CN103145112B - BN-Si2N2O composite ceramic and preparation method thereof - Google Patents

BN-Si2N2O composite ceramic and preparation method thereof Download PDF

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CN103145112B
CN103145112B CN201310106226.5A CN201310106226A CN103145112B CN 103145112 B CN103145112 B CN 103145112B CN 201310106226 A CN201310106226 A CN 201310106226A CN 103145112 B CN103145112 B CN 103145112B
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silicon
composite ceramics
boron nitride
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CN103145112A (en
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贾德昌
田卓
段小明
杨治华
叶书群
周玉
张培峰
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

The invention discloses a BN-Si2N2O composite ceramic and a preparation method thereof, relates to a boron nitride based ceramic material and a preparation method thereof, and aims to solve the problems that an existing method for preparing the boron nitride based composite material is high in preparation cost, low in efficiency and difficult in preparation of large-size boron nitride based ceramic components. The BN-Si2N2O composite ceramic is prepared from amorphous nano silicon dioxide, silicon nitride powder and hexagonal boron nitride powder. The preparation method comprises the following steps of: one, weighing; two, preparing slurry through ball milling; three, drying to prepare powder; four, prepressing and forming; five, performing isostatic cool pressing treatment; and six, performing sintering treatment to obtain the BN-Si2N2O composite ceramic. The preparation method has the advantages that the preparation cost is reduced, the efficiency is improved, and the difficulty for preparing the large-size boron nitride based ceramic components is reduced. The preparation method is mainly used for preparing the BN-Si2N2O composite ceramic.

Description

A kind of BN-Si 2n 2o composite ceramics and preparation method thereof
Technical field
The present invention relates to a kind of boron nitride-base ceramic material and preparation method thereof.
Background technology
Along with making rapid progress of science and technology, the maneuverability of the flight velocity of space vehicle is largely increased, and this has just proposed more harsh requirement to choosing of antenna windows or radome material.High Mach number aircraft requires electromagnetic wave transparent material to have high heat resistance, good thermal shock resistance and stable dielectric properties, but the performance of existing ceramic wave-transmitting material obviously cannot meet service requirements; Although boron nitride-base matrix material prepared by existing employing hot-press method meets the requirement of High Mach number aircraft, but existing employing hot-press method is prepared boron nitride-base matrix material and is had that preparation cost is high and efficiency is low, and adopting hot-press method to prepare in boron nitride-base matrix material preparation process has relatively high expectations and (requires the volume of hot pressing die to be greater than the volume of product hot pressing die, otherwise cannot prepare), be therefore difficult to prepare the problem of large size boron nitride-base ceramic member.
Summary of the invention
The preparation method who the object of the invention is to solve existing boron nitride-base matrix material exists that preparation cost is high, efficiency is low and is difficult to prepare the problem of large size boron nitride-base ceramic member, and a kind of BN-Si is provided 2n 2o composite ceramics and preparation method thereof.
A kind of BN-Si 2n 2o composite ceramics by volume per-cent is made up of 15%～40% amorphous nano silicon-dioxide, 5%～30% alpha-silicon nitride powders and 30%～80% hexagonal boron nitride powder; And the volume ratio of wherein said alpha-silicon nitride powders and amorphous nano silicon oxide is less than 1.
A kind of BN-Si 2n 2the preparation method of O composite ceramics, specifically carries out in accordance with the following steps:
One, weigh: first by volume per-cent measures 15%～40% amorphous nano silicon-dioxide, 5%～30% alpha-silicon nitride powders and 30%～80% hexagonal boron nitride powder, and the volume ratio of described alpha-silicon nitride powders and amorphous nano silicon oxide is less than 1;
Two, ball milling slurrying material: by volume per-cent measures 15%～40% amorphous silicon di-oxide, 5%～30% alpha-silicon nitride powders and 30%～80% hexagonal boron nitride powder is placed in container by step 1, then taking dehydrated alcohol as medium, taking zirconia ball as abrading-ball, in ratio of grinding media to material (10～20): 1 time ball milling 20h～24h, obtains slurry; The mass ratio of the dehydrated alcohol described in step 2 and hexagonal boron nitride powder is (1.5～2.5): 1;
Three, dry powder process: the slurry first step 2 being obtained is dried, and grinds after oven dry again, excessively obtains mixed powder after 200 mesh sieves;
Four, pre-molding: the mixed powder first step 3 being obtained packs in mould, is then under 10MPa～20MPa, to carry out pre-molding at pressure, obtains base substrate;
Five, isostatic cool pressing processing: the base substrate that step 4 is obtained is put into cold isostatic press, is pressurize 60s～120s under 150MPa～250MPa at pressure, obtains crude product to be sintered;
Six, sintering processes: being 1700 DEG C～1900 DEG C in temperature is the crude product sintering 30min～90min to be sintered under the nitrogen protection of 1 standard atmospheric pressure being prepared by step 5 with nitrogen pressure, then cools to room temperature with the furnace, obtains BN-Si 2n 2o composite ceramics.
Advantage of the present invention: one, the present invention utilizes hexagonal boron nitride as body material, adds silicon-dioxide or silicon sol as sintering aid, adds Si 3n 4as third phase, by cold isostatic compaction, pressureless sintering preparation technology, obtains the good electromagnetic wave transparent materials of over-all properties such as a kind of mechanical property and dielectric properties, all can the reach a high temperature service requirements of electromagnetic wave transparent material of its mechanical property and dielectric wave penetrate capability; Two,, in the boron nitride-base wave-penetrating composite material that prepared by the present invention, taking hexagonal boron nitride as body material, silicon-dioxide or silicon sol are sintering aid, Si 3n 4be distributed between blapharoplast as wild phase, play the effect of strengthening, and generate Si as reaction in－situ in the process of sintering 2n 2the forming core core of O; After sintering, the main thing of material is hexagonal boron nitride, Si mutually 2n 2o and a small amount of silicon-dioxide; The Si that reaction generates 2n 2o has excellent hot strength and resistance to oxidation stability, has lower thermal expansivity and good thermal shock resistance, also has excellent dielectric properties simultaneously, is very important structural ceramic material and functional materials; So BN-Si prepared by the present invention 2n 2si in O composite ceramics 2n 2o plays and improves material at high temperature intensity and thermal shock resistance, and improves the effect of high-temperature dielectric wave penetrate capability; Therefore the BN-Si that prepared by the present invention 2n 2o composite ceramics can meet the requirement of High Mach number aircraft; Three, utilization of the present invention cold pressing premolding, through etc. static pressure process after high temperature pressure-free sintering prepare BN-Si by reaction in－situ 2n 2o composite ceramics.In the premolding process of colding pressing low cost graphite or steel mould and etc. the employing of rubber package set in static pressure process, the demand to heat-resistant high-strength graphite jig and high temperature hot pressing apparatus expensive are avoided in hot pressing member process and to problems such as processing requirement complexity, thereby be conducive to improve yield rate and production efficiency, reduce preparation cost.
Brief description of the drawings
Fig. 1 is XRD figure spectrum, and in Fig. 1, A represents to test the BN-Si of a preparation 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 1, B represents to test the BN-Si of two preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 1, C represents to test the BN-Si of three preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 1, D represents to test the BN-Si of four preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 1, E represents to test the BN-Si of five preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 1, ■ represents the diffraction peak of BN, in Fig. 1 ◆ represent Si 2n 2the diffraction peak of O, in Fig. 1, ▽ represents α-Si 3n 4diffraction peak, in Fig. 1, ▼ represents β-Si 3n 4diffraction peak;
Fig. 2 is XRD figure spectrum, and in Fig. 2, A represents to test the BN-Si of six preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 2, B represents to test the BN-Si of seven preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 2, C represents to test the BN-Si of eight preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 2, D represents to test the BN-Si of nine preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 2, E represents to test the BN-Si of ten preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 2, ■ represents the diffraction peak of BN, in Fig. 2 ◆ represent Si 2n 2the diffraction peak of O, in Fig. 2, ▽ represents α-Si 3n 4diffraction peak.
Embodiment
Embodiment one: present embodiment is a kind of BN-Si 2n 2o composite ceramics by volume per-cent is made up of 15%～40% amorphous nano silicon-dioxide, 5%～30% alpha-silicon nitride powders and 30%～80% hexagonal boron nitride powder; And the volume ratio of wherein said alpha-silicon nitride powders and amorphous nano silicon oxide is less than 1.
The volume fraction sum of amorphous nano silicon-dioxide, alpha-silicon nitride powders and hexagonal boron nitride powder described in present embodiment is 100%.
BN-Si described in present embodiment 2n 2in O composite ceramics, contain Si 2n 2o, Si 2n 2o is at BN-Si 2n 2in O composite ceramics, play and improve material at high temperature intensity and thermal shock resistance, and improve the effect of high-temperature dielectric wave penetrate capability; So BN-Si described in present embodiment 2n 2o composite ceramics can meet the requirement of High Mach number aircraft;
Embodiment two: the difference of present embodiment and embodiment one is: described amorphous nano silicon-dioxide is amorphous nano SiO 2 powder or silicon sol; Wherein said amorphous nano SiO 2 powder median size is 0.9 μ m～3 μ m; Amorphous Si O in wherein said silicon sol 2granular mass mark is 30%, and amorphous Si O in silicon sol 2the median size of particle is 9nm～13nm.Other are identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two difference is: the median size of described alpha-silicon nitride powders is 1 μ m～1.5 μ m; The median size of described hexagonal boron nitride powder is 0.9 μ m～1.5 μ m.Other are identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three difference is: described BN-Si 2n 2o composite ceramics by volume per-cent is made up of 20%～30% amorphous nano silicon-dioxide, 10%～20% alpha-silicon nitride powders and 50%～70% hexagonal boron nitride powder.Other are identical with embodiment one to three.
The volume fraction sum of amorphous nano silicon-dioxide, alpha-silicon nitride powders and hexagonal boron nitride powder described in present embodiment is 100%.
Embodiment five: present embodiment is a kind of BN-Si 2n 2the preparation method of O composite ceramics, specifically carries out in accordance with the following steps:
One, weigh: first by volume per-cent measures 15%～40% amorphous nano silicon-dioxide, 5%～30% alpha-silicon nitride powders and 30%～80% hexagonal boron nitride powder, and the volume ratio of described alpha-silicon nitride powders and amorphous nano silicon oxide is less than 1;
Two, ball milling slurrying material: by volume per-cent measures 15%～40% amorphous silicon di-oxide, 5%～30% alpha-silicon nitride powders and 30%～80% hexagonal boron nitride powder is placed in container by step 1, then taking dehydrated alcohol as medium, taking zirconia ball as abrading-ball, in ratio of grinding media to material (10～20): 1 time ball milling 20h～24h, obtains slurry; The mass ratio of the dehydrated alcohol described in step 2 and hexagonal boron nitride powder is (1.5～2.5): 1;
Three, dry powder process: the slurry first step 2 being obtained is dried, and grinds after oven dry again, excessively obtains mixed powder after 200 mesh sieves;
Four, pre-molding: the mixed powder first step 3 being obtained packs in mould, is then under 10MPa～20MPa, to carry out pre-molding at pressure, obtains base substrate;
Five, isostatic cool pressing processing: the base substrate that step 4 is obtained is put into cold isostatic press, is pressurize 60s～120s under 150MPa～250MPa at pressure, obtains crude product to be sintered;
Six, sintering processes: being 1700 DEG C～1900 DEG C in temperature is the crude product sintering 30min～90min to be sintered under the nitrogen protection of 1 standard atmospheric pressure being prepared by step 5 with nitrogen pressure, then cools to room temperature with the furnace, obtains BN-Si 2n 2o composite ceramics.
The volume fraction sum of amorphous nano silicon-dioxide, alpha-silicon nitride powders and the hexagonal boron nitride powder described in present embodiment step 1 is 100%.
Present embodiment utilizes hexagonal boron nitride as body material, adds silicon-dioxide or silicon sol as sintering aid, adds Si 3n 4as third phase, by cold isostatic compaction, pressureless sintering preparation technology, obtains the good electromagnetic wave transparent materials of over-all properties such as a kind of mechanical property and dielectric properties, all can the reach a high temperature service requirements of electromagnetic wave transparent material of its mechanical property and dielectric wave penetrate capability.
In boron nitride-base wave-penetrating composite material prepared by present embodiment, taking hexagonal boron nitride as body material, silicon-dioxide or silicon sol are sintering aid, Si 3n 4be distributed between blapharoplast as wild phase, play the effect of strengthening, and generate Si as reaction in－situ in the process of sintering 2n 2the forming core core of O; After sintering, the main thing of material is hexagonal boron nitride, Si mutually 2n 2o and a small amount of silicon-dioxide; The Si that reaction generates 2n 2o has excellent hot strength and resistance to oxidation stability, has lower thermal expansivity and good thermal shock resistance, also has excellent dielectric properties simultaneously, is very important structural ceramic material and functional materials; So BN-Si prepared by present embodiment 2n 2si in O composite ceramics 2n 2o plays and improves material at high temperature intensity and thermal shock resistance, and improves the effect of high-temperature dielectric wave penetrate capability; Therefore the BN-Si that prepared by present embodiment 2n 2o composite ceramics can meet the requirement of High Mach number aircraft.
Present embodiment utilization cold pressing premolding, through etc. static pressure process after high temperature pressure-free sintering prepare BN-Si by reaction in－situ 2n 2o composite ceramics.In the premolding process of colding pressing low cost graphite or steel mould and etc. the employing of rubber package set in static pressure process, the demand to heat-resistant high-strength graphite jig and high temperature hot pressing apparatus expensive are avoided in hot pressing member process and to problems such as processing requirement complexity, thereby be conducive to improve yield rate and production efficiency, reduce preparation cost.
Embodiment six: the difference of present embodiment and embodiment five is: the amorphous nano silicon-dioxide described in step 1 is amorphous nano SiO 2 powder or silicon sol; Wherein said amorphous nano SiO 2 powder median size is 0.9 μ m～3 μ m; In wherein said silicon sol, amorphous Si 02 granular mass mark is 30%, and amorphous Si O in silicon sol 2the median size of particle is 9nm～13nm.Other are identical with embodiment five.
Embodiment seven: one of present embodiment and embodiment five or six difference is: the median size of alpha-silicon nitride powders described in step 1 is 1 μ m～1.5 μ m; The median size of hexagonal boron nitride powder described in step 1 is 0.9 μ m～1.5 μ m.Other are identical with embodiment five or six.
Embodiment eight: one of present embodiment and embodiment five to seven difference is: in step 1, first by volume per-cent measures 20%～30% amorphous nano silicon-dioxide, 10%～20% alpha-silicon nitride powders and 50%～70% hexagonal boron nitride powder.Other are identical with embodiment five to seven.
The volume fraction sum of amorphous nano silicon-dioxide, alpha-silicon nitride powders and hexagonal boron nitride powder described in present embodiment is 100%.
Embodiment nine: one of present embodiment and embodiment five to eight difference is: the base substrate in step 5, step 4 being obtained is put into cold isostatic press, is pressurize 90～120s under 200MPa～250MPa at pressure, obtains crude product to be sintered.Other are identical with embodiment five to eight.
Embodiment ten: one of present embodiment and embodiment five to nine difference is: being 1750 DEG C～1850 DEG C in temperature in step 6 is the crude product sintering 45min～75min to be sintered under the nitrogen protection of 1 standard atmospheric pressure being prepared by step 5 with nitrogen pressure; then cool to room temperature with the furnace, obtain BN-Si 2n 2o composite ceramics.Other are identical with embodiment five to nine.
Adopt following verification experimental verification effect of the present invention:
Test one: a kind of BN-Si 2n 2the preparation method of O composite ceramics, specifically carries out in accordance with the following steps:
One, weigh: first by volume per-cent measures 30% amorphous nano silicon-dioxide, 5% alpha-silicon nitride powders and 65% hexagonal boron nitride powder;
Two, ball milling slurrying material: by volume per-cent measures 30% amorphous nano silicon-dioxide, 5% alpha-silicon nitride powders and 65% hexagonal boron nitride powder is placed in container by step 1, then taking dehydrated alcohol as medium, taking zirconia ball as abrading-ball, ball milling 24h under ratio of grinding media to material 15:1, obtains slurry; The mass ratio of the dehydrated alcohol described in step 2 and hexagonal boron nitride powder is 2:1;
Three, dry powder process: the slurry first step 2 being obtained is dried, and grinds after oven dry again, excessively obtains mixed powder after 200 mesh sieves;
Four, pre-molding: the mixed powder first step 3 being obtained packs in mould, is then under 20MPa, to carry out pre-molding at pressure, obtains base substrate;
Five, isostatic cool pressing processing: the base substrate that step 4 is obtained is put into cold isostatic press, is pressurize 90s under 200MPa at pressure, obtains crude product to be sintered;
Six, sintering processes: being 1800 DEG C in temperature is the crude product sintering 60min to be sintered under the nitrogen protection of 1 standard atmospheric pressure being prepared by step 5 with nitrogen pressure, then cools to room temperature with the furnace, obtains BN-Si 2n 2o composite ceramics.
Amorphous nano silicon-dioxide described in this testing sequence one is amorphous nano SiO 2 powder; Wherein said amorphous nano SiO 2 powder median size is 0.9 μ m～3 μ m.
The median size of alpha-silicon nitride powders described in this testing sequence one is 1 μ m～1.5 μ m.
The median size of hexagonal boron nitride powder described in this testing sequence one is 0.9 μ m～1.5 μ m.
The BN-Si of this test preparation 2n 2the flexural strength of O composite ceramics (being labeled as BS5 pottery) adopts three-point bending method to test, fracture toughness property adopts monolateral breach beam three-point bending method test, and dielectric properties adopt high-q cavity method to carry out dielectric complex permittivity test under 18GHz～40GHz frequency; The flexural strength, fracture toughness property and the dielectric properties data that record are in table 1.
Table 1
Material Flexural strength/MPa Specific inductivity (21GHz) Loss tangent (21GHz)
BS5 pottery 24.2±1.1 2.93 0.0048
Test two: this test with the difference of embodiment one is: in step 1, first by volume per-cent measures 30% amorphous nano silicon-dioxide, 10% alpha-silicon nitride powders and 60% hexagonal boron nitride powder.Other are identical with test one.
The BN-Si of this test preparation 2n 2the flexural strength of O composite ceramics (being labeled as BS10 pottery) adopts three-point bending method to test, fracture toughness property adopts monolateral breach beam three-point bending method test, and dielectric properties adopt high-q cavity method to carry out dielectric complex permittivity test under 18GHz～40GHz frequency; The flexural strength, fracture toughness property and the dielectric properties data that record are in table 2.
Table 2
Material Flexural strength/MPa Specific inductivity (21GHz) Loss tangent (21GHz)
BS10 pottery 26.9±2.5 3.01 0.0044
Test three: this test with the difference of embodiment one is: in step 1, first by volume per-cent measures 30% amorphous nano silicon-dioxide, 15% alpha-silicon nitride powders and 55% hexagonal boron nitride powder.Other are identical with test one.
The BN-Si of this test preparation 2n 2the flexural strength of O composite ceramics (being labeled as BS15 pottery) adopts three-point bending method to test, fracture toughness property adopts monolateral breach beam three-point bending method test, and dielectric properties adopt high-q cavity method to carry out dielectric complex permittivity test under 18GHz～40GHz frequency; The flexural strength, fracture toughness property and the dielectric properties data that record are in table 3.
Table 3
Material Flexural strength/MPa Specific inductivity (21GHz) Loss tangent (21GHz)
BS15 pottery 52.5±3.3 3.11 0.0048
Test four: this test with the difference of embodiment one is: in step 1, first by volume per-cent measures 30% amorphous nano silicon-dioxide, 20% alpha-silicon nitride powders and 50% hexagonal boron nitride powder.Other are identical with test one.
The BN-Si of this test preparation 2n 2the flexural strength of O composite ceramics (being labeled as BS20 pottery) adopts three-point bending method to test, fracture toughness property adopts monolateral breach beam three-point bending method test, and dielectric properties adopt high-q cavity method to carry out dielectric complex permittivity test under 18GHz～40GHz frequency; The flexural strength, fracture toughness property and the dielectric properties data that record are in table 4.
Table 4
Material Flexural strength/MPa Specific inductivity (21GHz) Loss tangent (21GHz)
BS20 pottery 36.8±1.8 3.31 0.0051
Test five: this test with the difference of embodiment one is: in step 1, first by volume per-cent measures 30% amorphous nano silicon-dioxide, 30% alpha-silicon nitride powders and 40% hexagonal boron nitride powder.Other are identical with test one.
The BN-Si of this test preparation 2n 2the flexural strength of O composite ceramics (being labeled as BS30 pottery) adopts three-point bending method to test, fracture toughness property adopts monolateral breach beam three-point bending method test, and dielectric properties adopt high-q cavity method to carry out dielectric complex permittivity test under 18GHz～40GHz frequency; The flexural strength, fracture toughness property and the dielectric properties data that record are in table 5.
Table 5
Material Flexural strength/MPa Specific inductivity (21GHz) Loss tangent (21GHz)
BS30 pottery 35.9±3.6 3.16 0.0053
Adopt X-ray diffractometer to detect the BN-Si of test one to test five preparations 2n 2o composite ceramics, as shown in Figure 1, Fig. 1 is XRD figure spectrum to detected result, in Fig. 1, A represents to test the BN-Si of a preparation 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 1, B represents to test the BN-Si of two preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 1, C represents to test the BN-Si of three preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 1, D represents to test the BN-Si of four preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 1, E represents to test the BN-Si of five preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 1 ■represent the diffraction peak of BN, in Fig. 1 ◆ represent Si 2n 2the diffraction peak of O, in Fig. 1, ▽ represents α-Si 3n 4diffraction peak, in Fig. 1, ▼ represents β-Si 3n 4diffraction peak; As can be seen from Figure 1, in the time that amorphous silicon di-oxide is introduced with powder type, along with Si 3n 4introducing, after high temperature pressure-free sintering, in matrix material, have Si 2n 2the generation of O.
Test six: this test with the difference of embodiment one is: the amorphous nano silicon-dioxide described in step 1 is silicon sol; Amorphous Si 0 in wherein said silicon sol 2granular mass mark is 30%, and amorphous Si 0 in silicon sol 2the median size of particle is 9nm～13nm.。Other are identical with test one.
The BN-Si of this test preparation 2n 2the flexural strength of O composite ceramics (being labeled as BSR5 pottery) adopts three-point bending method to test, fracture toughness property adopts monolateral breach beam three-point bending method test, and dielectric properties adopt high-q cavity method to carry out dielectric complex permittivity test under 18GHz～40GHz frequency; The flexural strength, fracture toughness property and the dielectric properties data that record are in table 6.
Table 6
Material Flexural strength/MPa Specific inductivity (21GHz) Loss tangent (21GHz)
BSR5 pottery 14.5±2.0 2.90 0.0032
Test seven: this test with the difference of embodiment six is: in step 1, first by volume per-cent measures 30% amorphous nano silicon-dioxide, 10% alpha-silicon nitride powders and 60% hexagonal boron nitride powder.Other are identical with test six.
The BN-Si of this test preparation 2n 2the flexural strength of O composite ceramics (being labeled as BSR10 pottery) adopts three-point bending method to test, fracture toughness property adopts monolateral breach beam three-point bending method test, and dielectric properties adopt high-q cavity method to carry out dielectric complex permittivity test under 18GHz～40GHz frequency; The flexural strength, fracture toughness property and the dielectric properties data that record are in table 7.
Table 7
Material Flexural strength/MPa Specific inductivity (21GHz) Loss tangent (21GHz)
BSR10 pottery 23.2±5.2 2.90 0.0040
Test eight: this test with the difference of embodiment six is: in step 1, first by volume per-cent measures 30% amorphous nano silicon-dioxide, 15% alpha-silicon nitride powders and 55% hexagonal boron nitride powder.Other are identical with test six.
The BN-Si of this test preparation 2n 2the flexural strength of O composite ceramics (being labeled as BSR15 pottery) adopts three-point bending method to test, fracture toughness property adopts monolateral breach beam three-point bending method test, and dielectric properties adopt high-q cavity method to carry out dielectric complex permittivity test under 18GHz～40GHz frequency; The flexural strength, fracture toughness property and the dielectric properties data that record are in table 8.
Table 8
Material Flexural strength/MPa Specific inductivity (21GHz) Loss tangent (21GHz)
BSR15 pottery 21.1±2.3 3.33 0.0040
Test nine: this test with the difference of embodiment six is: in step 1, first by volume per-cent measures 30% amorphous nano silicon-dioxide, 20% alpha-silicon nitride powders and 50% hexagonal boron nitride powder.Other are identical with test six.
The BN-Si of this test preparation 2n 2the flexural strength of O composite ceramics (being labeled as BSR20 pottery) adopts three-point bending method to test, fracture toughness property adopts monolateral breach beam three-point bending method test, and dielectric properties adopt high-q cavity method to carry out dielectric complex permittivity test under 18GHz～40GHz frequency; The flexural strength, fracture toughness property and the dielectric properties data that record are in table 9.
Table 9
Material Flexural strength/MPa Specific inductivity (21GHz) Loss tangent (21GHz)
BSR20 25.9±1.9 3.24 0.0038
Test ten: this test with the difference of embodiment six is: in step 1, first by volume per-cent measures 30% amorphous nano silicon-dioxide, 30% alpha-silicon nitride powders and 40% hexagonal boron nitride powder.Other are identical with test six.
The BN-Si of this test preparation 2n 2the flexural strength of O composite ceramics (being labeled as BSR30 pottery) adopts three-point bending method to test, fracture toughness property adopts monolateral breach beam three-point bending method test, and dielectric properties adopt high-q cavity method to carry out dielectric complex permittivity test under 18GHz～40GHz frequency; The flexural strength, fracture toughness property and the dielectric properties data that record are in table 10.
Table 10
Material Flexural strength/MPa Specific inductivity (21GHz) Loss tangent (21GHz)
BSR30 33.2±1.2 3.19 0.0052
Adopt X-ray diffractometer to detect the BN-Si of test six to test ten preparations 2n 2o composite ceramics, as shown in Figure 2, Fig. 2 is XRD figure spectrum to detected result, in Fig. 2, A represents to test the BN-Si of six preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 2, B represents to test the BN-Si of seven preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 2, C represents to test the BN-Si of eight preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 2, D represents to test the BN-Si of nine preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 2, E represents to test the BN-Si of ten preparations 2n 2the XRD figure spectrum of O composite ceramics, in Fig. 2 ■represent the diffraction peak of BN, in Fig. 2 ◆ represent Si 2n 2the diffraction peak of O, in Fig. 2, ▽ represents α-Si 3n 4diffraction peak; As can be seen from Figure 2, in the time that amorphous silicon di-oxide is introduced with silicon sol form, along with Si 3n 4introducing, after high temperature pressure-free sintering, in matrix material, have Si 2n 2the generation of O.

Claims (10)

1. a BN-Si 2n 2o composite ceramics, is characterized in that BN-Si 2n 2o composite ceramics by volume per-cent is made up of 15%～40% amorphous nano silicon-dioxide, 5%～30% alpha-silicon nitride powders and 30%～80% hexagonal boron nitride powder; And the volume ratio of wherein said alpha-silicon nitride powders and amorphous nano silicon oxide is less than 1;
BN-Si 2n 2o composite ceramics is prepared according to the following steps:
One, weigh: first by volume per-cent measures 15%～40% amorphous nano silicon-dioxide, 5%～30% alpha-silicon nitride powders and 30%～80% hexagonal boron nitride powder, and the volume ratio of described alpha-silicon nitride powders and amorphous nano silicon oxide is less than 1;
Two, ball milling slurrying material: by volume per-cent measures 15%～40% amorphous silicon di-oxide, 5%～30% alpha-silicon nitride powders and 30%～80% hexagonal boron nitride powder is placed in container by step 1, then taking dehydrated alcohol as medium, taking zirconia ball as abrading-ball, in ratio of grinding media to material (10～20): 1 time ball milling 20h～24h, obtains slurry; The mass ratio of the dehydrated alcohol described in step 2 and hexagonal boron nitride powder is (1.5～2.5): 1;
Three, dry powder process: the slurry first step 2 being obtained is dried, and grinds after oven dry again, excessively obtains mixed powder after 200 mesh sieves;
Four, pre-molding: the mixed powder first step 3 being obtained packs in mould, is then under 10MPa～20MPa, to carry out pre-molding at pressure, obtains base substrate;
Five, isostatic cool pressing processing: the base substrate that step 4 is obtained is put into cold isostatic press, is pressurize 60s～120s under 150MPa～250MPa at pressure, obtains crude product to be sintered;
Six, sintering processes: being 1700 DEG C～1900 DEG C in temperature is the crude product sintering 30min～90min to be sintered under the nitrogen protection of 1 standard atmospheric pressure being prepared by step 5 with nitrogen pressure, then cools to room temperature with the furnace, obtains BN-Si 2n 2o composite ceramics.
2. a kind of BN-Si according to claim 1 2n 2o composite ceramics, is characterized in that described amorphous nano silicon-dioxide is silicon sol; Amorphous Si O in wherein said silicon sol 2granular mass mark is 30%, and amorphous Si O in silicon sol 2the median size of particle is 9nm～13nm.
3. a kind of BN-Si according to claim 1 2n 2o composite ceramics, is characterized in that the median size of described described alpha-silicon nitride powders is 1 μ m～1.5 μ m; The median size of described hexagonal boron nitride powder is 0.9 μ m～1.5 μ m.
4. according to a kind of BN-Si described in claim 1,2 or 3 2n 2o composite ceramics, is characterized in that described BN-Si 2n 2o composite ceramics by volume per-cent is made up of 20%～30% amorphous nano silicon-dioxide, 10%～20% alpha-silicon nitride powders and 50%～70% hexagonal boron nitride powder.
5. a kind of BN-Si as claimed in claim 1 2n 2the preparation method of O composite ceramics, is characterized in that BN-Si 2n 2the preparation method of O composite ceramics carries out in accordance with the following steps:
One, weigh: first by volume per-cent measures 15%～40% amorphous nano silicon-dioxide, 5%～30% alpha-silicon nitride powders and 30%～80% hexagonal boron nitride powder, and the volume ratio of described alpha-silicon nitride powders and amorphous nano silicon oxide is less than 1;
Two, ball milling slurrying material: by volume per-cent measures 15%～40% amorphous silicon di-oxide, 5%～30% alpha-silicon nitride powders and 30%～80% hexagonal boron nitride powder is placed in container by step 1, then taking dehydrated alcohol as medium, taking zirconia ball as abrading-ball, in ratio of grinding media to material (10～20): 1 time ball milling 20h～24h, obtains slurry; The mass ratio of the dehydrated alcohol described in step 2 and hexagonal boron nitride powder is (1.5～2.5): 1;
Three, dry powder process: the slurry first step 2 being obtained is dried, and grinds after oven dry again, excessively obtains mixed powder after 200 mesh sieves;
Four, pre-molding: the mixed powder first step 3 being obtained packs in mould, is then under 10MPa～20MPa, to carry out pre-molding at pressure, obtains base substrate;
Five, isostatic cool pressing processing: the base substrate that step 4 is obtained is put into cold isostatic press, is pressurize 60s～120s under 150MPa～250MPa at pressure, obtains crude product to be sintered;
Six, sintering processes: being 1700 DEG C～1900 DEG C in temperature is the crude product sintering 30min～90min to be sintered under the nitrogen protection of 1 standard atmospheric pressure being prepared by step 5 with nitrogen pressure, then cools to room temperature with the furnace, obtains BN-Si 2n 2o composite ceramics.
6. a kind of BN-Si according to claim 5 2n 2the preparation method of O composite ceramics, is characterized in that the amorphous nano silicon-dioxide described in step 1 is silicon sol; Amorphous Si O in wherein said silicon sol 2granular mass mark is 30%, and amorphous Si O in silicon sol 2the median size of particle is 9nm～13nm.
7. a kind of BN-Si according to claim 5 2n 2the preparation method of O composite ceramics, the median size that it is characterized in that alpha-silicon nitride powders described in step 1 is 1 μ m～1.5 μ m; The median size of hexagonal boron nitride powder described in step 1 is 0.9 μ m～1.5 μ m.
8. according to a kind of BN-Si described in claim 5,6 or 7 2n 2the preparation method of O composite ceramics, is characterized in that in step 1 that first by volume per-cent measures 20%～30% amorphous nano silicon-dioxide, 10%～20% alpha-silicon nitride powders and 50%～70% hexagonal boron nitride powder.
9. a kind of BN-Si according to claim 8 2n 2the preparation method of O composite ceramics, is characterized in that the base substrate in step 5, step 4 being obtained puts into cold isostatic press, is pressurize 90～120s under 200MPa～250MPa at pressure, obtains crude product to be sintered.
10. a kind of BN-Si according to claim 8 2n 2the preparation method of O composite ceramics; it is characterized in that in step 6, being 1750 DEG C～1850 DEG C in temperature is the crude product sintering 45min～75min to be sintered under the nitrogen protection of 1 standard atmospheric pressure being prepared by step 5 with nitrogen pressure; then cool to room temperature with the furnace, obtain BN-Si 2n 2o composite ceramics.
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