CN101555156B - Boron nitride crystal whisker/silicon nitride ceramic composite material and preparation method thereof - Google Patents
Boron nitride crystal whisker/silicon nitride ceramic composite material and preparation method thereof Download PDFInfo
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- CN101555156B CN101555156B CN2009100152573A CN200910015257A CN101555156B CN 101555156 B CN101555156 B CN 101555156B CN 2009100152573 A CN2009100152573 A CN 2009100152573A CN 200910015257 A CN200910015257 A CN 200910015257A CN 101555156 B CN101555156 B CN 101555156B
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Abstract
The invention relates to a boron nitride crystal whisker/silicon nitride ceramic composite material and a preparation method thereof, which belong to the technical field of the new material. The boronnitride crystal whisker, the silicon nitride powder, the sintering aid and other additives are mixed by ball milling to obtain ceramic slurry; the molding by slip casting is adopted, or the slurry is dried and prepared into power and then is molded by an isostatic cool pressing process; and the molded blank is dried and then is sintered in a nitrogen atmosphere at a pressure of 5 MPa to 8 MPa wit h a temperature preserved at 1700 DEG C to 1850 DEG C for one to three hours to obtain the boron nitride crystal whisker/silicon nitride ceramic composite material. The composite material has excellent mechanical property, good diectric property, good temperature resistance and ablation resistance and can be used for preparing the high-performance blister; and meanwhile, the preparation method of the material is simple and feasible and is suitable for the batch production.
Description
Technical field
The present invention relates to a kind of boron nitride crystal whisker/silicon nitride ceramic composite material and preparation method thereof, belong to new material technology field.
Background technology
Radome is the important component part of attacking weapon warhead structure; it is again the barrier that the protection antenna system is not subjected to the abominable pneumatic environmental influence that caused by high-speed flight; be a kind ofly to integrate ripple, solar heat protection, carrying and multi-functional parts such as against corrosion, so radome material to satisfy requirements such as dielectric properties, mechanical property, three anti-, life-span, manufacturability and weight.Silicon nitride (Si
3N
4) pottery has excellent mechanical property and high thermostability and have lower specific inductivity and dielectric loss.As radome material, silicon nitride had both had the advantage of alumina-ceramic, had the anti-ablation property not worse than fused quartz again, can stand greater than the thermal shocking under the 5 Mach number flying conditions.Boron nitride (BN) pottery has than better thermostability of silicon nitride ceramics and lower specific inductivity, dielectric loss, and has the fabulous thermal characteristics and the stability of electrical property in very wide temperature range.But the lower and easy moisture absorption of boron nitride intensity can not be made radome separately.Utilize boron nitride, silicon nitride advantage separately can prepare the radome matrix material of excellent combination property.
About boron nitride/silicon nitride composite material and existing document of preparation technology and patent report.It is introduced that France successfully adopts silicon nitride/boron nitride composite to prepare radome.Chinese patent application CN1569743A (200410023952.1) discloses " Silicon Nitride-Boron Nitride-Silica wave-transparent material and its preparation method ", described electromagnetic wave transparent material is characterised in that temperature tolerance, ablation resistance are good, and have good mechanical performance and dielectric properties, saturating ripple rate height.Zhang Weiru etc., silicate circular, 2003 (3): 3-6, the Si that adopted the gas pressure sintering prepared
3N
4-BN based composite ceramic material studies show that: the room temperature bending strength that contains the 30%BN matrix material is 160MPa, and Young's modulus is 99GPa, and specific inductivity is about 4.0.Wang Siqing etc., National University of Defense technology's journal, 2006,28 (2): 44-47, with Si powder, BN powder, SiO
2Powder is a main raw material, adopts reaction sintering to prepare Si
3N
4The base complex phase ceramic material, the result shows: Si, BN and SiO in raw material
2Be respectively 55%, 30% and at 10% o'clock, the strength of materials is 96.7MPa, and fracture toughness property can reach 1.80MPam
1/2, material has excellent dielectric properties and heat physical properties simultaneously.Zhang Qiang etc., silicate journal, 2007,35 (3): 337-341 is a raw material with silica flour, hexagonal boron nitride, adopts the synthetic gas-solid reaction method of burning, and original position generates silicon nitride/boron nitride complex phase ceramic, and the result shows: Si
3N
4In/h-BN the complex phase ceramic with column β-Si
3N
4Be principal phase, β-Si
3N
4Intergranule is a needle-like h-BN phase.The material bending strength is 122MPa when the h-BN phase content is 15%.
Though above-mentioned research by boron nitride particle and the compound dielectric properties that improve silicon nitride to a certain extent of silicon nitride, has reduced the mechanical property of silicon nitride.Be added in the silicon nitride as second with boron nitride crystal whisker, utilize the constructional feature of boron nitride crystal whisker to prepare and promptly have, have the boron nitride crystal whisker/silicon nitride ceramic composite material of higher mechanical property, temperature tolerance and ablation resistance again than low-k and dielectric loss.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of boron nitride crystal whisker/silicon nitride ceramic composite material with good mechanical property, dielectric properties, heat resistance and ablation resistance; Its simple, as to be fit to batch process preparation method is provided simultaneously.
Technical scheme of the present invention is as follows:
A kind of boron nitride crystal whisker/silicon nitride ceramic composite material, raw material is as follows: silicon nitride 60～90wt.%, boron nitride crystal whisker 5～35wt.% and sintering aid 3～10wt.%.
Described silicon nitride is high-purity submicron particles, and α phase silicon nitride content is not less than 93%, and contents of free si is not more than 0.3%, and particle diameter is 0.4～0.6 micron.
Described boron nitride crystal whisker is the long column shape monocrystalline, length-to-diameter ratio 40～100,1～3 micron of diameter.
Described sintering aid is selected one or more of yttrium oxide, silicon-dioxide, aluminum oxide, yttrium aluminum garnet for use.
Above-mentioned boron nitride crystal whisker/silicon nitride ceramic composite material adopts following method to make:
Raw material boron nitride crystal whisker, silicon nitride powder and sintering aid are mixed; Add the moulding additive of raw material gross weight 0.5-1.2%, ball milling is made ceramic size, directly adopts injection forming, perhaps will adopt the isostatic pressing process moulding after slurry drying, the powder process; Molding blank after drying, sintering under 1700～1850 ℃, 1～3 hour condition of insulation under 5～8MPa nitrogen atmosphere pressure.
The said injection forming of the present invention, isostatic pressing process moulding all get final product by state of the art.
Described boron nitride crystal whisker can be 200910020661.X by number of patent application, and name is called a kind of patent document preparation of preparation method of boron nitride crystal whisker.
The preparation method of boron nitride crystal whisker/silicon nitride ceramic composite material of the present invention, step is as follows:
(1) with the weighing mixing in proportion of boron nitride crystal whisker, silicon nitride, sintering aid, add the moulding additive of raw material gross weight 0.5-1.2%, ball milling mixes 1～2h and makes the ceramic size that mixes;
(2) ceramic size is adopted the gypsum mold injection forming after treatment, perhaps slurry is adopted isostatic pressing again by obtaining the boron nitride crystal whisker/silicon nitride composite granule after dry, the powder process;
(3) the gained molding blank is 5～8MPa at nitrogen atmosphere pressure after drying, and sintering, insulation are 1～3 hour under 1700～1850 ℃ of conditions, then naturally cool to room temperature with stove, make boron nitride crystal whisker/silicon nitride ceramic composite material.
The described isostatic pressing pressure of step (2) is 100～150MPa.
When step (2) adopted injection forming, used moulding additive was: water glass and yellow soda ash, yellow soda ash and carboxymethyl cellulose (CMC) or yellow soda ash and Sudan Gum-arabic.Addition is preferably the 0.6-1.0% of raw material gross weight.
When step (2) adopted isostatic pressing, used moulding additive was: polyvinyl alcohol or xylogen.Addition is preferably the 0.5-0.8% of raw material gross weight.
Step (1) ball milling gets final product by art technology.Need add water during ball milling and be controlled at generally that to make the slurry solid content be 40～70wt%.
The performance index of boron nitride crystal whisker/silicon nitride ceramic composite material of the present invention are: specific inductivity: 3～4.5; Tangent of the dielectric loss angle: 2～4 * 10
-3Room temperature flexural strength: 120～300MPa; Use temperature: 1400～1600 ℃.
The boron nitride crystal whisker/silicon nitride ceramic composite material excellent combination property of the present invention's preparation can be used for the preparation of high-performance blister.
Compared with prior art, characteristics of the present invention and excellent results are as follows:
1, the present invention utilizes boron nitride crystal whisker superior dielectric properties and structural performance, with the compound boron nitride crystal whisker/silicon nitride ceramic composite material of preparing excellent combination property of silicon nitride.
2, technology of the present invention simply is easy to realize suitability for industrialized production.
Embodiment
The invention will be further described below in conjunction with embodiment, but be not limited thereto.
Embodiment 1:
1, with the boron nitride crystal whisker of 10wt.%, the silicon nitride of 85wt.% and the sintering aid yttrium oxide of 5wt.%, and the additives polyvinyl alcohol of raw material gross weight 0.6% (mean polymerisation degree 1750 ± 50), add water for ball milling and mix 2h, the slurry that obtains mixing.The slurry solid content is 60wt%;
2, step 1 is made slurry drying, fragmentation, sieve, obtain mixed powder.
3, step 2 is made mixed powder and put into rubber mold, isostatic pressing under the 100MPa pressure.
4, with the body drying of step 3 moulding, putting into the gas pressure sintering stove then, is that 6MPa, temperature are 2 hours sintering of insulation under 1800 ℃ of conditions at nitrogen atmosphere pressure, then naturally cools to room temperature with stove, obtains boron nitride crystal whisker/silicon nitride ceramic composite material.
Embodiment 2:
1, with the boron nitride crystal whisker of 20wt.%, the silicon nitride of 77wt.% and the sintering aid silicon oxide of 3wt.%, and the additive xylogen (molecular weight 1 * 10 of raw material gross weight 0.7%
4～4 * 10
4), adding water for ball milling and mix 1h, the slurry that obtains mixing, slurry solid content are 55wt%;
2, step 1 is made slurry drying, fragmentation, sieve, obtain mixed powder.
3, step 2 is made mixed powder and put into rubber mold, isostatic pressing under the 100MPa pressure.
4, with the body drying of step 3 moulding, putting into the gas pressure sintering stove then, is that 7MPa, temperature are 2 hours sintering of insulation under 1700 ℃ of conditions at nitrogen atmosphere pressure, then naturally cools to room temperature with stove, obtains boron nitride crystal whisker/silicon nitride ceramic composite material.
Embodiment 3:
1, with the boron nitride crystal whisker of 5wt.%, the silicon nitride of 87wt.% and the sintering aid yttrium aluminum garnet of 8wt.%, and the additives polyvinyl alcohol of raw material gross weight 0.8% (mean polymerisation degree 1750 ± 50), add water for ball milling and mix 2h, the slurry that obtains mixing, slurry solid content are 65wt%;
2, step 1 is made slurry drying, fragmentation, sieve, obtain mixed powder.
3, step 2 is made mixed powder and put into rubber mold, isostatic pressing under the 120MPa pressure.
4, with the body drying of step 3 moulding, putting into the gas pressure sintering stove then, is that 8MPa, temperature are 3 hours sintering of insulation under 1850 ℃ of conditions at nitrogen atmosphere pressure, then naturally cools to room temperature with stove, obtains boron nitride crystal whisker/silicon nitride ceramic composite material.
Embodiment 4:
1, with 20% boron nitride crystal whisker, 72% silicon nitride and 8% sintering aid yttrium oxide, and based on 0.2% water glass and 0.6% yellow soda ash of raw material gross weight, add water for ball milling and mix 2h, the slurry that obtains mixing, slurry solid content are 60wt%;
2, the slurry with step 1 preparation slowly injects the gypsum mold moulding, and the demoulding then, drying obtain base substrate.
3, step 2 being made base substrate is under the condition of 6MPa at nitrogen atmosphere pressure, and sintering temperature is that 1750 ℃, insulation carried out sintering in 3 hours, then naturally cools to room temperature with stove, finally prepares boron nitride crystal whisker/silicon nitride ceramic composite material.
Embodiment 5:
1, with 35% boron nitride crystal whisker, 60% silicon nitride and 5% sintering aid yttrium aluminum garnet, and based on 0.2% yellow soda ash and the 0.8% Sudan Gum-arabic (molecular weight 2.5 * 10 of raw material gross weight
5), add water for ball milling and mix 2h, the slurry that obtains mixing, slurry solid content 50wt%;
2, the slurry with step 1 preparation slowly injects the gypsum mold moulding, and the demoulding then, drying obtain base substrate.
3, step 2 being made base substrate is under the condition of 8MPa at nitrogen atmosphere pressure, and sintering temperature is that 1800 ℃, insulation carried out sintering in 1 hour, then naturally cools to room temperature with stove, finally prepares boron nitride crystal whisker/silicon nitride ceramic composite material.
Relevant performance data of the boron nitride crystal whisker/silicon nitride ceramic composite material of above embodiment 1-5 such as following table:
Claims (3)
1. a boron nitride crystal whisker/silicon nitride ceramic composite material is characterized in that raw material is as follows: silicon nitride 60～90wt.%, boron nitride crystal whisker 5～35wt.% and sintering aid 3～10wt.%;
Described silicon nitride is high-purity submicron particles, and α phase silicon nitride content is not less than 93%, and contents of free si is not more than 0.3%, and particle diameter is 0.4～0.6 micron;
Described boron nitride crystal whisker is the long column shape monocrystalline, length-to-diameter ratio 40～100,1～3 micron of diameter;
Described sintering aid is selected one or more of yttrium oxide, silicon-dioxide, aluminum oxide, yttrium aluminum garnet for use;
Be to make by the following method:
Raw material boron nitride crystal whisker, silicon nitride powder and sintering aid are mixed; Add the moulding additive of raw material gross weight 0.5-1.2%, ball milling makes ceramic size, directly adopts injection forming, perhaps will adopt the isostatic pressing process moulding after slurry drying, the powder process; Molding blank after drying, sintering under 1700～1850 ℃, 1～3 hour condition of insulation under 5～8MPa nitrogen atmosphere pressure;
When adopting injection forming, used moulding additive is: water glass and yellow soda ash, yellow soda ash and carboxymethyl cellulose or yellow soda ash and Sudan Gum-arabic; When adopting isostatic pressing, used moulding additive is: polyvinyl alcohol or xylogen.
2. the preparation method of the described boron nitride crystal whisker/silicon nitride ceramic composite material of claim 1, step is as follows:
(1) with the weighing mixing in proportion of boron nitride crystal whisker, silicon nitride, sintering aid, add the moulding additive of raw material gross weight 0.5-1.2%, ball milling 1～2h makes the ceramic size that mixes;
(2) ceramic size is adopted the gypsum mold injection forming after treatment, perhaps slurry is adopted isostatic pressing again by obtaining the boron nitride crystal whisker/silicon nitride composite granule after dry, the powder process;
(3) the gained molding blank is 5～8MPa at nitrogen atmosphere pressure after drying, and sintering, insulation are 1～3 hour under 1700～1850 ℃ of conditions, then naturally cool to room temperature with stove, make boron nitride crystal whisker/silicon nitride ceramic composite material.
3. the preparation method of boron nitride crystal whisker/silicon nitride ceramic composite material as claimed in claim 2 is characterized in that the described isostatic pressing pressure of step (2) is 100～150MPa.
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| CN101555156B true CN101555156B (en) | 2011-11-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85104097A (en) * | 1985-05-24 | 1986-11-19 | 中国科学院上海硅酸盐研究所 | Boron nitride fiber reinforced reactively sintered silicon nitride ceramics |
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Non-Patent Citations (1)
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