CN108484201A - A kind of low-shrinkage porous silicon nitride ceramic and preparation method thereof - Google Patents
A kind of low-shrinkage porous silicon nitride ceramic and preparation method thereof Download PDFInfo
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Abstract
A kind of low-shrinkage porous silicon nitride ceramic of present invention offer and preparation method thereof, with alpha silicon nitride, aluminium oxide, yttrium oxide is primary raw material, prepare aqueous-based ceramic slurry, first emulsification forms ball-type drop in oil phase, then pass through freezing, oily ceramic microsphere separation, freeze-drying obtains porous ceramics green microspheres, then porous silicon nitride ceramic microballoon is obtained by sintering, carry out grain size grading proportioning, and it is molded by mold again, solidification, it is dry, sintering, it is final to obtain porous silicon nitride ceramic, compared with prior art, the beneficial effects of the present invention are, the present invention is combined with freeze forming using dropping liquid in oil and prepares the porous silicon nitride microballoon of different-grain diameter, the controllable of pore structure and the porosity is realized using freeze forming process advantage；It can be used for preparing large-scale porous silicon nitride abnormity component, eliminate the directionality of caused pore structure during freeze forming；Meanwhile greatly reducing the possibility that excessive caused fault of construction is shunk in sintering process.
Description
Technical field
The present invention relates to the field shaping techniques of porous ceramic film material, and in particular to a kind of low-shrinkage porous silicon nitride pottery
Porcelain and preparation method thereof.
Background technology
Porous silicon-nitride ceramic material has high more excellent than strong, high temperature resistant, anti-oxidant and wear-resistant and anti-thermal shock etc.
While comprehensive performance, also there are the excellent dielectric properties such as relatively low density and low dielectric constant, dielectric loss, because
It can give full play to the excellent properties of both silicon nitride ceramics and porous ceramics, be widely used in machinery, chemical industry, ocean work
The key areas such as journey, aerospace.
Prepare that porosity and pore structure be controllable, silicon nitride base porous ceramics of high intensity, low-k is to realize nitrogen
The key of SiClx Quito hole ceramic applications.The technology of preparing of silicon nitride base porous ceramics mainly partially sinters method, port-creating method (has
Machine object, carbon dust), casting and self- propagating sintering process etc..Fukasawa et al. makes Si by freezing3N4Ceramic slurry solidifies,
And freeze-dried, pressureless sintering, obtain the porous Si that porosity is more than 50%3N4Ceramics.However, in freeze forming mistake
The directionality of ice-crystal growth causes sintered porous ceramics pore structure to have certain orientation, this pore property limit in journey
Application of the porous silicon nitride ceramic under certain specific environments is made.
In addition, silicon nitride is a kind of covalent key compound, and Si-N keys have very high key strong, nitrogen-atoms and silicon atom
Self-diffusion coefficient very little.In sintering process, bulk diffusion and grain boundary decision speed, sintering driving force necessary to being densified are very
Small, conventional solid sintering is difficult to realize its densification.Therefore it needs addition sintering aid to generate liquid phase in the high temperature process, utilizes
Liquid-phase sintering principle promotes to be densified while alpha-beta phase transition.However, the process of densification has larger receipts along with sample
Shrinkage can be since the inconsistent formation stress of shrinking percentage be to keep test specimen after sintering cracked for special-shaped structural part, this is greatly
The development and application of anisotropic approach porous silicon nitride ceramic are influenced.
In view of drawbacks described above, creator of the present invention proposes the present invention by prolonged research and practice.
Invention content
The present invention is in order to which while the acquisition porosity controllable porous silicon nitride ceramic, solution is existing in the prior art
Larger problem is shunk in sintering process, a kind of preparation method of low-shrinkage porous silicon nitride ceramic is provided comprising following
Step：
The first step：After α-siliconnitride, aluminium oxide, yttrium oxide are mixed, wet mixing, nitrogen drying sieving are uniformly mixed
Powder；
Second step：Deionized water and dispersant A will be added in mixed-powder described in the first step, obtain uniform and stable water base
Ceramic slurry；
Third walks：Aqueous-based ceramic slurry described in second step is entered by shaking dropping liquid in oil phase, the aqueous-based ceramic is made
Slurry forms microspheric drop in oil phase；And by refrigerant carry out freezing processing after, be separated by filtration from the oil phase solidifying
Solid ceramic microsphere, using ethyl acetate at -20 DEG C Low-temperature cleaning repeatedly；
4th step：Third is walked the ceramic microsphere to be dried in freeze drier, and the boron nitride in graphite crucible
Buried powder, stirring carry out first time pressureless sintering under nitrogen atmosphere protection, obtain porous silicon nitride microballoon；
5th step：Porous silicon nitride microballoon described in 4th step was subjected to sieve classification；
6th step：Aluminium oxide, yttrium oxide, organic monomer and dispersant B are dissolved in solvent, obtains and stablizes aluminium oxide-
Yttrium slurry；
7th step：Porous silicon nitride microballoon after being classified described in 5th step is packed into mold according to a certain ratio, and by the 6th
It is shaken in the step alumina-yttria ceramic slurry injection mold, removes the extra ceramic slurry in upper layer, solidification 12 was as a child
After take out, obtain ceramic body after dry；
8th step：Will it is dry described in the 7th step after ceramic body, under nitrogen atmosphere protection carry out second burns without pressure
Knot obtains porous silicon nitride ceramic.
Preferably, dispersant A described in second step is Sodium Polyacrylate or polyvinyl alcohol, and the dispersant A accounts for described mix
Close the 0.5%-1% of powder quality.
Preferably, slurry solid content is 10-40vol% in aqueous-based ceramic slurry described in second step.
Preferably, it is that the refrigerant is alcohol that third, which walks the freezing processing condition, the cryogenic temperature is -30
℃--10℃。
Preferably, the condition that third walks the vibrations dropping liquid is that vibration frequency is 100-1000 times/min, and water dropper aperture is
Φ0.16-0.51mm。
Preferably, the process conditions of first time pressureless sintering described in the 4th step are, heated up with the heating rate of 20 DEG C/min
To 500 DEG C, 1h is kept the temperature, then heats to 1700 DEG C -1850 DEG C, keeps the temperature 2h；The technique of second of pressureless sintering described in 8th step
Condition is to be warming up to 500 DEG C with the heating rate of 20 DEG C/min, keep the temperature 1h, then heat to 1500 DEG C -1850 DEG C.
Preferably, the condition for crossing sieve classification described in the 5th step is, when the grain size of the porous silicon nitride microballoon is less than 100 μm
It is I grades to be, is II grade when the grain size of the porous silicon nitride microballoon is between 100-400 μm, when the porous silicon nitride
The grain size of microballoon is III grade when being more than 400 μm.
Preferably, organic monomer described in the 6th step is glycolylurea epoxide resin, and the organic monomer quality is the ceramics
The 2wt% of powder quality；The dispersant B is polyacrylic acid, and the quality of the dispersant B is the ceramic powders quality
0.6wt%.
Preferably, I grade described in the 7th step, the quality proportioning of II grade and III grade of the porous silicon nitride microballoon be 2:
10:0 or 2:10:10 or 0:3:10.
A kind of low-shrinkage porous silicon nitride ceramic prepared using the above method.
Compared with the prior art, the beneficial effects of the present invention are：
1, it is combined with freeze forming using dropping liquid in oil and prepares the porous silicon nitride microballoon of different-grain diameter, using being frozen into
Type process advantage realizes the controllable of pore structure and the porosity；
2, sintering process is breached with when double sintering using porous microsphere grain size and shrinks excessive problem, prepared
The porous silicon nitride ceramic porosity is 30-60%, and linear shrinkage ratio is less than 3%.
3, the preparation method of low-shrinkage porous silicon nitride ceramic of the invention can be used for preparing large-scale porous silicon nitride
Abnormity component eliminates the directionality of caused pore structure during freeze forming；Meanwhile it greatly reducing in sintering process and receiving
The possibility for the excessive caused fault of construction that contracts.
Specific implementation mode
With reference to embodiments, the forgoing and additional technical features and advantages are described in more detail.
Embodiment 1
The first step：By α-siliconnitride, aluminium oxide, yttrium oxide in mass ratio 93：2:5 mixing, and with silicon nitride ball and anhydrous
Ethyl alcohol is ball-milling medium, and after wet mixing 12 hours, nitrogen drying sieving obtains uniform mixed-powder；
Second step：Deionized water and dispersant A will be added in mixed-powder described in the first step, obtain uniform and stable water base
Ceramic slurry, wherein the dispersant A is Sodium Polyacrylate, and the dispersant A accounts for the 0.5% of the mixed-powder quality,
Slurry solid content is 20vol% in the aqueous-based ceramic slurry；
Third walks：Aqueous-based ceramic slurry described in second step is entered by shaking dropping liquid in oil phase, the aqueous-based ceramic is made
Slurry oil phase formed microspheric drop, and by refrigerant carry out freezing processing after, be separated by filtration from the oil phase solidifying
Solid ceramic microsphere, using ethyl acetate at -20 DEG C Low-temperature cleaning repeatedly, wherein the oil phase is corn oil；The vibrations
The condition of dropping liquid is that vibration frequency is 100 times/min, and water dropper aperture is Φ 0.16mm；The freezing processing condition is, described cold
Jelly medium is alcohol, and the cryogenic temperature is -30 DEG C；
4th step：Third is walked the ceramic microsphere to be dried in freeze drier, and the boron nitride in graphite crucible
Buried powder, appropriate stirring make green microspheres without contacting with each other, carry out pressureless sintering under nitrogen atmosphere protection, obtain porous silicon nitride
The process conditions of microballoon, the pressureless sintering are to be warming up to 500 DEG C with the heating rate of 20 DEG C/min, keep the temperature 1h, then heat up
To 1700 DEG C, 2h is kept the temperature；
5th step：Porous silicon nitride microballoon described in 4th step was subjected to sieve classification, the condition for crossing sieve classification is, when
It is I grades that the grain size of the porous silicon nitride microballoon, which is less than 100 μm to be, when the grain size of the porous silicon nitride microballoon is between 100-
It is II grade when between 400 μm, is III grade when the grain size of the porous silicon nitride microballoon is more than 400 μm；
6th step：Aluminium oxide, yttrium oxide, organic monomer and dispersant B are dissolved in solvent, obtaining solid content is
Stabilization aluminium oxide-yttrium slurry of 20vol%, wherein the mass fraction of the aluminium oxide and yttrium oxide ratio is 1:2；
The organic monomer is glycolylurea epoxide resin, and the 2wt% that the organic monomer quality is the ceramic powders quality；Described
Dispersant B is polyacrylic acid, and the 0.6wt% that the quality of the dispersant B is the ceramic powders quality；
7th step：By I grade described in the 5th step, II grade and III grade of the porous silicon nitride microballoon in mass ratio
2:10:0 is packed into mold, and will be shaken in the alumina-yttria ceramic slurry injection mold described in the 6th step, and it is more to remove upper layer
Remaining ceramic slurry, solidification 12 were as a child taken out afterwards, and ceramic body is obtained after dry；
8th step：Ceramic body after will be dry described in the 7th step, pressureless sintering is carried out under nitrogen atmosphere protection, described
The process conditions of pressureless sintering are to be warming up to 500 DEG C with the heating rate of 20 DEG C/min, keep the temperature 1h, then heat to 1500 DEG C,
2h is kept the temperature, porous silicon nitride ceramic is finally obtained.
The present invention is combined with freeze forming using dropping liquid in oil and prepares the porous silicon nitride microballoon of different-grain diameter, and utilization is cold
The type process advantage of being frozen into realizes the controllable of pore structure and the porosity；It is breached with when double sintering using porous microsphere grain size
Sintering process shrinks excessive problem, and the porous silicon nitride ceramic porosity prepared is 30-60%, and linear shrinkage ratio is less than
3%, main cause is that the porous ceramic ball prepared the first stage has been subjected to high temperature sintering, and second stage uses porous microsphere grain
When diameter proportioning prepares porous ceramic film material, the solid-liquid phase reaction during sintering is mainly carried out in Ceramic Balls contact point, to
Cause shrinking percentage relatively low.Therefore, the preparation method of low-shrinkage porous silicon nitride ceramic of the invention can be used for preparing large-scale
Porous silicon nitride abnormity component eliminates the directionality of caused pore structure during freeze forming；Meanwhile greatly reducing burning
The possibility of excessive caused fault of construction is shunk during knot.
Embodiment 2
The present embodiment difference from example 1 is that, the first step is, by α-siliconnitride, aluminium oxide, yttrium oxide
After mixing, in mass ratio 90：3:After 7 wet mixings 12 hours, nitrogen drying sieving obtains uniform mixed powder, other with 1 phase of embodiment
Together.
Embodiment 3
The present embodiment difference from example 1 is that, dispersant A described in second step is polyvinyl alcohol, and described point
Powder A accounts for the 1% of the mixed-powder quality, other same as Example 1.
Embodiment 4
The present embodiment difference from example 1 is that, slurry solid content is in aqueous-based ceramic slurry described in second step
10vol%., other same as Example 1.
Embodiment 5
The present embodiment difference from example 1 is that, slurry solid content is in aqueous-based ceramic slurry described in second step
40vol%, it is other same as Example 1.
Embodiment 6
The present embodiment difference from example 1 is that, third walk it is described vibrations dropping liquid condition be that vibration frequency is
1000 times/min, water dropper aperture is Φ 0.51mm, other same as Example 1.
Embodiment 7
The present embodiment difference from example 1 is that, third walk it is described vibrations dropping liquid condition be that vibration frequency is
400 times/min, water dropper aperture is Φ 0.34mm, other same as Example 1.
Embodiment 8
The present embodiment difference from example 1 is that, the process conditions of first time pressureless sintering described in the 4th step are,
500 DEG C are warming up to the heating rate of 20 DEG C/min, keeps the temperature 1h, then heats to 1800 DEG C, keeps the temperature 2h；Second described in 8th step
The process conditions of secondary pressureless sintering are to be warming up to 500 DEG C with the heating rate of 20 DEG C/min, keep the temperature 1h, then heat to 1700
DEG C, it is other same as Example 1.
Embodiment 9
The present embodiment difference from example 1 is that, the process conditions of first time pressureless sintering described in the 4th step are,
500 DEG C are warming up to the heating rate of 20 DEG C/min, keeps the temperature 1h, then heats to 1850 DEG C, keeps the temperature 2h；Second described in 8th step
The process conditions of secondary pressureless sintering are to be warming up to 500 DEG C with the heating rate of 20 DEG C/min, keep the temperature 1h, then heat to 1850
DEG C, it is other same as Example 1.
Embodiment 10
The present embodiment difference from example 1 is that, I grade described in the 7th step, II grade and III grade more
The quality proportioning of hole silicon nitride microballoon is 2:10:10 or 0:3:10.
Embodiment 11
The present embodiment difference from example 1 is that, I grade described in the 7th step, II grade and III grade more
The quality proportioning of hole silicon nitride microballoon is 0:3:10.
The foregoing is merely presently preferred embodiments of the present invention, is merely illustrative for the purpose of the present invention, and not restrictive
's.Those skilled in the art understand that in the spirit and scope defined by the claims in the present invention many changes can be carried out to it,
It changes or even equivalent, but falls in protection scope of the present invention.
Claims (10)
1. a kind of preparation method of low-shrinkage porous silicon nitride ceramic, which is characterized in that it includes the following steps：
The first step：After α-siliconnitride, aluminium oxide, yttrium oxide are mixed, wet mixing, nitrogen drying sieving obtain uniform mixed-powder；
Second step：Deionized water and dispersant A will be added in mixed-powder described in the first step, obtains uniform and stable aqueous-based ceramic
Slurry；
Third walks：Aqueous-based ceramic slurry described in second step is entered by shaking dropping liquid in oil phase, the aqueous-based ceramic slurry is made
Microspheric drop is formed in oil phase；And by refrigerant carry out freezing processing after, be separated by filtration solidification from the oil phase
Ceramic microsphere, using ethyl acetate at -20 DEG C Low-temperature cleaning repeatedly；
4th step：Third is walked the ceramic microsphere to be dried in freeze drier, and the boron nitride buried powder in graphite crucible,
Stirring carries out first time pressureless sintering under nitrogen atmosphere protection, obtains porous silicon nitride microballoon；
5th step：Porous silicon nitride microballoon described in 4th step was subjected to sieve classification；
6th step：Aluminium oxide, yttrium oxide, organic monomer and dispersant B are dissolved in solvent, obtains and stablizes alumina-silica
Yttrium ceramic slurry；
7th step：Porous silicon nitride microballoon after being classified described in 5th step is packed into mold according to a certain ratio, and by the 6th step institute
It is shaken in the alumina-yttria ceramic slurry injection mold stated, removes the extra ceramic slurry in upper layer, solidification 12 as a child took afterwards
Go out, ceramic body is obtained after dry；
8th step：Ceramic body after will be dry described in the 7th step, carries out second of pressureless sintering under nitrogen atmosphere protection, obtains
Obtain porous silicon nitride ceramic.
2. the preparation method of low-shrinkage porous silicon nitride ceramic according to claim 1, which is characterized in that second step institute
It is Sodium Polyacrylate or polyvinyl alcohol to state dispersant A, and the dispersant A accounts for the 0.5%-1% of the mixed-powder quality.
3. the preparation method of low-shrinkage porous silicon nitride ceramic according to claim 2, which is characterized in that second step institute
It is 10-40vol% to state slurry solid content in aqueous-based ceramic slurry.
4. the preparation method of low-shrinkage porous silicon nitride ceramic according to claim 1, which is characterized in that third walks institute
Stating freezing processing condition is, the refrigerant is alcohol, and the cryogenic temperature is -30 DEG C -- 10 DEG C.
5. the preparation method of low-shrinkage porous silicon nitride ceramic according to claim 1, which is characterized in that third walks institute
The condition for stating vibrations dropping liquid is that vibration frequency is 100-1000 times/min, and water dropper aperture is Φ 0.16-0.51mm.
6. the preparation method of low-shrinkage porous silicon nitride ceramic according to claim 1, which is characterized in that the 4th step institute
The process conditions for stating first time pressureless sintering are to be warming up to 500 DEG C with the heating rate of 20 DEG C/min, keep the temperature 1h, then heat up
To 1700 DEG C -1850 DEG C, 2h is kept the temperature；The process conditions of second of pressureless sintering described in 8th step are, with the heating of 20 DEG C/min
Rate is warming up to 500 DEG C, keeps the temperature 1h, then heats to 1500 DEG C -1850 DEG C.
7. the preparation method of low-shrinkage porous silicon nitride ceramic according to claim 1, which is characterized in that the 5th step institute
The condition for stating sieve classification is, is I grades when the grain size of the porous silicon nitride microballoon is less than 100 μm to be, when the nitride porous
It is II grade when the grain size of silicon microballoon is between 100-400 μm, is when the grain size of the porous silicon nitride microballoon is more than 400 μm
III grade.
8. the preparation method of low-shrinkage porous silicon nitride ceramic according to claim 1, which is characterized in that the 6th step institute
It is glycolylurea epoxide resin to state organic monomer, and the 2wt% that the organic monomer quality is the ceramic powders quality；Point
Powder B is polyacrylic acid, and the 0.6wt% that the quality of the dispersant B is the ceramic powders quality.
9. the preparation method of low-shrinkage porous silicon nitride ceramic according to claim 1, which is characterized in that the 7th step institute
State I grade, the quality proportioning of II grade and III grade of the porous silicon nitride microballoon be 2:10:0 or 2:10:10 or 0:3:10.
10. according to a kind of low-shrinkage porous silicon nitride ceramic prepared using claim 1-9 any one of them methods.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN111484351A (en) * | 2019-12-31 | 2020-08-04 | 新兴远建（天津）新材料科技有限公司 | Preparation method and application of lightweight porous ceramic hollow microspheres |
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| CN111196729B (en) * | 2020-01-09 | 2021-08-06 | 中国科学院上海硅酸盐研究所 | Method for preparing porous silicon nitride ceramic by using ultralow-content sintering aid |
| CN111470870A (en) * | 2020-03-26 | 2020-07-31 | 清华大学 | Composite ceramic microsphere and preparation method thereof |
| CN111559918A (en) * | 2020-05-27 | 2020-08-21 | 中国科学院上海硅酸盐研究所 | Method for preparing porous ceramic body by combining microemulsion with freeze drying |
| CN111559918B (en) * | 2020-05-27 | 2021-10-01 | 中国科学院上海硅酸盐研究所 | Method for preparing porous ceramic body by combining microemulsion with freeze drying |
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