CN102718217B - High purity linear silicon carbide powder and preparation method - Google Patents
High purity linear silicon carbide powder and preparation method Download PDFInfo
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- CN102718217B CN102718217B CN201210156070.7A CN201210156070A CN102718217B CN 102718217 B CN102718217 B CN 102718217B CN 201210156070 A CN201210156070 A CN 201210156070A CN 102718217 B CN102718217 B CN 102718217B
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Abstract
The invention relates to a high purity linear silicon carbide powder and a preparation method, the linear silicon carbide powder product presents light green color and has a cubic crystal system, a microstructure presents a linear state, and the content of the silicon carbide is no less than 99%. The preparation method provided by the present invention comprises the following steps: silica sol and oxidized graphene are uniformly mixed, then subjected to ultrasonic treatment, and completely stirred to obtain a composite precursor. The composite precursor is subjected to solidification, drying and grinding to obtain a powdery precursor with fine and uniform quality. Argon is introduced in the powdery precursor, a carbon thermal reduction is carried out under high temperature in a high temperature tubular furnace to obtain the carbonized silicon powder crude product; the carbonized silicon powder crude product is immersed in inorganic acid and then the pumping filtration is carried out, the unreacted carbon is removed, and cooled to obtain the silicon carbide powder with content of less than 99%. According to the invention, a silicon source is silica sol, a carbon source is oxidized grapheme, the invention has the advantages of no requirement of subsequent processing, no requirement of pressurization, addition of metal catalyst, simple process and short production period; the precursor with homogeneousness is prepared in advance, then the carbon thermal reduction is carried out, the product purity is high, and the method provided by the invention enables large-scale industrial production.
Description
Technical field
The invention belongs to ceramics processing field, be specifically related to a kind of high-purity wire carborundum powder and preparation method thereof.
Background technology
Silicon carbide (SiC) material be continue two generation a kind of novel semiconductor material of growing up of semi-conductor.Its peculiar broad-band gap (Eg>2.3ev), high heat conductance (θ
k=4.9W cm
-1k
-1), high critical breakdown electric field (V=3.0MV cm
-1), the saturated drift of high carrier (ζ sat=2.0 * 10
7cm S
-1) etc. feature, larger at the application potential of the aspects such as high temperature, high-power, high frequency, photoelectron and radioprotective.As fields such as geothermal drilling, oil, aerospace, nuclear energy exploitations, its high temperature and radiation-resistant property have been used; For high frequency, superpower, SiC device is to be used in radar, communication and field of broadcast televisions.Can find out, SiC material will represent its important using value with its excellent physics and chemistry performance future in high-tech area.
Typical SiC crystalline structure is generally divided into two large classes: a class is cube SiC crystal formation that is called the zincblende lattce structure of 3C or β-SiC, and another kind of is the large period structure that is called hexangle type or the diamond structure of α-SiC, typically has 6H, 4H, 15R etc.Because the bond energy of β-SiC is minimum, lattice free energy is maximum, so its also the easiest nucleation, and the needed temperature of growing is also relatively minimum.Chemical property, because spacing is substantially equal between carbon silicon stack lamination, different SiC polytypes are identical in the lattice arrangement of the double-deck solid matter face of Si-C, so the chemical property that they have is basic identical; And for physical properties, owing to having very high energy barrier between these homogeneity polytypes, therefore, even in the situation that basal component is identical, the physical properties between them, particularly characteristic of semiconductor are also different.In addition, β-SiC is one of the hardest high performance material being only second to diamond, and its ultrahigh hardness and density make it can be ideally suited for standing the parts of high wearing and tearing and skimming wear, are applicable to especially ultraprecision grinding of various grindings.
Carbothermic reduction reaction is one of main method of current synthesizing silicon carbide powder, is called Acheson method in industrial production, and traditional method is to adopt quartz sand, silicon-dioxide powdery, silica flour as silicon source; Graphite, carbon dust and some containing carbon macromolecule if starch, resol, pitch are as carbon source, in order to obtain the silicon carbide powder of different-shape, also have and adopt the resinous material with fibrous texture as carbon source in recent years, can find out, the own foreign matter content in silicon source using in this method is many, be unfavorable for obtaining the product that purity is higher, the carbon source of using is also very limited, and the solid state reaction contact area occurring when using powder body material as reaction carbon source He Gui source is limited, is unfavorable for abundant reaction.Exist silicon source foreign matter content high, react the problem such as insufficient, income rate is low,
Patent application prepared by relevant silicon carbide powder is more, as the patent application of publication number CN101597059, CN101704523, CN101215187, CN101177268, CN101876095, CN1844493, CN1834309, CN1724351, CN101850972, CN1472136.These methods adopt silica flour, silicon dioxide powder Wei Gui source mostly, and graphite, carbon black, gaseous hydride are carbon source, and what have has also used metal as catalyzer, and the methods such as pressurization expend mass energy and preparation process complicated.
The graphene oxide of usining also there is not yet report as carbon source.And due to the excellent properties of graphene oxide, its many-sided applied research is of great significance tool
Summary of the invention
The object of the invention is for above-mentioned present situation, aim to provide a kind of high-purity wire carborundum powder that a kind of preparation technology is simple, production cost is low, with short production cycle, product purity is high and preparation method thereof.
The implementation of the object of the invention is, a kind of high-purity wire carborundum powder, is light green, isometric system, and microtexture is wire, and the content of silicon carbide is not less than 99%.
A preparation method for high-purity wire carborundum powder, concrete steps are as follows:
(1), after silicon sol is mixed by the weight percent of 100:16-36 with graphene oxide, first through ultrasonication 15-30 minute, ultrasonic frequency 20-120kHz, then strong stirring 2-4 hour, obtain composite precursor;
Described silicon sol is dioxide-containing silica 5%-30%, pH value 2-7, and size is the acidic silicasol between 6-30nm;
Described graphene oxide is the carbon material with good laminated structure;
(2) composite precursor is solidified after dry 48h in loft drier, adopt high speed ball mill to grind 2 hours, obtain Powdered presoma fine and smooth and homogeneous;
Described drying means is vacuum-drying, forced air drying or lyophilize,
(3) Powdered presoma is put into high temperature process furnances, pass into purity and reach 99.99% argon gas, at 1400-1600 ℃, carry out carbothermic reduction reaction 2-8 hour, obtain silicon carbide micro-powder crude product;
(4) silicon carbide micro-powder crude product is soaked in mineral acid to suction filtration after 2-4 hour, filter residue under air existence condition at 400-700 ℃ sintering 1-9 hour, remove unreacted carbon, obtain content after cooling to be not less than 99% silicon carbide powder;
Described mineral acid is that concentration is hydrofluoric acid and/or the nitric acid of 10%-20%, the ratio of mixture of hydrofluoric acid and nitric acid be arbitrarily than.
The present invention silicon source used is the silicon sol of the Nano particles of silicon dioxide that contains high reaction activity, carbon source is the graphene oxide with laminated structure, has not only avoided polymer carbon source residual harmful derivative in reduction reaction, without subsequent disposal; Whole reaction does not relate to pressurization and uses metal catalyst, thereby has further simplified production craft step.Utilize the good dispersion of graphene oxide fully to mix with silicon sol, first make uniformity presoma, then carry out carbothermic reduction reaction, thereby guaranteed the adequacy of follow-up reduction reaction, productive rate is high.
Technique of the present invention is simple, production cost is low, with short production cycle, product purity is high, can mass industrialized production.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of the β-SiC of example 1 preparation,
Fig. 2 is scanning electronic microscope (SEM) figure of the β-SiC of example 1 preparation.
Embodiment
Graphene oxide is a kind of important derivatives of Graphene, between carbon atom, to be a kind of plates that hexagonal annular is arranged, by one deck carbon atom, formed, can infinitely extend at two-dimensional space, on two dimension basal plane, be connected with some oxygen-containing functional groups, this makes it can absorb large quantity of moisture, has good wetting ability, dispersed, with the compatibility of polymkeric substance, thereby can fully mix with silicon sol in the present invention.
Product of the present invention is light green, isometric system, and microtexture is wire, and the content of silicon carbide is not less than 99%.
Preparation method of the present invention is, silicon sol mixes with graphene oxide, ultrasonication, and strong stirring, obtains composite precursor.Composite precursor solidify dry after, grind fine and smoothly and the Powdered presoma of homogeneous.Powdered presoma passes into argon gas, carries out carbothermic reduction and obtain silicon carbide micro-powder crude product under high temperature; Silicon carbide micro-powder crude product in mineral acid after suction filtration, filter residue sintering is removed unreacted carbon, obtains content after cooling to be not less than 99% silicon carbide powder.
Below in conjunction with embodiment in detail the present invention is described in detail.
Embodiment mono-:
(1) after 5.0 grams of silicon sol are mixed with 1.15 grams of graphene oxides, first through ultrasonication 30 minutes, ultrasonic frequency 20-120kHz, then under powerful mechanical stirring, stir 3 hours, obtain composite precursor; In selected acidic silicasol, dioxide-containing silica is that 30%, pH value is 2.0, and size is 6nm;
(2) in air dry oven, after curing dry 48h, adopt high speed ball mill to grind 2 hours the composite precursor obtaining, obtain exquisiteness and the Powdered presoma of homogeneous;
(3) Powdered presoma is put into high temperature process furnances, pass into high-purity argon gas, at 1500 ℃, carry out carbothermic reduction reaction 6 hours; Obtain silicon carbide micro-powder crude product;
(4) in the hydrofluoric acid that is 20% by gained silicon carbide micro-powder crude product in concentration, soak suction filtration after 2 hours, filter residue is under air existence condition, and 400 ℃ of sintering 9 hours, remove unreacted carbon, obtains pure silicon carbide powder after cooling.
Embodiment bis-:
(1) after 7.2 grams of silicon sol are mixed with 1.15 grams of graphene oxides, first through ultrasonication 15 minutes, ultrasonic frequency 20kHz, then under powerful mechanical stirring, stir 2 hours, obtain composite precursor; In selected acidic silicasol, dioxide-containing silica is that 20%, pH value is 2.4, and size is 20nm;
(2) in vacuum drying oven, after curing dry 24h, adopt high speed ball mill to grind 2 hours the composite precursor obtaining, obtain exquisiteness and the Powdered presoma of homogeneous;
(3) Powdered presoma is put into high temperature process furnances, pass into high-purity argon gas, at 1400 ℃, carry out carbothermic reduction reaction 8 hours; Obtain silicon carbide micro-powder crude product;
(4) in the hydrofluoric acid that is 10% by gained silicon carbide micro-powder crude product in concentration, soak suction filtration after 2 hours, filter residue is under air existence condition, and 700 ℃ of sintering 5 hours, remove unreacted carbon, obtains pure silicon carbide powder after cooling.
Embodiment tri-:
(1) after 5.0 grams of silicon sol are mixed with 1.8 grams of graphene oxides, first through ultrasonication 20 minutes, ultrasonic frequency 80kHz, then under powerful mechanical stirring, stir 4 hours, obtain composite precursor; In selected acidic silicasol, dioxide-containing silica is that 30%, pH value is 2.0, and size is 6nm;
(2) in air dry oven, after curing dry 24h, adopt high speed ball mill to grind 2 hours the composite precursor obtaining, obtain exquisiteness and the Powdered presoma of homogeneous;
(3) Powdered presoma is put into high temperature process furnances, pass into high-purity argon gas, at 1600 ℃, carry out carbothermic reduction reaction 2 hours; Obtain silicon carbide micro-powder crude product;
(4) in the mixing acid that the hydrofluoric acid that is 10% by gained silicon carbide micro-powder crude product in concentration and the acid of 10% nitric acid form, soak suction filtration after 3 hours, filter residue is under air existence condition, 500 ℃ of sintering 8 hours, remove unreacted carbon, obtain pure silicon carbide powder after cooling.
Embodiment tetra-:
(1) after 5.0 grams of silicon sol are mixed with 0.8 gram of graphene oxide, first through ultrasonication 15 minutes, ultrasonic frequency 60kHz, then under powerful mechanical stirring, stir 3 hours, obtain composite precursor; In selected acidic silicasol, dioxide-containing silica is that 10%, pH value is 7.0, and size is 20nm;
(2) in freeze drying box, after curing dry 24h, adopt high speed ball mill to grind 2 hours the composite precursor obtaining, obtain exquisiteness and the Powdered presoma of homogeneous;
(3) Powdered presoma is put into high temperature process furnances, pass into high-purity argon gas, at 1600 ℃, carry out carbothermic reduction reaction 2 hours; Obtain silicon carbide micro-powder crude product;
(4) in the nitric acid that is 20% by gained silicon carbide micro-powder crude product in concentration, soak suction filtration after 4 hours, filter residue is under air existence condition, and 600 ℃ of sintering 5 hours, remove unreacted carbon, obtains pure silicon carbide powder after cooling.
Embodiment five:
(1) after 5.0 grams of silicon sol are mixed with 0.8 gram of graphene oxide, first through ultrasonication 25 minutes, ultrasonic frequency 120kHz, then under powerful mechanical stirring, stir 4 hours, obtain composite precursor; In selected acidic silicasol, dioxide-containing silica is that 5%, pH value is 6.0, and size is 20nm;
(2) in vacuum drying oven, after curing dry 24h, adopt high speed ball mill to grind 2 hours the composite precursor obtaining, obtain exquisiteness and the Powdered presoma of homogeneous;
(3) Powdered presoma is put into high temperature process furnances, pass into high-purity argon gas, at 1500 ℃, carry out carbothermic reduction reaction 7 hours; Obtain silicon carbide micro-powder crude product;
(4) in the hydrofluoric acid that is 8% by gained silicon carbide micro-powder crude product in concentration, soak suction filtration after 3.5 hours, filter residue is under air existence condition, and 700 ℃ of sintering 1 hour, remove unreacted carbon, obtains pure silicon carbide powder after cooling.
Embodiment six:
(1) after 5.0 grams of silicon sol are mixed with 1.15 grams of graphene oxides, elder generation 20 minutes through ultrasonic wave place, ultrasonic frequency 120kHz, then under powerful mechanical stirring, stir 2 hours, obtain composite precursor; In selected acidic silicasol, dioxide-containing silica is that 20%, pH value is 3.0, and size is 30nm;
(2) in vacuum drying oven, after curing dry 24h, adopt high speed ball mill to grind 2 hours the composite precursor obtaining, obtain exquisiteness and the Powdered presoma of homogeneous;
(3) Powdered presoma is put into high temperature process furnances, pass into high-purity argon gas, at 1400 ℃, carry out carbothermic reduction reaction 7 hours; Obtain silicon carbide micro-powder crude product;
(4) in the nitric acid that is 10% by gained silicon carbide micro-powder crude product in concentration, soak suction filtration after 3 hours, filter residue is under air existence condition, and 600 ℃ of sintering 4 hours, remove unreacted carbon, obtains pure silicon carbide powder after cooling.
Claims (2)
1. a preparation method for high-purity wire carborundum powder, is characterized in that concrete steps are as follows:
(1) after silicon sol is mixed by the weight percent of 100:16-36 with graphene oxide, first through ultrasonication 15-30 minute, ultrasonic frequency 20-120kHz, then at strong stirring 2-4 hour, obtain composite precursor;
Described silicon sol is dioxide-containing silica 5%-30%, pH value 2-7, and size is the acidic silicasol between 6-30nm;
Described graphene oxide is the carbon material with good laminated structure;
(2) composite precursor is solidified after dry 48h in loft drier, adopt high speed ball mill to grind 2 hours, obtain Powdered presoma fine and smooth and homogeneous;
Described drying means is vacuum-drying, forced air drying or lyophilize,
(3) Powdered presoma is put into high temperature process furnances, pass into purity and reach 99.99% argon gas, at 1400-1600 ℃, carry out carbothermic reduction reaction 2-8 hour, obtain silicon carbide micro-powder crude product;
(4) silicon carbide micro-powder crude product is soaked in mineral acid to suction filtration after 2-4 hour, filter residue under air existence condition at 400-700 ℃ sintering 1-9 hour, remove unreacted carbon, obtain content after cooling to be not less than 99% silicon carbide powder;
Described mineral acid is that concentration is hydrofluoric acid and/or the nitric acid of 10%-20%, the ratio of mixture of hydrofluoric acid and nitric acid be arbitrarily than.
2. the preparation method of a kind of high-purity wire carborundum powder according to claim 1, is characterized in that presoma is to be placed in to put into high temperature process furnances after corundum crucible and pass into argon gas, carries out carbothermic reduction reaction.
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| CN103864076A (en) * | 2012-12-11 | 2014-06-18 | 河南工业大学 | Preparation method of silicon carbide aerogel on basis of SiO2 aerogel as template |
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| CN108285145A (en) * | 2018-04-27 | 2018-07-17 | 中国人民解放军国防科技大学 | Three-dimensional multi-level structure nano silicon carbide, preparation method and application thereof |
| CN111232983A (en) * | 2020-03-27 | 2020-06-05 | 泉州师范学院 | Method for large-scale preparation of SiC nanowires by using spongy graphene or derivatives thereof as carbon source |
| CN111591995B (en) * | 2020-06-22 | 2021-08-13 | 黑龙江冠瓷科技有限公司 | Preparation method of nano silicon carbide particles based on NaF shape regulator |
| CN111533131B (en) * | 2020-06-22 | 2021-08-13 | 黑龙江冠瓷科技有限公司 | Based on CaCl2Preparation method of nano silicon carbide particles of shape regulator |
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| CN115521162B (en) * | 2022-10-17 | 2023-08-22 | 峨眉山市鑫锐新材料有限公司 | Preparation method of hollow silicon carbide microbeads |
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| JP3834639B2 (en) * | 2002-12-27 | 2006-10-18 | 独立行政法人物質・材料研究機構 | Method for producing silicon nitride nanowire coated with boron nitride |
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| CN1834309A (en) * | 2006-03-02 | 2006-09-20 | 浙江理工大学 | Method of synthetizing two kinds of different shaped silicon carbid nano wire |
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