CN101570438B - Method for preparing superfine boron carbide powder - Google Patents
Method for preparing superfine boron carbide powder Download PDFInfo
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- CN101570438B CN101570438B CN2009100495427A CN200910049542A CN101570438B CN 101570438 B CN101570438 B CN 101570438B CN 2009100495427 A CN2009100495427 A CN 2009100495427A CN 200910049542 A CN200910049542 A CN 200910049542A CN 101570438 B CN101570438 B CN 101570438B
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Abstract
The invention discloses a method for preparing boron carbide powder, which comprises the following steps: A, mixing borate, magnesium powder and carbon powder according to a mol ratio of 1-10:6-70:1-10, compacting the mixture and putting the mixture into an upright annular cylinder or a discoid container made from carbon felts, putting the upright annular cylinder or the discoid container into a high-pressure vessel to perform combustion synthesis in an argon gas atmosphere, and cooling the mixture naturally after the combustion synthesis; and B, taking out the product subjected to the combustion synthesis, crushing the product, soaking the product in 1 to 10 mol/L hydrochloric acid solution for 1 to 5 hours, so that a synthesis byproduct MgO impurity is completely dissolved in the hydrochloric acid solution, performing suction filtration on the mixture, adding deionized water to wash the mixture, repeating the suction filtration and the washing for a plurality of times until no Cl<->is detected in the filtrate by using AgNO3, and finally drying the material after the washing at a temperature of between 100 and 110 DEG C for 1 to 5 hours in a baking oven to obtain the final product of the boron carbide powder. The method has low raw material cost and simple process equipment.
Description
Technical field
The present invention relates to the preparation method at a kind of ceramic ultrafine powder end, relate to a kind of method of the synthesizing superfine boron carbide powder that burns in particular.
Background technology
Norbide (B
4C) have low density, superhard, HMP, high-modulus, good neutron-absorption cross-section, characteristic of semiconductor, strong preservative property and good a series of good physical and chemical performances such as oxidation-resistance; At aspects such as bullet-resistant ceramic material, aerospace industry, nuclear industry, durable protective material, abrasive materials application is very widely arranged, receive the extensive attention of countries in the world.
In industry, B
4The C powder produce main employing carbon tube furnace and electric arc furnace carbothermic method; But carbon tube furnace and electric arc furnace carbothermic method energy consumption are big, throughput is lower, under the high temperature to the well damage of body of heater; Especially synthetic starting powder median size big (20～40 μ m), sintering B
4The raw material of C also needs a large amount of break process operations, has increased production cost greatly.In recent years, B
4The C powder produce novel methods such as laser chemistry gas-phase reaction method (LICVD), so-gel carbothermic method have occurred.The shortcoming of LICVD method is an apparatus expensive, and throughput is lower, and the reaction raw materials cost is high, and byproduct of reaction is an acids, etching apparatus, and contaminate environment.The shortcoming of so-gel carbothermic method is that reaction raw materials is more expensive, complex technical process.Zhang Huayu etc. are in the synthetic Mg-B4C microtexture research [J] of self propagating high temperature. aerospace material technology, and 2000,2:25-28 discloses burning synthetic (CS) technology at B
4Application in the C powder preparing, it is a raw material with the boron oxide, utilizes chemical reaction self heat release of boron oxide and magnesium and carbon; Mode synthesizing boron carbide so that combustion wave spreads has save energy, is swift in response and easy advantage such as large-scale production, but aforesaid method raw materials used be boron oxide; Be prone to suction and form boric acid; Be difficult for preserving, and particle is bigger, needs the pulverization process in early stage.If improve this method, adopting the prime raw material borate of boron oxide is that raw material prepares norbide, adopts energy-conservation, preparation technology efficiently, and the shortcoming that will overcome prior art also can reduce production costs greatly.
Summary of the invention
It is the method for feedstock production superfine boron carbide powder that technical problem to be solved by this invention provides a kind of borate that adopts, and the inventive method raw materials cost is cheap, and processing unit is simple.
Technical scheme of the present invention, a kind of preparation method of superfine boron carbide powder comprises the following steps:
A, with borate, magnesium powder, carbon dust according to the mol ratio borate: magnesium powder: carbon dust=1～10: 6～70: 1～10 mixed; Compacting is packed in the upright ring-type tube or disc shaped container of carbon felt system then; Packing into, it is synthetic in argon gas atmosphere, to burn in the high pressure vessel, the synthetic back of burning naturally cooling;
B, taking-up combustion synthesized product are carried out the material fragmentation, in the hydrochloric acid soln of 1～10mol/L, soak 1～5 hour, and synthesising by-product MgO impurity is dissolved in the hydrochloric acid fully, and suction filtration adds deionized water wash, repeat suction filtration and wash repeatedly, up to using AgNO
3Detect in the filtrating and do not have Cl
-Till, last in baking oven the dry materials after will washing under 100～110 ℃ of temperature 1～5 hour, obtain the end product superfine boron carbide powder.
Borate described in the steps A is selected from Sodium Tetraborate, lime borate or ammonium borate, and borate granularity particle size range is 0.5～100 μ m.
The particle size range of the magnesium powder described in the steps A is 0.3～50 μ m, and the particle size range of described carbon dust is 0.01～10 μ m.
The argon pressure that reacts in the steps A is 0.1～15MPa.
To the further optimization of steps A be with borate, magnesium powder, carbon dust according to the mol ratio borate: magnesium powder: carbon dust=1～10: 6～70: after 1～10 ratio is weighed; The external reinforcement body additives; Uniform mixing, during the upright ring-type tube or disc shaped container of carbon felt system packed in compacting into then, it was synthetic in argon gas atmosphere, to burn in the high pressure vessel of packing into; The synthetic back of burning naturally cooling, wherein said solid additive is selected from NaCl, MgCl
2, NaF, MgF
2, KCl one of them or more than one mixture, the add-on of said solid additive is 1～10wt%. of borate, magnesium powder and carbon dust gross weight
After the mixture compacted of borate powder, magnesium powder, carbon dust and solid additive, compacted density is 2.0～4.0g/cm
3
Beneficial effect of the present invention; High pressure vessel that the present invention uses and general burning synthesis method (SHS) high pressure vessel are similar; Need not particular requirement; But compacting is placed in the upright ring-type tube or disc shaped container of carbon felt system after requiring reactant or having added the reactant uniform mixing of solid additive, and naturally cooling is adopted in the synthetic back of burning.The present invention compared with prior art has advantage:
The first, energy consumption of the present invention is low, except that starting combustion synthesis reaction, does not need any energy;
The second, the present invention adopts simple technology and equipment, and output is big, and efficient is high, helps reducing cost, and is easy to industrialization;
Three, the present invention is starting material with the relative more cheap borate of price, has reduced the flow chart from the raw mineral materials to the product producing process, helps reducing the production cost of norbide;
Four, solid additive is that halogenide can separate the combination of norbide in the building-up process effectively and suppresses its particulate and grow up, and helps the synthesizing superfine granular powder, with the powder compacting, can make the abundant contact of reactant, improves reaction conversion ratio;
Five, the present invention reacts the volatilization that helps preventing magnesium under the high pressure argon gas of 0.1～15MPa, furnishes ample material for fully reacting.
Description of drawings
Fig. 1 is the upright ring-type tube of carbon felt system, and wherein 1 is that tungsten filament heating element, 2 is that priming mixture, 3 is that reactant, 4 is carbon felt container;
Fig. 2 is the disc shaped container of carbon felt system, and wherein 1 is that tungsten filament heating element, 2 is that priming mixture, 3 is that reactant, 4 is carbon felt container;
Fig. 3 is the XRD figure spectrum of embodiment 1;
Fig. 4 is the SEM electromicroscopic photograph of embodiment 1.
Embodiment
Through accompanying drawing and embodiment the present invention is described in further detail below, a kind of preparation method of superfine boron carbide powder comprises the following steps:
A, with borate, magnesium powder, carbon dust according to the mol ratio borate: magnesium powder: carbon dust=1～10: 6～70: 1～10 mixed; Compacting is packed in the upright ring-type tube or disc shaped container of carbon felt system then; Packing into, it is synthetic in argon gas atmosphere, to burn in the high pressure vessel, the synthetic back of burning naturally cooling;
B, taking-up combustion synthesized product are carried out the material fragmentation, in the hydrochloric acid soln of 1～10mol/L, soak 1～5 hour, and synthesising by-product MgO impurity is dissolved in the hydrochloric acid fully, and suction filtration adds deionized water wash, repeat suction filtration and wash repeatedly, up to using AgNO
3Detect in the filtrating and do not have Cl
-Till, last in baking oven the dry materials after will washing under 100～110 ℃ of temperature 1～5 hour, obtain the end product superfine boron carbide powder.Borate described in the steps A is selected from Sodium Tetraborate, lime borate or ammonium borate, and borate granularity particle size range is 0.5～100 μ m.The particle size range of the magnesium powder described in the steps A is 0.3～50 μ m, the particle size range of described carbon dust is 0.01～10 μ m.The argon pressure that reacts in the steps A is 0.1～15MPa.
Under the situation of adding solid additive; Be with borate, magnesium powder, carbon dust according to the mol ratio borate: magnesium powder: carbon dust=1～10: 6～70: after 1～10 ratio is weighed, external reinforcement body additives, uniform mixing; Compacting is packed in the upright ring-type tube or disc shaped container of carbon felt system then; Packing into, it is synthetic in argon gas atmosphere, to burn in the high pressure vessel, the synthetic back of burning naturally cooling, and wherein said solid additive is selected from NaCl, MgCl
2, NaF, MgF
2, KCl one of them or more than one mixture or other may be dissolved in the solid additive in the water, the add-on of said solid additive is 1～10wt% of borate, magnesium powder and carbon dust gross weight.After the mixture compacted of above-mentioned borate powder, magnesium powder, carbon dust and solid additive, compacted density is 2.0～4.0g/cm
3
Sodium Tetraborate, magnesium powder and carbon dust are pressed=10: 63: 10 molar ratio batchings, behind the uniform mixing, compacting again; In the upright ring-type tube of the carbon felt system of packing into; As shown in Figure 1, in the high pressure vessel of packing into then, charge into the argon gas of 3MPa after vacuumizing; Self-propagating combustion after igniting, naturally cooling is adopted in the synthetic back of burning.Take out combustion synthesized product, carry out the material fragmentation, add the hydrochloric acid soln of 2mol/L then, soaked 2 hours, MgO impurity is dissolved in the hydrochloric acid fully, suction filtration adds deionized water wash, repeats suction filtration and washs repeatedly, up to using AgNO
3Detect in the filtrating and do not have Cl
-Till, then in baking oven, in 105 ℃ of dry materials after will washing down 2 hours.Press the product that present embodiment obtains, its XRD and SEM figure are respectively like Fig. 3 and shown in Figure 4, and visible from XRD figure, product is the norbide phase basically, from SEM figure, can find out that the median size of boron carbide powder is 0.6 μ m.
With Sodium Tetraborate, magnesium powder and carbon dust by=1: 6: 1 molar ratio batchings, all the other implementation conditions comprise material purity and particle diameter all with embodiment 1, have obtained the boron carbide powder that median size is about 0.72 μ m.
Sodium Tetraborate, magnesium powder and carbon dust are pressed=10: 63: 10 molar ratio batchings; Behind the uniform mixing, compacting again, the plate-like of the carbon felt system of packing into (long 2000mm * wide 400mm * high 200mm) container; As shown in Figure 2; Put into high pressure vessel then and burn syntheticly, all the other conditions comprise material purity and particle diameter all with embodiment 1, obtain the boron carbide powder that median size is about 0.65 μ m.
Sodium Tetraborate, magnesium powder and carbon dust are pressed=2: molar ratio was prepared burden in 13: 2, added 2% MgCl
2, all the other implementation conditions comprise material purity and particle diameter all with embodiment 1, have obtained the boron carbide powder that median size is about 0.52 μ m.
Embodiment 5
With lime borate, magnesium powder and carbon dust in=5: 32: 5 ratios batching, add 5% NaCl, all the other implementation conditions comprise material purity and particle diameter all with embodiment 1, have obtained the boron carbide powder that median size is about 0.55 μ m.
Embodiment 6
With Sodium Tetraborate, magnesium powder and carbon dust by=10: 70: 9 molar ratio batchings, add 3% KCl, all the other implementation conditions comprise material purity and particle diameter all with embodiment 1, have obtained the boron carbide powder that median size is about 0.48 μ m.
The content of the foregoing description is merely the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (3)
1. the preparation method of a superfine boron carbide powder comprises the following steps:
A, with borate, magnesium powder, carbon dust according to the mol ratio borate: magnesium powder: carbon dust=1～10: 6～70: 1～10 mixed; Compacting is packed in the upright ring-type tube or disc shaped container of carbon felt system then; Packing into, it is synthetic in argon gas atmosphere, to burn in the high pressure vessel, the synthetic back of burning naturally cooling;
B, taking-up combustion synthesized product are carried out the material fragmentation, in the hydrochloric acid soln of 1～10mol/L, soak 1～5 hour, and synthesising by-product MgO impurity is dissolved in the hydrochloric acid fully, and suction filtration adds deionized water wash, repeat suction filtration and wash repeatedly, up to using AgNO
3Detect in the filtrating and do not have Cl
-Till, last in baking oven the dry materials after will washing under 100～110 ℃ of temperature 1～5 hour, obtain the end product superfine boron carbide powder; Borate described in the steps A is selected from Sodium Tetraborate, lime borate or ammonium borate, and borate granularity particle size range is 0.5～100 μ m; The particle size range of the magnesium powder described in the steps A is 0.3～50 μ m, and the particle size range of described carbon dust is 0.01～10 μ m; The argon pressure that reacts in the steps A is 0.1～15Mpa.
2. according to the preparation method of the said boron carbide powder of claim 1; It is characterized in that: in the steps A with borate, magnesium powder, carbon dust according to the mol ratio borate: magnesium powder: carbon dust=1～10: 6～70: after 1～10 ratio is weighed, external reinforcement body additives, uniform mixing; Compacting is packed in the upright ring-type tube or disc shaped container of carbon felt system then; Packing into, it is synthetic in argon gas atmosphere, to burn in the high pressure vessel, the synthetic back of burning naturally cooling, and wherein said solid additive is selected from NaCl, MgCl
2, NaF, MgF
2, KCl one of them or more than one mixture, the add-on of said solid additive is 1～10wt%. of borate, magnesium powder and carbon dust gross weight
3. according to the preparation method of the said boron carbide powder of claim 2, it is characterized in that: after the mixture compacted of borate powder, magnesium powder, carbon dust and solid additive, compacted density is 2.0～4.0g/cm
3
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| CN102432014B (en) * | 2011-10-17 | 2013-08-28 | 宁波伏尔肯机械密封件制造有限公司 | Preparation method of submicron carbonized boron powder |
| CN105502404B (en) * | 2016-01-22 | 2018-05-22 | 东北大学 | A kind of smelting preparation method of high-quality boron carbide ingot |
| CN106082228B (en) * | 2016-06-12 | 2018-03-23 | 郑州航空工业管理学院 | A kind of B4The preparation method and B of C nano piece4C nano piece |
| CN106116588A (en) * | 2016-06-29 | 2016-11-16 | 北京光科博冶科技有限责任公司 | Self-spreading high-temperature synthesizing device and SHS process method |
| CN108862243B (en) * | 2018-08-31 | 2020-10-27 | 北京化工大学 | Method for preparing carbon nano tube by self-propagating combustion |
| CN109574014B (en) * | 2018-10-22 | 2022-04-19 | 西安建筑科技大学 | B4C fiber felt and preparation method thereof |
| CN114940498A (en) * | 2022-05-20 | 2022-08-26 | 西安建筑科技大学 | Superfine B 4 C powder, preparation method and application for preparing microwave absorbent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1408639A (en) * | 2002-09-23 | 2003-04-09 | 中国科学院长春应用化学研究所 | Process for preparing boron carbide powder |
| CN101172606A (en) * | 2007-10-26 | 2008-05-07 | 哈尔滨工程大学 | Method for synthesizing boron carbide in low-temperature |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1408639A (en) * | 2002-09-23 | 2003-04-09 | 中国科学院长春应用化学研究所 | Process for preparing boron carbide powder |
| CN101172606A (en) * | 2007-10-26 | 2008-05-07 | 哈尔滨工程大学 | Method for synthesizing boron carbide in low-temperature |
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Application publication date: 20091104 Assignee: Shanghai Zhentai New Material Science & Technology Co., Ltd. Assignor: Shanghai Institute of Technology Contract record no.: 2013320010137 Denomination of invention: Method for preparing superfine boron carbide powder Granted publication date: 20120725 License type: Exclusive License Record date: 20130802 |
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