CN104313678A - Whisker-like SiC/Si3N4/Si2N2O composite powder and preparation method thereof - Google Patents

Whisker-like SiC/Si3N4/Si2N2O composite powder and preparation method thereof Download PDF

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Publication number
CN104313678A
CN104313678A CN201410540609.8A CN201410540609A CN104313678A CN 104313678 A CN104313678 A CN 104313678A CN 201410540609 A CN201410540609 A CN 201410540609A CN 104313678 A CN104313678 A CN 104313678A
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sic
crystal whisker
composite granule
preparation
shaped sic
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CN104313678B (en
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鄢文
陈俊峰
李楠
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Wuhan University of Science and Engineering WUSE
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Wuhan University of Science and Engineering WUSE
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Abstract

The invention specifically relates to whisker-like SiC/Si3N4/Si2N2O composite powder and a preparation method thereof. According to the technical scheme, by using 54-87wt% of monatomic silicon powder and 13-46% of carbon powder as raw materials, in addition with 3-6wt% of a modified binding agent, uniformly stirring, mechanically pressing and drying a moulded blank body at 110 DEG C for 12-48 hours; then, sintering the dried blank body in a carbon-burying atmosphere: insulating for 2-6 hours at 1180-1280 DEG C, continuously heating to 1420-1480 DEG C and insulating for 3-6 hours; and then, naturally cooling along with the furnace to room temperature and crushing to prepare the whisker-like SiC/Si3N4/Si2N2O composite powder. The whisker-like SiC/Si3N4/Si2N2O composite powder is prepared by treatment which is higher than the silicon melting point without catalysts, so that the process is simple. The prepared whisker-like SiC/Si3N4/Si2N2O composite powder is low in content of impurities and the phase content and the diameters and shapes of SiC whiskers are controllable.

Description

A kind of crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule and preparation method thereof
Technical field
The invention belongs to carbon composite refractory field.Be specifically related to a kind of crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule and preparation method thereof.
Background technology
SiC is widely used in matrix material mutually as toughness reinforcing, to improve intensity and the toughness of material.And SiC whisker is better anchored in its matrix embedded as toughness reinforcing meeting, therefore the SiC(of one dimension Nano structure is as crystal whisker-shaped SiC) toughening effect can be more obvious than particulate state SiC effect in the composite.
In carbon composite refractory, SiC is generally with Si and C for main raw material is formed by serial reaction, reaction conditions, particularly calcining system and the impact of catalyst type on SiC growing amount and pattern very large.In calcining system affects, technical literature (Rayisa Voytovych, et al. Reactivity between liquid Si or Si alloys and graphite. Journal of the European Ceramic Society 32 (2012) 3825 – 3835.) when studying the reaction of C and silica flour, when finding the Temperature Treatment higher than elemental silicon fusing point, SiC exists with particulate state.In catalysts influence, there are some researches show, after adding a certain amount of catalyzer (Ni, Fe...), can solid-liquid-gas phase be partially formed, although the growing amount of the limited raising SiC whisker of energy, can at a large amount of unreacted silicon of sample internal residual and carbon; Meanwhile, catalyzer belongs to impurity for refractory materials, crosses the introducing of multi-catalyst, can affect the high-temperature behavior of refractory materials.
Visible, at present about the synthesis of SiC and application, there are the following problems: (1) during thermal treatment, solid-solid reaction occurs under lower than Si melting temperature, react very slow, generate SiC whisker amount limited, the prolongation reaction times then can consume more multiple-energy-source, and remaining silicon and carbon can not be eliminated, this certainly will affect high-temperature behavior; (2) thermal treatment under higher than Si melting temperature, can generate particulate state SiC, the toughening effect for matrix material is not remarkable; (3) although single-phase SiC whisker can be toughness reinforcing to carbon composite refractory, compare other non-oxidized substance, it is not remarkable to raising slag resistance.
Summary of the invention
The present invention is intended to overcome prior art defect, and object is to provide a kind of technique simply, at catalyst-free and warp can prepare crystal whisker-shaped SiC/Si higher than the process of silicon melting temperature 3n 4/ Si 2n 2the method of O composite granule, prepared crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule foreign matter content is low, phase content and morphology controllable.
For achieving the above object, the technical scheme that the present invention takes is: with the carbon dust of the simple substance silica flour of 54 ~ 87wt% and 13 ~ 46wt% for raw material, the modify cement of additional described raw material 3 ~ 6wt%, stirs, mechanical pressing, the base substrate after shaping under 110 DEG C of conditions dry 12 ~ 48 hours.Again dried base substrate is burnt till in burying in carbon atmosphere: under 1180 ~ 1280 DEG C of conditions, be incubated 2 ~ 6 hours, continue to be warming up to 1420 ~ 1480 DEG C, be incubated 3 ~ 6 hours.Then room temperature is naturally cooled to stove, broken, obtained crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule.
Wherein, the preparation method of modify cement is: be first compound mixing by 45 ~ 60wt% resol and 40 ~ 55wt% elemental silicon, the dehydrated alcohol of additional described compound 12 ~ 25wt%, stirs 1 hour, namely obtain modify cement in the water-bath of 55 ~ 65 DEG C.
Described carbon dust is more than one in crystalline flake graphite and carbon black; The C content of crystalline flake graphite is greater than 97wt%, and particle diameter is less than 88 μm; The C content of carbon black is greater than 99wt%, and particle diameter is less than 60nm.
The Si content of described elemental silicon is greater than 97wt%, and particle diameter is less than 40 μm.
The Residual carbon of described resol is greater than 35wt%.
Described typed pressure is 50 ~ 150MPa.
Owing to adopting technique scheme, the present invention compared with prior art has following positively effect:
The present invention is by controlling calcining system control SiC/Si 3n 4/ Si 2n 2the nucleation of O and growth process, finally synthesized crystal whisker-shaped SiC/Si under higher than elemental silicon melting temperature and additive-free condition 3n 4/ Si 2n 2o composite granule, preparation technology is simple; Owing to controlling solid-solid reaction and solid-liquid-gas-phase reaction in preparation process, make SiC/Si 3n 4/ Si 2n 2the nucleation amount of O and coarsening rate are all very fast, therefore can generate a large amount of SiC/Si 3n 4/ Si 2n 2o crystal whisker-shaped material; Wherein SiC diameter of whiskers scope is 70 ~ 480nm.
The crystal whisker-shaped SiC/Si that the present invention obtains 3n 4/ Si 2n 2o matrix material is with crystal whisker-shaped SiC, Si 3n 4and Si 2n 2o is principal crystalline phase, and SiC whisker mean diameter is 79nm ~ 480nm, not containing remaining elemental silicon and carbon dust.
Therefore, the present invention is at catalyst-free with through obtaining crystal whisker-shaped SiC/Si higher than the process of silicon melting temperature 3n 4/ Si 2n 2o compound, technique is simple; Prepared crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule foreign matter content is low, phase content, SiC diameter of whiskers and morphology controllable.
Embodiment
Below in conjunction with embodiment, the invention will be further described, the restriction not to its protection domain.
For avoiding repetition, first by the modify cement in this embodiment and raw material Unify legislation as follows, repeat no more in embodiment:
The preparation method of modify cement is: be first compound mixing by 45 ~ 60wt% resol and 40 ~ 55wt% elemental silicon, the dehydrated alcohol of additional described compound 12 ~ 25wt%, stirs 1 hour, namely obtain modify cement in the water-bath of 55 ~ 65 DEG C.
The C content of crystalline flake graphite is greater than 97wt%, and particle diameter is less than 88 μm; The carbon content of carbon black is greater than 99wt%, and particle diameter is less than 60nm.
The Si content of described elemental silicon is greater than 97wt%, and particle diameter is less than 40 μm.
The Residual carbon of described resol is greater than 35wt%.
embodiment 1
A kind of crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule and preparation method thereof.With the crystalline flake graphite of the simple substance silica flour of 65 ~ 76wt% and 24 ~ 35wt% for raw material, the modify cement of additional described raw material 3 ~ 5wt%, stirs, mechanical pressing under pressure is 50 ~ 80MPa condition, the base substrate after shaping under 110 DEG C of conditions dry 24 ~ 36 hours.Again dried base substrate is burnt till in burying in carbon atmosphere: under 1180 ~ 1200 DEG C of conditions, be incubated 4 ~ 6 hours, continue to be warming up to 1420 ~ 1440 DEG C, be incubated 4 ~ 6 hours.Then room temperature is naturally cooled to stove, broken, obtained crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule.
Adopt technical scheme described in the present embodiment, obtained crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule is with crystal whisker-shaped SiC, Si 3n 4and Si 2n 2o is principal crystalline phase, and SiC whisker mean diameter is 148nm ~ 353nm, not containing remaining elemental silicon and carbon.
embodiment 2
A kind of crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule and preparation method thereof.With the carbon black of the simple substance silica flour of 54 ~ 65wt% and 35 ~ 46wt% for raw material, the modify cement of additional described raw material 4 ~ 6wt%, stirs, mechanical pressing under pressure is 70 ~ 100MPa condition, the base substrate after shaping under 110 DEG C of conditions dry 12 ~ 18 hours.Again dried base substrate is burnt till in burying in carbon atmosphere: under 1200 ~ 1230 DEG C of conditions, be incubated 4 ~ 6 hours, continue to be warming up to 1430 ~ 1450 DEG C, be incubated 3 ~ 5 hours.Then room temperature is naturally cooled to stove, broken, obtained crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule.
Adopt technical scheme described in the present embodiment, obtained crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule is with crystal whisker-shaped SiC, Si 3n 4and Si 2n 2o is principal crystalline phase, and SiC whisker mean diameter is 79nm ~ 269nm, not containing remaining elemental silicon and carbon.
embodiment 3
A kind of crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule and preparation method thereof.With the carbon dust of the simple substance silica flour of 75 ~ 87wt% and 13 ~ 25wt% for raw material, the modify cement of additional described raw material 4 ~ 6wt%, stirs, mechanical pressing under pressure is 90 ~ 140MPa condition, the base substrate after shaping under 110 DEG C of conditions dry 18 ~ 24 hours.Again dried base substrate is burnt till in burying in carbon atmosphere: under 1230 ~ 1250 DEG C of conditions, be incubated 3 ~ 5 hours, continue to be warming up to 1450 ~ 1480 DEG C, be incubated 3 ~ 5 hours.Then room temperature is naturally cooled to stove, broken, obtained crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule.
Carbon dust described in the present embodiment is made up of crystalline flake graphite and carbon black, and crystalline flake graphite accounts for solid carbon 50 ~ 70wt%, and carbon black accounts for solid carbon 30 ~ 50wt%.
Adopt technical scheme described in the present embodiment, obtained crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule is with crystal whisker-shaped SiC, Si 3n 4and Si 2n 2o is principal crystalline phase, and SiC whisker mean diameter is 100nm ~ 280nm, not containing remaining elemental silicon and carbon.
embodiment 4
A kind of crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule and preparation method thereof.With the modify cement that the carbon black of the simple substance silica flour of 65 ~ 76wt% and 24 ~ 35wt% is the additional described raw material 4 ~ 6wt% of raw material, stir, mechanical pressing under pressure is 120 ~ 150MPa condition, the base substrate after shaping under 110 DEG C of conditions dry 36 ~ 48 hours.Again dried base substrate is burnt till in burying in carbon atmosphere: under 1230 ~ 1280 DEG C of conditions, be incubated 2 ~ 5 hours, continue to be warming up to 1460 ~ 1480 DEG C, be incubated 3 ~ 5 hours.Then room temperature is naturally cooled to stove, broken, obtained crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule.
Adopt technical scheme described in the present embodiment, obtained crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule is with crystal whisker-shaped SiC, Si 3n 4and Si 2n 2o is principal crystalline phase, and SiC whisker mean diameter is 240nm ~ 480nm, not containing remaining elemental silicon and carbon.
 
This embodiment is by controlling calcining system control SiC/Si 3n 4/ Si 2n 2the nucleation of O and growth process, finally synthesized crystal whisker-shaped SiC/Si under higher than elemental silicon melting temperature and additive-free condition 3n 4/ Si 2n 2o composite granule, preparation technology is simple; Owing to controlling solid-solid reaction and solid-liquid-gas-phase reaction in preparation process, make SiC/Si 3n 4/ Si 2n 2the nucleation amount of O and coarsening rate are all very fast, therefore can generate a large amount of SiC/Si 3n 4/ Si 2n 2o crystal whisker-shaped material.
The crystal whisker-shaped SiC/Si that this embodiment is obtained 3n 4/ Si 2n 2o matrix material is with crystal whisker-shaped SiC, Si 3n 4and Si 2n 2o is principal crystalline phase, and SiC whisker mean diameter is 79nm ~ 480nm, not containing remaining elemental silicon and carbon.
Therefore, this embodiment is at catalyst-free with through obtaining crystal whisker-shaped SiC/Si higher than the process of silicon melting temperature 3n 4/ Si 2n 2o compound, technique is simple; Prepared crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule foreign matter content is low, phase content, SiC diameter of whiskers and morphology controllable.

Claims (6)

1. a crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2the preparation method of O composite granule, it is characterized in that the modify cement of additional described raw material 3 ~ 6wt%, stirs with the carbon dust of the simple substance silica flour of 54 ~ 87wt% and 13 ~ 46wt% for raw material, mechanical pressing, the base substrate after shaping under 110 DEG C of conditions dry 12 ~ 48 hours; Again dried base substrate is burnt till in burying in carbon atmosphere: under 1180 ~ 1280 DEG C of conditions, be incubated 2 ~ 6 hours, continue to be warming up to 1420 ~ 1480 DEG C, be incubated 3 ~ 6 hours; Then room temperature is naturally cooled to stove, broken, obtained crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule;
Wherein, the preparation method of modify cement is: be first compound mixing by 45 ~ 60wt% resol and 40 ~ 55wt% elemental silicon, the dehydrated alcohol of additional described compound 12 ~ 25wt%, stirs 1 hour, namely obtain modify cement in the water-bath of 55 ~ 65 DEG C.
2. crystal whisker-shaped SiC/Si according to claim 1 3n 4/ Si 2n 2the preparation method of O composite granule, is characterized in that described carbon dust is more than one in crystalline flake graphite and carbon black; The C content of crystalline flake graphite is greater than 97wt%, and particle diameter is less than 88 μm; The C content of carbon black is greater than 99wt%, and particle diameter is less than 60nm.
3. crystal whisker-shaped SiC/Si according to claim 1 3n 4/ Si 2n 2the preparation method of O composite granule, it is characterized in that the Si content of described elemental silicon is greater than 97wt%, particle diameter is less than 40 μm.
4. crystal whisker-shaped SiC/Si according to claim 1 3n 4/ Si 2n 2the preparation method of O composite granule, is characterized in that the Residual carbon of described resol is greater than 35wt%.
5. crystal whisker-shaped SiC/Si according to claim 1 3n 4/ Si 2n 2the preparation method of O composite granule, is characterized in that described typed pressure is 50 ~ 150MPa.
6. a crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule, is characterized in that described crystal whisker-shaped SiC/Si 3n 4/ Si 2n 2o composite granule is the crystal whisker-shaped SiC/Si according to any one of claim 1 ~ 5 3n 4/ Si 2n 2crystal whisker-shaped SiC/Si prepared by the preparation method of O composite granule 3n 4/ Si 2n 2o composite granule.
CN201410540609.8A 2014-10-14 2014-10-14 Whisker-like SiC/Si3N4/Si2N2O composite powder and preparation method thereof Expired - Fee Related CN104313678B (en)

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Cited By (1)

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CN106431431A (en) * 2016-08-31 2017-02-22 江苏诺明高温材料股份有限公司 In-situ generating method for Si2N2O ceramic bonding phases in aluminum-carbon fireproof material with carbon thermal reduction method

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