CN104313678B - 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 PDFInfo
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- CN104313678B CN104313678B CN201410540609.8A CN201410540609A CN104313678B CN 104313678 B CN104313678 B CN 104313678B CN 201410540609 A CN201410540609 A CN 201410540609A CN 104313678 B CN104313678 B CN 104313678B
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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
The invention belongs to carbon composite refractory field.Specifically related to a kind of crystal whisker-shaped SiC/Si3N4/Si2N2O composite powders
Body and preparation method thereof.
Background technology
SiC is mutually widely used in composite as toughness reinforcing, to improve the intensity and toughness of material.And SiC whiskers
Meet as toughness reinforcing and be more preferably anchored in its embedded substrate, therefore the SiC of one-dimensional nano structure（Such as crystal whisker-shaped SiC）Compound
In material, toughening effect can be become apparent from than graininess SiC effect.
In carbon composite refractory, SiC is usually to be formed by serial reaction with Si and C as primary raw material, reacts bar
Part, the particularly impact of calcining system and catalyst type to SiC growing amounts and pattern are very big.In terms of calcining system impact,
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.）
During the reaction of research C and silica flour, when finding the Temperature Treatment higher than elemental silicon fusing point, SiC is present with graininess.In catalyst shadow
Aspect is rung, be there are some researches show, add a certain amount of catalyst（Ni、Fe...）After being partially formed solid-liquid-gas phase, although
The growing amount of the limited raising SiC whiskers of energy, but can be in a large amount of unreacted silicons of sample internal residual and carbon；Meanwhile, catalyst for
Belong to impurity for refractory material, cross the introducing of multi-catalyst, the high-temperature behavior of refractory material can be affected.
It can be seen that, there are the following problems for the synthesis with regard to SiC at present and application:（1）Less than heat treatment under Si melting temperatures
Shi Fasheng solid-solid reactions, reaction are very slow, and it is limited to generate SiC whisker amounts, extend the response time and can then consume more multiple-energy-source, and not
Remaining silicon and carbon can be eliminated, this certainly will affect high-temperature behavior；（2）Higher than heat treatment under Si melting temperatures, granule can be generated
Shape SiC is not notable for the toughening effect of composite；(3) although single-phase SiC whiskers can increase to carbon composite refractory
It is tough, but other non-oxidized substances are compared, which is not notable to improving slag resistance.
The content of the invention
It is contemplated that overcoming prior art defect, it is therefore an objective to provide a kind of process is simple, without catalyst and Jing be higher than
The process of silicon melting temperature can prepare crystal whisker-shaped SiC/Si3N4/Si2N2The method of O composite granules, prepared crystal whisker-shaped SiC/
Si3N4/Si2N2O composite granule impurity contents are low, phase content and morphology controllable.
For achieving the above object, the present invention is adopted the technical scheme that：With the simple substance silica flour and 13 ~ 46wt% of 54 ~ 87wt%
Carbon dust be raw material, the modified bonding agent of the additional 3 ~ 6wt% of raw material stirs, and mechanical pressing, the base substrate after molding exist
It is dried 12 ~ 48 hours under the conditions of 110 DEG C.Again dried base substrate is burnt till in carbon atmosphere in burying：Under the conditions of 1180 ~ 1280 DEG C
Insulation 2 ~ 6 hours, is continuously heating to 1420 ~ 1480 DEG C, is incubated 3 ~ 6 hours.Then room temperature is naturally cooled to stove, crush, system
Obtain crystal whisker-shaped SiC/Si3N4/Si2N2O composite granules.
Wherein, the preparation method of modified bonding agent is：It is first mixed by 45 ~ 60wt% phenolic resin and 40 ~ 55wt% elemental silicons
Material mixing is closed, the dehydrated alcohol of the additional 12 ~ 25wt% of compound is stirred 1 hour in 55 ~ 65 DEG C of water-bath, obtained final product
To modified bonding agent.
The carbon dust is one or more of crystalline flake graphite and carbon black；The C content of crystalline flake graphite is more than 97wt%, and particle diameter is little
In 88 μm；The C content of carbon black is more than 99wt%, and particle diameter is less than 60nm.
The Si contents of the elemental silicon are more than 97wt%, and particle diameter is less than 40 μm.
The Residual carbon of the phenolic resin is more than 35wt%.
The typed pressure is 50 ~ 150MPa.
There is following good effect compared with prior art due to adopting above-mentioned technical proposal, the present invention：
The present invention controls SiC/Si by controlling calcining system3N4/Si2N2The nucleation and growth process of O, be higher than finally
Elemental silicon melting temperature and it is additive-free under the conditions of synthesized crystal whisker-shaped SiC/Si3N4/Si2N2O composite granules, preparation technology letter
It is single；As solid-solid reaction and solid-liquid-gas phase reaction are controlled in preparation process so that SiC/Si3N4/Si2N2The nucleation amount of O
With coarsening rate all quickly, thus substantial amounts of SiC/Si can be generated3N4/Si2N2O crystal whisker-shaped materials；Wherein SiC diameter of whiskers scope
For 70 ~ 480nm.
Crystal whisker-shaped SiC/Si obtained in of the invention3N4/Si2N2O composites are with crystal whisker-shaped SiC, Si3N4And Si2N2Based on O
Crystalline phase, SiC whiskers average diameter are 79nm ~ 480nm, without remaining elemental silicon and carbon dust.
Therefore, the present invention is processing prepared crystal whisker-shaped SiC/Si higher than silicon melting temperature without catalyst and Jing3N4/Si2N2O
It is compound, process is simple；Prepared crystal whisker-shaped SiC/Si3N4/Si2N2O composite granule impurity contents are low, and phase content, SiC are brilliant
Must diameter and morphology controllable.
Specific embodiment
With reference to specific embodiment, the invention will be further described, not the restriction to its protection domain.
To avoid repeating, first will be the modified bonding agent and raw material Unify legislation in this specific embodiment as follows, embodiment
In repeat no more：
The preparation method of modified bonding agent is：First will be 45 ~ 60wt% phenolic resin and 40 ~ 55wt% elemental silicons mixed for compound
Close, the dehydrated alcohol of the additional 12 ~ 25wt% of compound, stir 1 hour in 55 ~ 65 DEG C of water-bath, that is, be modified
Bonding agent.
The C content of crystalline flake graphite is more than 97wt%, and particle diameter is less than 88 μm；The carbon content of carbon black is more than 99wt%, and particle diameter is less than
60nm。
The Si contents of the elemental silicon are more than 97wt%, and particle diameter is less than 40 μm.
The Residual carbon of the phenolic resin is more than 35wt%.
Embodiment 1
A kind of crystal whisker-shaped SiC/Si3N4/Si2N2O composite granules and preparation method thereof.With the simple substance silica flour of 65 ~ 76wt% and
The crystalline flake graphite of 24 ~ 35wt% is raw material, and the modified bonding agent of the additional 3 ~ 5wt% of raw material stirs, pressure be 50 ~
Mechanical pressing under the conditions of 80MPa, the base substrate after molding are dried 24 ~ 36 hours under the conditions of 110 DEG C.Again by dried base substrate in
Burn till in burying carbon atmosphere：4 ~ 6 hours are incubated under the conditions of 1180 ~ 1200 DEG C, 1420 ~ 1440 DEG C are continuously heating to, insulation 4 ~ 6 is little
When.Then room temperature being naturally cooled to stove, being crushed, crystal whisker-shaped SiC/Si is obtained3N4/Si2N2O composite granules.
Using technical scheme described in the present embodiment, obtained crystal whisker-shaped SiC/Si3N4/Si2N2O composite granules are with crystal whisker-shaped
SiC、Si3N4And Si2N2O is principal crystalline phase, and SiC whiskers average diameter is 148nm ~ 353nm, without remaining elemental silicon and carbon.
Embodiment 2
A kind of crystal whisker-shaped SiC/Si3N4/Si2N2O composite granules and preparation method thereof.With the simple substance silica flour of 54 ~ 65wt% and
The carbon black of 35 ~ 46wt% is raw material, and the modified bonding agent of the additional 4 ~ 6wt% of raw material stirs, pressure be 70 ~
Mechanical pressing under the conditions of 100MPa, the base substrate after molding are dried 12 ~ 18 hours under the conditions of 110 DEG C.Again by dried base substrate
Burn till in carbon atmosphere is buried：4 ~ 6 hours are incubated under the conditions of 1200 ~ 1230 DEG C, 1430 ~ 1450 DEG C are continuously heating to, insulation 3 ~ 5
Hour.Then room temperature being naturally cooled to stove, being crushed, crystal whisker-shaped SiC/Si is obtained3N4/Si2N2O composite granules.
Using technical scheme described in the present embodiment, obtained crystal whisker-shaped SiC/Si3N4/Si2N2O composite granules are with crystal whisker-shaped
SiC、Si3N4And Si2N2O is principal crystalline phase, and SiC whiskers average diameter is 79nm ~ 269nm, without remaining elemental silicon and carbon.
Embodiment 3
A kind of crystal whisker-shaped SiC/Si3N4/Si2N2O composite granules and preparation method thereof.With the simple substance silica flour of 75 ~ 87wt% and
The carbon dust of 13 ~ 25wt% is raw material, and the modified bonding agent of the additional 4 ~ 6wt% of raw material stirs, pressure be 90 ~
Mechanical pressing under the conditions of 140MPa, the base substrate after molding are dried 18 ~ 24 hours under the conditions of 110 DEG C.Again by dried base substrate
Burn till in carbon atmosphere is buried：3 ~ 5 hours are incubated under the conditions of 1230 ~ 1250 DEG C, 1450 ~ 1480 DEG C are continuously heating to, insulation 3 ~ 5
Hour.Then room temperature being naturally cooled to stove, being crushed, crystal whisker-shaped SiC/Si is obtained3N4/Si2N2O composite granules.
Carbon dust described in the present embodiment is made up of crystalline flake graphite and carbon black, and crystalline flake graphite accounts for 50 ~ 70wt% of solid carbon, and carbon black is accounted for
30 ~ 50wt% of solid carbon.
Using technical scheme described in the present embodiment, obtained crystal whisker-shaped SiC/Si3N4/Si2N2O composite granules are with crystal whisker-shaped
SiC、Si3N4And Si2N2O is principal crystalline phase, and SiC whiskers average diameter is 100nm ~ 280nm, without remaining elemental silicon and carbon.
Embodiment 4
A kind of crystal whisker-shaped SiC/Si3N4/Si2N2O composite granules and preparation method thereof.With the simple substance silica flour of 65 ~ 76wt% and
The white carbon black of 24 ~ 35wt% for the additional 4 ~ 6wt% of raw material of raw material modified bonding agent, stir, pressure be 120 ~
Mechanical pressing under the conditions of 150MPa, the base substrate after molding are dried 36 ~ 48 hours under the conditions of 110 DEG C.Again by dried base substrate
Burn till in carbon atmosphere is buried：2 ~ 5 hours are incubated under the conditions of 1230 ~ 1280 DEG C, 1460 ~ 1480 DEG C are continuously heating to, insulation 3 ~ 5
Hour.Then room temperature being naturally cooled to stove, being crushed, crystal whisker-shaped SiC/Si is obtained3N4/Si2N2O composite granules.
Using technical scheme described in the present embodiment, obtained crystal whisker-shaped SiC/Si3N4/Si2N2O composite granules are with crystal whisker-shaped
SiC、Si3N4And Si2N2O is principal crystalline phase, and SiC whiskers average diameter is 240nm ~ 480nm, without remaining elemental silicon and carbon.
This specific embodiment controls SiC/Si by controlling calcining system3N4/Si2N2The nucleation and growth process of O, most
Eventually higher than elemental silicon melting temperature and it is additive-free under the conditions of synthesized crystal whisker-shaped SiC/Si3N4/Si2N2O composite granules, system
Standby process is simple；As solid-solid reaction and solid-liquid-gas phase reaction are controlled in preparation process so that SiC/Si3N4/Si2N2O
Nucleation amount and coarsening rate all quickly, therefore substantial amounts of SiC/Si can be generated3N4/Si2N2O crystal whisker-shaped materials.
Crystal whisker-shaped SiC/Si obtained in this specific embodiment3N4/Si2N2O composites are with crystal whisker-shaped SiC, Si3N4With
Si2N2O is principal crystalline phase, and SiC whiskers average diameter is 79nm ~ 480nm, without remaining elemental silicon and carbon.
Therefore, this specific embodiment is processing prepared crystal whisker-shaped SiC/ higher than silicon melting temperature without catalyst and Jing
Si3N4/Si2N2O is combined, process is simple；Prepared crystal whisker-shaped SiC/Si3N4/Si2N2O composite granule impurity contents are low, thing phase
Content, SiC diameter of whiskers and morphology controllable.
Claims (5)
1. a kind of crystal whisker-shaped SiC/Si3N4/Si2N2The preparation method of O composite granules, it is characterised in that with the simple substance of 54～87wt%
The carbon dust of silica flour and 13～46wt% is raw material, and the modified bonding agent of the additional 3～6wt% of raw material stirs, and machine is pressed into
Type, the base substrate after molding are dried 12～48 hours under the conditions of 110 DEG C；Again dried base substrate is burnt till in carbon atmosphere in burying：
2～6 hours are incubated under the conditions of 1180～1280 DEG C, 1420～1480 DEG C are continuously heating to, 3～6 hours are incubated；Then with stove
Room temperature is naturally cooled to, is crushed, crystal whisker-shaped SiC/Si is obtained3N4/Si2N2O composite granules；
Wherein, the preparation method of modified bonding agent is：It is first mixed by 45～60wt% phenolic resin and 40～55wt% elemental silicons
Close material to mix, the dehydrated alcohol of the additional 12～25wt% of compound, stirring 1 hour in 55～65 DEG C of water-bath, i.e.,
Obtain modified bonding agent.
2. crystal whisker-shaped SiC/Si according to claim 13N4/Si2N2The preparation method of O composite granules, it is characterised in that institute
Carbon dust is stated for one or more of crystalline flake graphite and carbon black；The C content of crystalline flake graphite is more than 97wt%, and particle diameter is less than 88 μm；Carbon
Black C content is more than 99wt%, and particle diameter is less than 60nm.
3. crystal whisker-shaped SiC/Si according to claim 13N4/Si2N2The preparation method of O composite granules, it is characterised in that institute
The Si contents of elemental silicon are stated more than 97wt%, particle diameter is less than 40 μm.
4. crystal whisker-shaped SiC/Si according to claim 13N4/Si2N2The preparation method of O composite granules, it is characterised in that institute
The Residual carbon for stating phenolic resin is more than 35wt%.
5. crystal whisker-shaped SiC/Si according to claim 13N4/Si2N2The preparation method of O composite granules, it is characterised in that institute
Typed pressure is stated for 50～150MPa.
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| US6696514B1 (en) * | 2001-02-22 | 2004-02-24 | Council Of Scientific & Industrial Research | Process useful for making in-situ silicon carbide in the form of particulate, whiskers and fibres in an inorganic composite matrix |
| CN1844493A (en) * | 2006-03-16 | 2006-10-11 | 武汉科技大学 | Method for synthesizing bionic silicon carbide crystal whisker |
| CN102229498A (en) * | 2011-04-27 | 2011-11-02 | 中国科学院上海硅酸盐研究所 | Si3N4-Si2N2O double-phase ceramic material and preparation method thereof |
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