23 | 安阳工学院 | Method for refining hexaboride powder |
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| CN101298389A (en) * | 2008-06-23 | 2008-11-05 | 东北大学 | Boron-containing additive for carbide refractory and preparation thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2540277C1 (en) * | 2013-09-27 | 2015-02-10 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Кабардино-Балкарский государственный университет им. Х.М. Бербекова (КГБУ) | Electrolytic method of obtaining nanosized cerium hexaboride powder |
| US20200062655A1 (en) * | 2018-08-21 | 2020-02-27 | Korea Institute Of Science And Technology | Method of preparing cerium boride powder |
| KR20200021641A (en) * | 2018-08-21 | 2020-03-02 | 한국과학기술연구원 | Methods for fabricating cerium boride powder |
| KR102118428B1 (en) * | 2018-08-21 | 2020-06-03 | 한국과학기술연구원 | Methods for fabricating cerium boride powder |
| US10793476B2 (en) | 2018-08-21 | 2020-10-06 | Korea Institute Of Science And Technology | Method of preparing cerium boride powder |
| WO2020168883A1 (en) * | 2019-02-21 | 2020-08-27 | 刘丽 | Method for preparing metal powder material |
| US11491544B2 (en) | 2019-02-21 | 2022-11-08 | Li Liu | Preparation method of metal powder material |
| CN112811457A (en) * | 2021-03-03 | 2021-05-18 | 甘肃农业大学 | Preparation method of loose porous nano cerium oxide |
| CN114933311A (en) * | 2022-06-02 | 2022-08-23 | 安阳工学院 | Method for refining hexaboride powder |
| CN114933311B (en) * | 2022-06-02 | 2023-08-25 | 安阳工学院 | Method for refining hexaboride powder |
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