CN109574680A - A kind of method that gas-solid reaction combination lqiuid phase sintering method prepares porous silicon nitride ceramic - Google Patents

A kind of method that gas-solid reaction combination lqiuid phase sintering method prepares porous silicon nitride ceramic Download PDF

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CN109574680A
CN109574680A CN201811459224.3A CN201811459224A CN109574680A CN 109574680 A CN109574680 A CN 109574680A CN 201811459224 A CN201811459224 A CN 201811459224A CN 109574680 A CN109574680 A CN 109574680A
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silicon nitride
gas
porous silicon
nitride ceramic
solid reaction
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王波
智强
张建飞
周小楠
黄鑫
李紫璇
丁克
杨建锋
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Xian Jiaotong University
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Xian Jiaotong University
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Abstract

The invention discloses a kind of methods that gas-solid reaction combination lqiuid phase sintering method prepares porous silicon nitride ceramic, with the α-Si of nano carbon black and micro-meter scale3N4For raw material, rare earth oxide is sintering aid, and under the conditions of nitrogen atmosphere, the gas phase evaporated first by SiO powder is reacted with the carbothermal reduction-nitridation of nanometer carbon black obtains nano Si3N4Equally distributed block, is sintered using high-temperature liquid-phase, and single β-Si is prepared3N4The porous silicon nitride ceramic of phase.Material has~1% line expansion after high temperature sintering, realizes the dead size molding of material substantially；The porosity of porous material can be regulated and controled on a large scale by regulation raw material proportioning, forming pressure and sintering temperature, and intensity with higher.When the porosity is 50%, porous Si3N4The bending strength of material is up to 160.5MPa.The porous SiN ceramic that the present invention obtains can be widely applied to the fields such as high-temperature filter or catalyst carrier.

Description

A kind of method that gas-solid reaction combination lqiuid phase sintering method prepares porous silicon nitride ceramic
Technical field
The present invention relates to a kind of methods that gas-solid reaction combination lqiuid phase sintering method prepares porous silicon nitride ceramic, are suitable for each Kind high temperature filtration separator, catalyst carrier, sound-absorbing material and electromagnetic wave transparent material etc..
Background technique
Porous silicon nitride ceramic is due to high-specific surface area, low-density, lower dielectric constant, dielectric absorption, well Anti-oxidant, anti-thermal shock, heat resistanceheat resistant chemical corrosion resistance and excellent room temperature and elevated temperature strength be widely used in high-temperature metal mistake Filter, radiant burner, heat exchanger, catalyst carrier, radar and missile-borne radome etc..Silicon nitride such as generally has at the shaft-like α- Si3N4With rodlike β-Si3N4Two kinds of crystal morphologies, wherein by rodlike β-Si3N4Crystal grain mutually overlaps the structure of composition, has more excellent Mechanical property more.Currently, preparing the method and technique of porous silicon nitride there are many kind, there are commonly the method that partially sinters, gels Injection molding, sol-gal process, freeze-drying add pore creating material method, template, foaming, reaction-sintered and self-propagating combustion Synthetic method etc..However the technique of most of the above is with α-Si3N4For raw material, caused caused by the particle re-arrangement in sintering process Before densification betides phase transition, and by α-Si3N4To β-Si3N4The phase transition of silicon nitride often can further promote again Into densification.So passing through direct sintering α-Si3N4When powder prepares porous silicon nitride, in the case where guaranteeing the complete situation of phase transition, Generally it is difficult to be provided simultaneously with it higher porosity (>=50%), and sintering process is with biggish volume contraction.Although logical Cross freeze-drying, the method for addition pore creating material can be further improved the porosity, but usually exist greatly in its microstructure The defects of hole, and the structure in hole and aperture size are unevenly distributed, and cause intensity lower.Additionally, due to commercially available nitrogen SiClx powder, usual price is more expensive, and is sintered preparation β-Si by beta-silicon nitride powder3N4When porous ceramics, generally require higher Temperature, so relatively high using the cost that above method prepares porous silicon nitride.
Using silicon powder as raw material, silicon powder Direct-Nitridation is prepared by porous nitrogen using reaction-sintered or Self- propagating Sintering Synthetic method SiClx ceramics, although the cost and preparation temperature of raw material can be effectively reduced, and due to not receiving during reaction-sintered Compression deformation realizes net-shape-sinter, therefore finally accurately controls the size of sintered body.But since the product of acquisition fails shape At mutual overlapped the interlocking structure of rodlike crystal phase, thus it is lower there are still intensity the problems such as.
Summary of the invention
The purpose of the present invention is to provide the sides that a kind of gas-solid reaction combination lqiuid phase sintering method prepares porous silicon nitride ceramic Method, for this method using nanometer carbon black as carbon source, silicon monoxide is silicon source, prepares nitride porous by gas-solid reaction combination liquid-phase sintering Silicon ceramics.On the one hand in the complete situation of phase transition, net-shape-sinter is realized, the porosity of obtained silicon nitride material can A wide range of regulation.On the other hand it is raw material because using cheap nano carbon black and silicon monoxide powder, effectively reduces nitrogen The preparation cost of SiClx.
The present invention, which adopts the following technical scheme that, to be achieved:
A kind of method that gas-solid reaction combination lqiuid phase sintering method prepares porous silicon nitride ceramic, comprising the following steps:
1) according to mass percent by the nano carbon black of 18.9~83.0wt%, the α-Si of 0~73.5wt%3N4, and Green compact are formed after the rare earth oxide mixed-powder compression molding of 7.7~17.0wt%, SiO powder is placed in crucible bottom, it will Green compact are placed in the middle part of crucible, then crucible is placed in multifunctional sintering furnace, are passed through nitrogen, small in 1500~1700 DEG C of heat preservations 1~6 When, it carries out carbothermal reduction-nitridation reaction and generates silicon nitride green body, wherein the mass ratio of SiO and nano carbon black is 10:1；
2) 1700~1850 DEG C of progress liquid-phase sintering 0.5~2 hour are continuously heating to, generation phase transition during this, i.e., Obtain porous silicon nitride ceramic.
A further improvement of the present invention lies in that selecting the crystal seed model UBE-10 of silicon nitride, average grain diameter in step 1) It is 0.2~0.5 μm.
A further improvement of the present invention lies in that the rare earth oxide of selection is Y in step 1)2O3、Lu2O3、Yb2O3、La2O3 Or Eu2O3。
A further improvement of the present invention lies in that the pressure of compression molding is 10~80MPa in step 1).
A further improvement of the present invention lies in that nitrogen atmosphere pressure is 1~20atm in step 1).
1100 DEG C of heating is risen to from room temperature a further improvement of the present invention lies in that in step 1), in multifunctional sintering furnace Speed is 500~700 DEG C/h, and the heating rate that sintering temperature is warming up to from 1100 DEG C is 100~300 DEG C/h.
A further improvement of the present invention lies in that gas-solid reaction temperature rises to the heating speed of liquid phase sintering conditions in step 2) Degree is 50~100 DEG C/h.
The present invention has following beneficial technical effect:
The method that a kind of gas-solid reaction combination lqiuid phase sintering method provided by the invention prepares porous silicon nitride ceramic, this method Using micron silicon nitride as skeleton, using nano carbon black as carbon source, silicon monoxide powder is silicon by thermogenetic silicon monoxide vapor volume Source obtains nano-silicon nitride by carbothermal reduction-nitridation, is sintered using high-temperature liquid-phase, porous Si is prepared3N4Material.It is high Sample has~1% line expansion after temperature sintering, realizes the dead size molding of sample；And the porosity of porous material can pass through tune Control forming pressure and sintering temperature are regulated and controled on a large scale, and the porous silicon nitride being prepared has the high porosity, while simultaneous Has high obdurability.When the porosity is 50%, porous Si3N4The bending strength of material is up to 160.5MPa.In addition, this technique Using cheap nano carbon black as raw material, preparation cost is lower, and process controllability is preferable.
Detailed description of the invention
Fig. 1 schemes for the SEM of sample after liquid-phase sintering after the first gas-solid reaction of embodiment 5.
Fig. 2 is the XRD diagram of sample after liquid-phase sintering after the first gas-solid reaction of embodiment 2.
Fig. 3 is gas-solid reaction schematic diagram.
Specific embodiment
Below in conjunction with drawings and examples, the present invention is described in further detail.
The method that a kind of gas-solid reaction combination lqiuid phase sintering method provided by the invention prepares porous silicon nitride ceramic is implemented Example composition as shown in table 1, in the embodiment 1~13 shown in table 1, adds a certain proportion of nano-silicon nitride in nano carbon black Crystal seed reacts with silicon monoxide steam generation carbon tropical resources after certain briquetting pressure is pressed into green compact, is changed into nitridation Silicon.
The raw material of the porous SiN ceramic of the present invention of table 1. forms
The sintering process parameter of the porous SiN ceramic of the present invention of table 2.
1 embodiment of table is the preparation method of porous SiN ceramic, first presses nano carbon black and silicon nitride powder described in table 1 not It is weighed respectively with composition, uses dehydrated alcohol to be prepared into uniform mixed-powder as solvent wet mixing, then rotate mixed-powder It is dry, it places into 70 DEG C of baking oven and thoroughly dries, cross 200 meshes after dry, be put into metal die compression moulding and implemented The green compact sample of example 1~10, briquetting pressure are controlled in 10~80MPa.SiO powder is placed in crucible bottom, green compact are placed in earthenware In the middle part of crucible, then crucible is placed in multifunctional sintering furnace, is first risen in a nitrogen atmosphere with the heating rate of 500~700 DEG C/h 1100 DEG C, then 1500 DEG C~1700 DEG C heat preservations, 2~5 hours progress gas-solid carbon heat is warming up to the heating rate of 100~300 DEG C/h Nitridation reaction obtains silicon nitride green body；Then it is warming up to 1700-1850 DEG C with the speed of 50~100 DEG C/h, in a nitrogen atmosphere Phase transition is partially sintered and completed, porous silicon nitride ceramic is obtained.
The formulation of technique is for consideration: the volume by changing nitridation silicon seed, thus it is possible to vary crystallite dimension is adjusted The ratio for saving rodlike crystalline substance of thickness, obtains the sample of the rodlike brilliant ratio of different thicknesses, and then the regulation of realization crystal grain distribution, green compact at The pressure of type should be controlled in 10~80MPa, and in the case where food ingredient determines, the green body porosity is determined by precast body briquetting pressure Fixed, it directly affects the porosity of final ceramics.The porous SiN ceramic obtained by the above method, is measured with three-point bending method Bending strength at room temperature；Open porosity is measured with Archimedes's drainage；It is seen on sample section with scanning electron microscope Examine microscopic structure；With the object phase composition of X-ray diffractometer analysis sintered body.The results of property of these porositys and bending strength is such as Shown in table 2.
Using the nano carbon black of 83.0wt% as raw material, the yttrium oxide of 17.0wt% is embodiment 1 as can be seen from Table 3 Sintering aid, briquetting pressure 10MPa by 1700 DEG C of heat preservation 2h gas-solid reactions, then keep the temperature 2h at 1750 DEG C and carry out liquid phase Sintering, the porous Si of gained3N4The porosity of ceramic material is 60%, and bending strength is up to 30.8MPa.It can be seen that from attached drawing 1 It is mutually overlapped between silicon nitride rod-like crystalline substance, forms porous ceramics.
The performance of the porous SiN ceramic sintered body of the present invention of table 3.
Embodiment 4 is using the nano carbon black of 51.9wt% and the silicon nitride powder of 35.6wt% as former as can be seen from Table 3 Material, the europium oxide of 12.5wt% are sintering aid, briquetting pressure 80MPa, by 1550 DEG C of heat preservation 5h gas-solid reactions, then 2h is kept the temperature at 1700 DEG C carries out liquid-phase sintering, the porous Si of gained3N4The porosity of ceramic material is 48%, and intensity is reachable 90.3MPa。
Embodiment 8 is using the nano carbon black of 18.9wt% and the silicon nitride powder of 73.4wt% as former as can be seen from Table 3 Material, the ytterbium oxide of 7.7wt% is that sintering aid briquetting pressure is 20MPa, by 1650 DEG C of heat preservation 5h gas-solid reactions, then 1700 2h is kept the temperature at DEG C carries out liquid-phase sintering, the porous Si of gained3N4The porosity of ceramic material is 58%, and intensity is up to 100.5MPa.
Embodiment 12 uses the silicon nitride powder conduct of the nano carbon black and 35.6wt% of 51.9.wt% as can be seen from Table 3 Raw material, the luteium oxide of 12.5wt% are sintering aid, briquetting pressure 20MPa, by 1550 DEG C of heat preservation 5h gas-solid reactions, then 0.5h is kept the temperature at 1700 DEG C carries out liquid-phase sintering, the porous Si of gained3N4The porosity of ceramic material is 58%, and intensity is reachable 110.8MPa。
Embodiment 13 uses the silicon nitride powder conduct of the nano carbon black and 43.6wt% of 44.9.wt% as can be seen from Table 3 Raw material, the ytterbium oxide of 11.5wt% are sintering aid, briquetting pressure 80MPa, by 1500 DEG C of heat preservation 5h gas-solid reactions, then 2h is kept the temperature at 1850 DEG C carries out liquid-phase sintering, the porous Si of gained3N4The porosity of ceramic material is 55%, and intensity is reachable 125.0MPa。
From attached drawing 1 as can be seen that mutually overlap joint forms porous pottery between the silicon nitride rod-like crystalline substance of the micron of high length-diameter ratio Porcelain.
Fig. 2 is the porous Si obtained of embodiment 23N4The XRD diagram of ceramic material.As shown, after liquid-phase sintering, Phase obtained is single β-Si3N4。
Fig. 3 is gas-solid reaction schematic diagram, wherein serial number 1 is sintering furnace, and serial number 2 is the graphite cover that surface coats BN, serial number 3 be Si3N4+ C, serial number 4 are the graphite plate with holes that surface coats BN, and serial number 5 is SiO powder.

Claims (7)

1. a kind of method that gas-solid reaction combination lqiuid phase sintering method prepares porous silicon nitride ceramic, which is characterized in that including following Step:
1) according to mass percent by the nano carbon black of 18.9~83.0wt%, the α-Si of 0~73.5wt%3N4And 7.7~ Green compact are formed after the rare earth oxide mixed-powder compression molding of 17.0wt%, SiO powder is placed in crucible bottom, green compact are set It is placed in multifunctional sintering furnace in the middle part of crucible, then by crucible, is passed through nitrogen, keep the temperature 1~6 hour at 1500~1700 DEG C, into The reaction of row carbothermal reduction-nitridation generates silicon nitride green body, and wherein the mass ratio of SiO and nano carbon black is 10:1；
2) 1700~1850 DEG C of progress liquid-phase sintering 0.5~2 hour are continuously heating to, generation phase transition, that is, obtain during this Porous silicon nitride ceramic.
2. the method that a kind of gas-solid reaction combination lqiuid phase sintering method according to claim 1 prepares porous silicon nitride ceramic, It is characterized in that, selecting the crystal seed model UBE-10 of silicon nitride in step 1), average grain diameter is 0.2~0.5 μm.
3. the method that a kind of gas-solid reaction combination lqiuid phase sintering method according to claim 1 prepares porous silicon nitride ceramic, It is characterized in that, the rare earth oxide of selection is Y in step 1)2O3、Lu2O3、Yb2O3、La2O3Or Eu2O3。
4. the method that a kind of gas-solid reaction combination lqiuid phase sintering method according to claim 1 prepares porous silicon nitride ceramic, It is characterized in that, the pressure of compression molding is 10~80MPa in step 1).
5. the method that a kind of gas-solid reaction combination lqiuid phase sintering method according to claim 1 prepares porous silicon nitride ceramic, It is characterized in that, nitrogen atmosphere pressure is 1~20atm in step 1).
6. the method that a kind of gas-solid reaction combination lqiuid phase sintering method according to claim 1 prepares porous silicon nitride ceramic, It from the heating rate that room temperature rises to 1100 DEG C is 500~700 DEG C/h in multifunctional sintering furnace it is characterized in that, in step 1), from 1100 DEG C of heating rates for being warming up to sintering temperature are 100~300 DEG C/h.
7. the method that a kind of gas-solid reaction combination lqiuid phase sintering method according to claim 1 prepares porous silicon nitride ceramic, It is characterized in that, the heating rate that gas-solid reaction temperature rises to liquid phase sintering conditions is 50~100 DEG C/h in step 2).
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111196729A (en) * 2020-01-09 2020-05-26 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
CN111285692A (en) * 2020-02-21 2020-06-16 武汉理工大学 High-thermal-conductivity Si3N4Ceramic and preparation method thereof
CN112159236A (en) * 2020-10-19 2021-01-01 江苏贝色新材料有限公司 High-thermal-conductivity silicon nitride ceramic substrate and preparation method thereof
CN115930779A (en) * 2022-12-05 2023-04-07 江苏富乐华功率半导体研究院有限公司 Quantitative evaluation test method for silicon nitride ceramic grains

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107337186A (en) * 2017-06-20 2017-11-10 西安交通大学 A kind of preparation method of low-dimensional silicon nitride nano-material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107337186A (en) * 2017-06-20 2017-11-10 西安交通大学 A kind of preparation method of low-dimensional silicon nitride nano-material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王旭东: "气压烧结氮化硅陶瓷组织及性能研究", 《中国优秀硕士学位论文全文数据库工程科技I辑》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111196729A (en) * 2020-01-09 2020-05-26 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
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
CN111285692A (en) * 2020-02-21 2020-06-16 武汉理工大学 High-thermal-conductivity Si3N4Ceramic and preparation method thereof
CN112159236A (en) * 2020-10-19 2021-01-01 江苏贝色新材料有限公司 High-thermal-conductivity silicon nitride ceramic substrate and preparation method thereof
CN115930779A (en) * 2022-12-05 2023-04-07 江苏富乐华功率半导体研究院有限公司 Quantitative evaluation test method for silicon nitride ceramic grains
CN115930779B (en) * 2022-12-05 2023-11-14 江苏富乐华功率半导体研究院有限公司 Quantitative evaluation test method for silicon nitride ceramic grains

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