CN109369194A - A kind of low dielectric, High Strength Properties Porous Silicon Nitride Ceramics and preparation method thereof - Google Patents

A kind of low dielectric, High Strength Properties Porous Silicon Nitride Ceramics and preparation method thereof Download PDF

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CN109369194A
CN109369194A CN201811331959.8A CN201811331959A CN109369194A CN 109369194 A CN109369194 A CN 109369194A CN 201811331959 A CN201811331959 A CN 201811331959A CN 109369194 A CN109369194 A CN 109369194A
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silicon nitride
porous silicon
green body
nitride ceramic
preparation
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CN109369194B (en
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张柳
李庆刚
史国普
吴俊彦
王志
黄世峰
程新
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University of Jinan
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Abstract

The invention discloses a kind of preparation processes that low dielectric, high-intensitive porous silicon nitride ceramic are prepared by regulating microstructure, include the following steps: preparation, blank forming, the drying of green body, the sintering of the dumping of green body, green body of gel.The present invention is in order to improve β-Si3N4Conversion ratio, in the slurry add zirconium boride promote α-Si3N4To β-Si3N4Conversion, high length-diameter ratio β-Si can be formed3N4Column crystal mutually overlaps the pore framework for constituting porous silicon nitride ceramic, improves its intensity.The preparation process of porous silicon nitride ceramic provided by the invention is at low cost, simple process, the obtained high and low dielectric constant of porous silicon nitride ceramic porosity and mechanical property is good.Porosity is >=50%, and dielectric constant 3.3 ± 0.1, anti-bending strength is in 99.89~131.67MPa.Final porous silicon nitride ceramic microstructure such as attached drawing.

Description

A kind of low dielectric, High Strength Properties Porous Silicon Nitride Ceramics and preparation method thereof
Technical field
The present invention relates to technical field of material, and in particular to a kind of preparation process of porous silicon nitride ceramic.
Background technique
Porous silicon nitride ceramic has corrosion-resistant, high temperature resistant, wear-resistant, high-specific surface area, low-k and dielectric damage The advantages that consumption, in high temperature air filtration, sensor exploitation, catalyst carrier and separation film preparation and missile-borne radome processing etc. Field has boundless application prospect, therefore, has become current research heat for the preparation of porous silicon nitride ceramic One of point.
The most important feature of porous silicon nitride ceramic is porous, and the currently used method for preparing porous ceramics such as adds Add pore creating material method, foaming, reaction sintering, extrusion moulding and gel casting forming etc., and is prepared by these methods Porous ceramics otherwise be that obtained product voidage is low, pore size is different, be unevenly distributed, intensity is not high enough or just It is drying condition harshness, high production cost, complex process, it is difficult to meet the needs of modern production processing.
Summary of the invention
It is an object of the invention in view of the above shortcomings of the prior art, provide a kind of simple process, it is at low cost, have compared with The preparation process of the porous silicon nitride ceramic of high porosity and strength character and uniform stomata.
To achieve the above object, the present invention adopts the following technical scheme that.
A kind of low dielectric, the preparation process of High Strength Properties Porous Silicon Nitride Ceramics, include the following steps:
(1) gel prepare: by beta-silicon nitride powder, zirconium boride powder, sintering aid, crosslinking agent, dispersing agent, defrother and go from Sub- water presses (52~98): (3~9): (2~7): and (0.52~0.98): (0.15~1.8): 100 mixing, with the hydroxide of 0.01M Sodium solution tune pH to 8.2~11.5,2.5~10h of ball milling make to be uniformly mixed to get gel；
(2) molding of green body: by gel obtained by step (1) after carrying out vacuum defoamation in vacuum degasing machine and handling 10~30min, Die for molding is injected, is demoulded after carrying out curing process；
(3) drying of green body: after the green body after demoulding is first cooled to room temperature, sample fully charge is made to carry out freeze-drying system again Obtain silicon nitride green body；
(4) dumping of green body: silicon nitride green body obtained is heated up dumping in air；It is risen to the heating rate of 1 DEG C/min 150 DEG C, 400 DEG C are risen to 1.2 DEG C/min, rises to 600 DEG C with 1.5 DEG C/min, then keeps the temperature 1.5~6h；
(5) sintering of green body: by the green body after dumping in sintering furnace, in a nitrogen atmosphere with, 5 DEG C/min be raised to 1700 DEG C ~ 1800 DEG C, and keep the temperature 2~3h；Then temperature is increased to 1800 DEG C ~ 2000 DEG C progress gas pressure sinterings, keeps the temperature 1~2h furnace cooling Up to the porous silicon nitride ceramic.
(6) porous silicon nitride the aftertreatment technology of porous silicon nitride ceramic: is improved by pre-oxidation treatment and annealing process The intensity of ceramics, the dielectric loss for reducing porous silicon nitride ceramic.
The dispersing agent is preferably ammonium polyacrylate of the molecular weight 3500~4500.
The crosslinking agent is polyvinyl alcohol, polyacrylamide and methylcellulose, any one in Isabam.
Wherein use Isabam as dispersing agent and crosslinking agent, i.e. when Isabam is unique organic additive, solvent is Deionized water.
The sintering aid be yttrium oxide, lanthana, cerium oxide, luteium oxide, praseodymium oxide, etc. rare earth oxides and aluminium oxide With the mixture of silica, its ratio be 1:1:1.
The defrother is preferably the alcohol of C7-C9, preferably n-octyl alcohol.
β-the Si3N4Promotor be boronation zirconium powder, additive amount Si3N4The 5%-30% of volume content.
In step (3), the processing of sample fully charge is to place 24-36h at -25 DEG C.
In step (3), freeze-drying process is to be freeze-dried 15-36h at -60~-80 DEG C.
Curing process is in vacuum oven in 55~80 DEG C of fixed 60min in step (2).
Sintering method uses two-step sintering method in step (5): 1700 DEG C ~ 1800 DEG C progress are normal pressure-sintered；1800℃~2000 DEG C carry out gas pressure sintering, gas pressure 0.6MPa.
The post-processing approach of porous silicon nitride ceramic in step (6): 1000 DEG C ~ 1300 DEG C are carried out to porous silicon nitride ceramic High temperature pre-oxidation treatment or 500 DEG C ~ 800 DEG C of annealing process is carried out to porous silicon nitride ceramic.
Beneficial effect is the present invention compared with prior art:
(1) present invention using Isobam as unique organic additive as dispersing agent and gelling agent in use, solvent uses Deionized water prepares water-based slurry；
(2) present invention molding Si3N4 ceramics have simple process, and organic additive is few, environmental-friendly, cheap advantage, It can be widely applied to preparation low cost, have excellent performance, the product of complicated shape；
(3) present invention is using boronation zirconium powder as β-Si3N4Promotor, to porous silicon nitride ceramic carry out microstructure tune Control；
(4) present invention is using two-step sintering method and post-processing porous silicon nitride ceramic, makes it have low dielectric, high-strength Degree；
(5) porous silicon nitride ceramic porosity prepared by the present invention is high, stomata is uniform, mechanics and dielectric properties are had excellent performance, hole Gap rate is >=50%, and dielectric constant 3.3 ± 0.1, anti-bending strength is in 99.89~131.67MPa.
Detailed description of the invention
Fig. 1 is 1 final products microstructure of embodiment；
Fig. 2 is 1 final products mechanical property of embodiment；
Fig. 3 is 1 final products dielectric properties of embodiment.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail and completely.However, described in embodiment Material ratio, technological parameter and result are merely to illustrate the present invention, it is impossible to be used in the limitation present invention.
Embodiment 1
(1) prepared by gel: by 52g beta-silicon nitride powder, 5g boronation zirconium powder, 5g sintering aid, 3gIsobam polymer, 1g de-bubble Agent and 100g deionized water mixing, with the sodium hydroxide solution tune pH to 9 of 0.01M, ball milling 3h make be uniformly mixed prepare it is solidifying Glue；Wherein sintering aid is yttrium oxide, aluminium oxide and silica 1: the mixture of 1:1 mixing, crosslinking agent is polyvinyl alcohol, point Powder is the ammonium polyacrylate that average molecular weight is 3500, and defrother is n-heptanol；
(2) it the molding of green body: by step gel after carrying out Fruit storage 15min in vacuum oven, injects in mold Molding, in being demoulded after 55 DEG C of fixed 60min are handled in baking oven；
(3) drying of green body: after the green body after demoulding is first cooled to room temperature, sample places for 24 hours that fully charge is again at -25 DEG C It is freeze-dried 15h at -60 DEG C, silicon nitride green body is made；
(4) dumping of green body: silicon nitride green body obtained is heated up dumping in air；It is risen to the heating rate of 1 DEG C/min 150 DEG C, 400 DEG C are risen to 1.2 DEG C/min, 600 DEG C is risen to 1.5 DEG C/min, then keeps the temperature 2h；
(5) by the green body after dumping in sintering furnace, in a nitrogen atmosphere with 5 DEG C/min is raised to 1700 DEG C ~ 1800 DEG C, and protects 2~3h of temperature；Then temperature is increased to 1800 DEG C ~ 2000 DEG C progress gas pressure sinterings, keeps the temperature 1~2h furnace cooling up to described more Hole silicon nitride ceramics；
(6) porous silicon nitride ceramic the aftertreatment technology of porous silicon nitride ceramic: is improved by pre-oxidation treatment and annealing process Intensity, reduce porous silicon nitride ceramic dielectric loss.
Through detecting, the porosity of obtained porous silicon nitride ceramic is 67.23%, 100.89 MPa of anti-bending strength.
Embodiment 2
(1) gel prepare: by 65g beta-silicon nitride powder, 6g sintering aid, 3g crosslinking agent, 0.7g dispersing agent, 1.2g defrother and The mixing of 100g deionized water makes to be uniformly mixed and prepares gel with the sodium hydroxide solution tune pH to 9.5 of 0.01M, ball milling 5h；Its Middle sintering aid is yttrium oxide, aluminium oxide and silica 1: the mixture of 1:1 mixing, crosslinking agent is polyvinyl alcohol, dispersing agent The ammonium polyacrylate for being 3750 for average molecular weight, defrother are n-octyl alcohol；
(2) it the molding of green body: by step gel after carrying out Fruit storage 15min in vacuum oven, injects in mold Molding, in being demoulded after 60 DEG C of fixed 60min are handled in baking oven；
(3) drying of green body: after the green body after demoulding is first cooled to room temperature, sample places for 24 hours that fully charge is again at -20 DEG C It is freeze-dried 15h at -60 DEG C, silicon nitride green body is made；
(4) dumping of green body: silicon nitride green body obtained is heated up dumping in air；It is risen to the heating rate of 1 DEG C/min 150 DEG C, 400 DEG C are risen to 1.2 DEG C/min, 600 DEG C is risen to 1.5 DEG C/min, then keeps the temperature 3h；
(5) by the green body after dumping in sintering furnace, in a nitrogen atmosphere with 5 DEG C/min is raised to 1700 DEG C ~ 1800 DEG C, and protects 2~3h of temperature；Then temperature is increased to 1800 DEG C ~ 2000 DEG C progress gas pressure sinterings, keeps the temperature 1~2h furnace cooling up to described more Hole silicon nitride ceramics；
(6) porous silicon nitride ceramic the aftertreatment technology of porous silicon nitride ceramic: is improved by pre-oxidation treatment and annealing process Intensity, reduce porous silicon nitride ceramic dielectric loss.
Through detecting, the porosity of obtained porous silicon nitride ceramic is 66.34%, 110.72 MPa of anti-bending strength.
Embodiment 3
(1) gel prepare: by 73g beta-silicon nitride powder, 6g sintering aid, 6g crosslinking agent, 0.7g dispersing agent, 1.5g defrother and The mixing of 100g deionized water makes to be uniformly mixed and prepares gel with the sodium hydroxide solution tune pH to 10 of 0.01M, ball milling 7h；Its Middle sintering aid is yttrium oxide, aluminium oxide and silica 1: the mixture of 1:1 mixing, crosslinking agent is polyvinyl alcohol, dispersing agent The ammonium polyacrylate for being 4000 for average molecular weight, defrother are n-octyl alcohol；
(2) it the molding of green body: by step gel after carrying out Fruit storage 20min in vacuum oven, injects in mold Molding, in being demoulded after 65 DEG C of fixed 60min are handled in baking oven；
(3) drying of green body: after the green body after demoulding is first cooled to room temperature, sample places 30h fully charge again at -20 DEG C It is freeze-dried 20h at -70 DEG C, silicon nitride green body is made；
(4) dumping of green body: silicon nitride green body obtained is heated up dumping in air；It is risen to the heating rate of 1 DEG C/min 150 DEG C, 400 DEG C are risen to 1.2 DEG C/min, 600 DEG C is risen to 1.5 DEG C/min, then keeps the temperature 3h；
(5) by the green body after dumping in sintering furnace, in a nitrogen atmosphere with 5 DEG C/min is raised to 1700 DEG C ~ 1800 DEG C, and protects 2~3h of temperature；Then temperature is increased to 1800 DEG C ~ 2000 DEG C progress gas pressure sinterings, keeps the temperature 1~2h furnace cooling up to described more Hole silicon nitride ceramics；
(6) porous silicon nitride ceramic the aftertreatment technology of porous silicon nitride ceramic: is improved by pre-oxidation treatment and annealing process Intensity, reduce porous silicon nitride ceramic dielectric loss.
Through detecting, the porosity of obtained porous silicon nitride ceramic is 65.16%, 115.89 MPa of anti-bending strength.
Embodiment 4
(1) gel prepare: by 85g beta-silicon nitride powder, 7g sintering aid, 7g crosslinking agent, 0.8g dispersing agent, 1.8g defrother and The mixing of 100g deionized water makes to be uniformly mixed and prepares gel with the sodium hydroxide solution tune pH to 10.5 of 0.01M, ball milling 7h； Wherein sintering aid is yttrium oxide, aluminium oxide and silica 1: the mixture of 1:1 mixing, crosslinking agent is polyvinyl alcohol, dispersion Agent is the ammonium polyacrylate that average molecular weight is 4000, and defrother is n-octyl alcohol；
(2) it the molding of green body: by step gel after carrying out Fruit storage 20min in vacuum oven, injects in mold Molding, in being demoulded after 70 DEG C of fixed 60min are handled in baking oven；
(3) drying of green body: after the green body after demoulding is first cooled to room temperature, sample places 36h fully charge again at -20 DEG C It is freeze-dried 30h at -80 DEG C, silicon nitride green body is made；
(4) dumping of green body: silicon nitride green body obtained is heated up dumping in air；It is risen to the heating rate of 1 DEG C/min 150 DEG C, 400 DEG C are risen to 1.2 DEG C/min, 600 DEG C is risen to 1.5 DEG C/min, then keeps the temperature 4h；
(5) by the green body after dumping in sintering furnace, in a nitrogen atmosphere with 5 DEG C/min is raised to 1700 DEG C ~ 1800 DEG C, and protects 2~3h of temperature；Then temperature is increased to 1800 DEG C ~ 2000 DEG C progress gas pressure sinterings, keeps the temperature 1~2h furnace cooling up to described more Hole silicon nitride ceramics；
(6) porous silicon nitride ceramic the aftertreatment technology of porous silicon nitride ceramic: is improved by pre-oxidation treatment and annealing process Intensity, reduce porous silicon nitride ceramic dielectric loss.
Through detecting, the porosity of obtained porous silicon nitride ceramic is 62.69%, 127.25 MPa of anti-bending strength.
Embodiment 5
(1) gel prepare: by 98g beta-silicon nitride powder, 9g sintering aid, 7g crosslinking agent, 0.98g dispersing agent, 1.8g defrother with And 100g deionized water mixing, with the sodium hydroxide solution tune pH to 11.5 of 0.01M, ball milling 10h make be uniformly mixed prepare it is solidifying Glue；Wherein sintering aid is yttrium oxide, aluminium oxide and silica 1: the mixture of 1:1 mixing, crosslinking agent is polyvinyl alcohol, point Powder is the ammonium polyacrylate that average molecular weight is 4500, and defrother is n-octyl alcohol；
(2) it the molding of green body: by step gel after carrying out Fruit storage 30min in vacuum oven, injects in mold Molding, in being demoulded after 80 DEG C of fixed 60min are handled in baking oven；
(3) drying of green body: after the green body after demoulding is first cooled to room temperature, sample places 36h fully charge again at -20 DEG C It is freeze-dried 36h at -80 DEG C, silicon nitride green body is made；
(4) dumping of green body: silicon nitride green body obtained is heated up dumping in air；It is risen to the heating rate of 1 DEG C/min 150 DEG C, 400 DEG C are risen to 1.2 DEG C/min, 600 DEG C is risen to 1.5 DEG C/min, then keeps the temperature 6h；
(5) by the green body after dumping in sintering furnace, in a nitrogen atmosphere with 5 DEG C/min is raised to 1700 DEG C ~ 1800 DEG C, and protects 2~3h of temperature；Then temperature is increased to 1800 DEG C ~ 2000 DEG C progress gas pressure sinterings, keeps the temperature 1~2h furnace cooling up to described more Hole silicon nitride ceramics；
(6) porous silicon nitride ceramic the aftertreatment technology of porous silicon nitride ceramic: is improved by pre-oxidation treatment and annealing process Intensity, reduce porous silicon nitride ceramic dielectric loss.
Through detecting, the porosity of obtained porous silicon nitride ceramic is 59.58%, 131.67 MPa of anti-bending strength.

Claims (10)

1. a kind of low dielectric, the preparation method of High Strength Properties Porous Silicon Nitride Ceramics, which comprises the steps of:
(1) gel prepare: by beta-silicon nitride powder, zirconium boride powder, sintering aid, crosslinking agent, dispersing agent, defrother and go from Sub- water 52~98:3 in mass ratio~9:2~7:0.52~0.98:0.15~1.8:100 mixing, it is molten with the sodium hydroxide of 0.01M Liquid tune pH to 8.2~11.5,2.5~10h of ball milling make to be uniformly mixed to get gel；
(2) molding of green body: by gel obtained by step (1) after carrying out vacuum defoamation in vacuum degasing machine and handling 10~30min, Die for molding is injected, is demoulded after carrying out curing process；
(3) drying of green body: after the green body after demoulding is first cooled to room temperature, sample fully charge is made to carry out freeze-drying system again Obtain silicon nitride green body；
(4) dumping of green body: silicon nitride green body obtained is heated up dumping in air；It is risen to the heating rate of 1 DEG C/min 150 DEG C, 400 DEG C are risen to 1.2 DEG C/min, rises to 600 DEG C with 1.5 DEG C/min, then keeps the temperature 1.5~6h；
(5) sintering of green body: by the green body after dumping in sintering furnace, in a nitrogen atmosphere with, 5 DEG C/min be raised to 1700 DEG C ~ 1800 DEG C, and keep the temperature 2~3h；Then temperature is increased to 1800 DEG C ~ 2000 DEG C progress gas pressure sinterings, keeps the temperature 1~2h furnace cooling Up to the porous silicon nitride ceramic；
(6) porous silicon nitride ceramic the aftertreatment technology of porous silicon nitride ceramic: is improved by pre-oxidation treatment and annealing process Intensity, reduce porous silicon nitride ceramic dielectric loss.
2. low dielectric according to claim 1, the preparation method of High Strength Properties Porous Silicon Nitride Ceramics, which is characterized in that institute Stating dispersing agent is ammonium polyacrylate of the molecular weight 3500~4500；Defrother is the alcohol of C7-C9, preferably n-octyl alcohol.
3. low dielectric according to claim 1, the preparation method of High Strength Properties Porous Silicon Nitride Ceramics, which is characterized in that institute Crosslinking agent is stated as any one in polyvinyl alcohol, polyacrylamide and methylcellulose, Isobam.
4. low dielectric according to claim 1, the preparation method of High Strength Properties Porous Silicon Nitride Ceramics, which is characterized in that make Use Isobam as dispersing agent and crosslinking agent, i.e. when Isobam is unique organic additive, solvent uses deionized water.
5. low dielectric according to claim 1, the preparation method of High Strength Properties Porous Silicon Nitride Ceramics, which is characterized in that institute State sintering aid be yttrium oxide, lanthana, cerium oxide, luteium oxide, praseodymium oxide, etc. rare earth oxides and aluminium oxide and silica Mixture, its ratio be 1:1:1.
6. low dielectric according to claim 1, the preparation method of High Strength Properties Porous Silicon Nitride Ceramics, which is characterized in that institute β-the Si stated3N4Promotor be boronation zirconium powder, additive amount Si3N4The 5%-30% of volume content.
7. the preparation process of porous silicon nitride ceramic according to claim 1, which is characterized in that sample is complete in step (3) Freeze processing entirely to place 24-36h at -25 DEG C；Freeze-drying process is to be freeze-dried 15-36h at -60~-80 DEG C.
8. the preparation process of porous silicon nitride ceramic according to claim 1, which is characterized in that in step (2) at solidification Reason is in vacuum oven in 55~80 DEG C of curing process 60min.
9. the preparation method of porous silicon nitride ceramic according to claim 1, which is characterized in that sintering side in step (5) Method uses two-step sintering method: 1700 DEG C ~ 1800 DEG C progress are normal pressure-sintered；1800 DEG C ~ 2000 DEG C progress gas pressure sinterings, gas pressure 0.6MPa；Sintering atmosphere is high pure nitrogen.
10. the preparation method of porous silicon nitride ceramic according to claim 1, which is characterized in that porous nitrogen in step (6) The aftertreatment technology of SiClx ceramics include: to porous silicon nitride ceramic carry out 1000 DEG C ~ 1300 DEG C high temperature pre-oxidation treatment or 500 DEG C ~ 800 DEG C of annealing process is carried out to porous silicon nitride ceramic.
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