CN105439620A - Method for preparing porous silicon nitride by spark plasma sintering - Google Patents

Method for preparing porous silicon nitride by spark plasma sintering Download PDF

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CN105439620A
CN105439620A CN201410535921.8A CN201410535921A CN105439620A CN 105439620 A CN105439620 A CN 105439620A CN 201410535921 A CN201410535921 A CN 201410535921A CN 105439620 A CN105439620 A CN 105439620A
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sintering
silicon nitride
porous silicon
plasma sintering
prepares
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张长森
冯厚坤
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Yangcheng Institute of Technology
Yancheng Institute of Technology
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Yangcheng Institute of Technology
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Abstract

The invention discloses a method for preparing porous silicon nitride by spark plasma sintering and relates to the technical field of preparation of a ceramic material. The method comprises: mixing an Si3N4 powdery material with certain fineness, a sintering aid and a pore forming substance; after grinding and drying the mixture, performing mould pressing to form a formed body in a certain shape; then obtaining a blank with certain porosity through a glue discharging process; and quickly sintering the blank in an SPS sintering furnace to prepare the porous silicon nitride. The method disclosed by the invention is simple in preparation process, short in sintering time, low in sintering temperature and low in energy consumption. By taking silicon nitride as a main raw material, a porous silicon nitride ceramic is prepared by virtue of a spark plasma sintering technology. The total porosity of the product is 40-60%, and the bending strength is 40-75 MPa.

Description

Discharge plasma sintering prepares the method for porous silicon nitride
Technical field
The present invention relates to ceramic materials preparation technology field, particularly a kind of discharge plasma sintering prepares the method for porous silicon nitride.
Background technology
Since China's reform and opening-up, national economy is increased fast, and " scientific and technical innovation, autonomous innovation " has become current industrial main flow.China's industry is progressively to the future development of intensive style, energy-saving and emission-reduction, low-carbon (LC).Porous silicon-nitride ceramic material has high temperature resistant because of it, and material is light, and the advantage of good corrosion resistance, adds the characteristic that it has porous, is normally used for high-temperature gas filter (as vehicle maintenance service), separatory membrane, absorption and support of the catalyst etc.In recent years, the technology of preparing of porous silicon-nitride ceramic material becomes the hot issue of people's research.Chinese patent literature CN103121854A discloses by the method for self-propagating legal system for porous silicon nitride ceramic, CN101407420A discloses a kind of method preparing non-grain boundary phase porous silicon nitride ceramic based on carbothermic reduction, and CN102320856B discloses a kind of method that injection forming is fired into porous silicon nitride.Above-mentioned several technology of preparing, all also exists the problems such as sintering temperature is too high, sintering time is oversize, complex process, void content are low.The continuous research and discovery of scientific research personnel of the same trade, although achieve some progress technically, still also exists the technical barrier not yet overcome in practice.Utilize discharge plasma sintering method to prepare porous silicon-nitride ceramic material at present and have no identical report.
Summary of the invention
The object of the invention is to overcome above deficiency, provide a kind of discharge plasma sintering to prepare the method for porous silicon nitride, preparation technology is simple, and sintering time is short, sintering temperature is low, it is low to consume energy.Obtained porous silicon nitride ceramic has high porosity, excellent mechanical performances.
The technical solution adopted for the present invention to solve the technical problems is: discharge plasma sintering prepares the method for porous silicon nitride, comprises the following steps:
1. by Si 3n 4powder, sintering aid, pore-forming material put into agate ball milling, then add dehydrated alcohol grinding 2h, and obtained slip, is placed in electric drying oven with forced convection and dries 5h ~ 8h at 70 DEG C ~ 90 DEG C by slurry; 100 object sieves crossed by material after oven dry;
2. add binding agent in powder after sizing, put into ceramic mixer and carry out batch mixing, obtain compound;
3. by compound compression molding, base substrate is obtained;
4. base substrate is placed in air furnace and carries out binder removal, binder removal process is from room temperature to 550 DEG C, temperature rise rate is 1 DEG C/and min ~ 3 DEG C/min, after being incubated 2h after arriving 550 DEG C, naturally cool to room temperature;
5. the base substrate after binder removal is placed in Fast Sintering in SPS sintering oven, and condition is that vacuum tightness is less than 10Pa, and sintering pressure is less than 6MPa; Be heated to 1000 DEG C with the temperature rise rate of 70 ~ 110 DEG C/min, then be heated to 1400 ~ 1600 DEG C with the temperature rise rate of 20 ~ 40 DEG C/min, be incubated 5 ~ 10 minutes, obtain based on β phase, the nitride porous Si composite ceramic that β phase and α phase coexist.
Above-mentioned Si 3n 4powder particle size is 0.5 ~ 10 μm, purity is 88% ~ 97%.
Above-mentioned sintering aid is MgO, Al 2o 3, Y 2o 3wherein one or more.
Above-mentioned binding agent is the PVA of concentration 5%.
Step of the present invention 1. in, Si 3n 4the mass ratio of powder, sintering aid, pore-forming material is (65 ~ 85): (4 ~ 12): (10 ~ 30); Dehydrated alcohol is 1.5 ~ 1.2 times of above-mentioned raw materials quality.
Step of the present invention 3. in, compression molding pressure is 6 ~ 10MPa.
The invention has the beneficial effects as follows: the present invention by by have certain fineness Si 3n 4powder, sintering aid, pore-forming material mix, and grinding is molded into the formed body with definite shape after drying, and then obtains the base substrate with certain porosity by binder removal process, base substrate is put into SPS sintering oven and carry out Fast Sintering, obtained porous silicon nitride ceramic.Preparation technology of the present invention is simple, sintering time is short, sintering temperature is low, it is low to consume energy, take silicon nitride as main raw material, utilize discharge plasma sintering technique to prepare porous silicon nitride ceramic, the total porosity of goods is 40% ~ 60%, and bending strength is 40 ~ 75MPa.
Accompanying drawing explanation
Here further describes the present invention in conjunction with the accompanying drawings and embodiments:
It is the XRD figure of the porous silicon-nitride ceramic material that embodiment 1 obtains in figure.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail and completely, but the present invention is not limited in the content in following embodiment.
Embodiment 1
1. be 70%Si by massfraction 3n 4, 4%Al 2o 3and 6%Y 2o 3, 20% starch powder put into agate ball milling, add the dehydrated alcohol grinding 2h of above-mentioned quality of material 1.5 times, obtained slip, is placed in electric drying oven with forced convection and dries 6h at 80 DEG C by slurry; 100 mesh sieve crossed by material after oven dry;
2. add the PVA that concentration is 5% in powder after sizing, put into ceramic mixer mixing 20min, obtain compound;
3. by compound compression molding under 6MPa, base substrate is obtained;
4. base substrate is placed in air furnace and carries out binder removal, be raised to 250 DEG C with the temperature rise rate of 2 DEG C/min, then be warmed up to 550 DEG C with 1 DEG C/min temperature rise rate, after 550 DEG C of insulation 2h, naturally cool to room temperature;
5. the base substrate after binder removal is placed in SPS sintering oven and carries out Fast Sintering, and condition is that vacuum tightness is less than 10Pa, sintering pressure 5MPa; Be warming up to 1000 DEG C with the temperature rise rate of 100 DEG C/min, then be heated to 1450 DEG C with the temperature rise rate of 30 DEG C/min, be incubated 7 minutes, obtain based on β phase, the nitride porous Si composite ceramic that β phase and α phase coexist.
Performance: adopting three-point bending method to record bending strength is 47.6MPa, and the ventilate rate that Archimedes's drainage is surveyed is 51.6%.
Be the XRD figure of the porous silicon-nitride ceramic material that the present embodiment obtains in figure, principal crystalline phase is beta phase silicon nitride, also has part α phase silicon nitride.
Embodiment 2
1. be 70%Si by massfraction 3n 4, 4%Al 2o 3and 6%Y 2o 3, 20% starch powder put into agate ball milling, add the dehydrated alcohol grinding 2h of above-mentioned raw materials quality 1.5 times, obtained slip, is placed in electric drying oven with forced convection and dries 6h at 80 DEG C by slurry; 100 mesh sieves crossed by material after oven dry;
2. add the PVA that concentration is 5% in powder after sizing, put into ceramic mixer mixing 20min, obtain compound;
3. by compound compression molding under 6MPa, base substrate is obtained;
4. base substrate is placed in air furnace and carries out binder removal, be raised to 250 DEG C with the temperature rise rate of 2 DEG C/min, then be warmed up to 550 DEG C with 1 DEG C/min temperature rise rate, after 550 DEG C of insulation 2h, naturally cool to room temperature;
5. the base substrate after binder removal is placed in SPS sintering oven and carries out Fast Sintering, and condition is that vacuum tightness is less than 10Pa, sintering pressure 5MPa; Be warming up to 1000 DEG C with the temperature rise rate of 100 DEG C/min, then be heated to 1500 DEG C with the temperature rise rate of 30 DEG C/min, be incubated 7 minutes, obtain based on β phase, the nitride porous Si composite ceramic that β phase and α phase coexist.
Performance: adopting three-point bending method to record curved bending strength is 55.3MPa, and the ventilate rate that Archimedes's drainage is surveyed is 49.6%.
Embodiment 3
1. be 70%Si by massfraction 3n 4, 4%Al 2o 3and 6%Y 2o 3, 20% starch powder put into agate ball milling, add the dehydrated alcohol grinding 2h of above-mentioned raw materials quality 1.5 times, obtained slip, is placed in electric drying oven with forced convection and dries 6h at 80 DEG C by slurry; 100 mesh sieves crossed by material after oven dry;
2. add the PVA that concentration is 5% in powder after sizing, put into ceramic mixer mixing 20min, obtain compound;
3. by compound compression molding under 6MPa, base substrate is obtained;
4. base substrate is placed in air furnace and carries out binder removal, be raised to 250 DEG C with the temperature rise rate of 2 DEG C/min, then be warmed up to 550 DEG C with 1 DEG C/min temperature rise rate, after 550 DEG C of insulation 2h, naturally cool to room temperature;
5. the base substrate after binder removal is placed in SPS sintering oven and carries out Fast Sintering, and condition is that vacuum tightness is less than 10Pa, sintering pressure 5MPa; Be warming up to 1000 DEG C with the temperature rise rate of 100 DEG C/min, then be heated to 1600 DEG C with the temperature rise rate of 30 DEG C/min, be incubated 7 minutes, obtain based on β phase, the nitride porous Si composite ceramic that β phase and α phase coexist.
Performance: adopting three-point bending method to record curved bending strength is 71.2MPa, and the ventilate rate that Archimedes's drainage is surveyed is 47.3%.
Embodiment 4
1. be 70%Si by massfraction 3n 4, 4%MgO and 6%Y 2o 3, 20% starch powder put into agate ball milling, add the dehydrated alcohol grinding 2h of above-mentioned raw materials quality 1.5 times, obtained slip, is placed in electric drying oven with forced convection and dries 6h at 80 DEG C by slurry; 100 mesh sieves crossed by material after oven dry;
2. add the PVA that concentration is 5% in powder after sizing, put into ceramic mixer mixing 20min, obtain compound;
3. by compound compression molding under 6MPa, base substrate is obtained;
4. base substrate is placed in air furnace and carries out binder removal, be raised to 250 DEG C with the temperature rise rate of 2 DEG C/min, then be warmed up to 550 DEG C with 1 DEG C/min temperature rise rate, after 550 DEG C of insulation 2h, naturally cool to room temperature;
5. the base substrate after binder removal is placed in SPS sintering oven and carries out Fast Sintering, and condition is that vacuum tightness is less than 10Pa, sintering pressure 5MPa; Be warming up to 1000 DEG C with the temperature rise rate of 100 DEG C/min, then be heated to 1600 DEG C with the temperature rise rate of 30 DEG C/min, be incubated 7 minutes, obtain based on β phase, the nitride porous Si composite ceramic that β phase and α phase coexist.
Performance: adopting three-point bending method to record curved bending strength is 62.3MPa, and the ventilate rate that Archimedes's drainage is surveyed is 48.7%.
Embodiment 5
1. be 65%Si by massfraction 3n 4, 4%Al 2o 3and 6%Y 2o 3, 25% starch powder put into agate jar, add the dehydrated alcohol grinding 2h of above-mentioned raw materials quality 1.5 times, obtained slip, is placed in electric drying oven with forced convection and dries 6h at 80 DEG C by slurry; 100 mesh sieves crossed by material after oven dry;
2. add the PVA that concentration is 5% in powder after sizing, put into ceramic mixer mixing 20min, obtain compound;
3. by compound compression molding under 6MPa, base substrate is obtained;
4. base substrate is placed in air furnace and carries out binder removal, be raised to 250 DEG C with the temperature rise rate of 2 DEG C/min, then be warmed up to 550 DEG C with 1 DEG C/min temperature rise rate, after 550 DEG C of insulation 2h, naturally cool to room temperature;
5. the base substrate after binder removal is placed in SPS sintering oven and carries out Fast Sintering, and condition is that vacuum tightness is less than 10Pa, sintering pressure 5MPa; Be warming up to 1000 DEG C with the temperature rise rate of 100 DEG C/min, then be heated to 1600 DEG C with the temperature rise rate of 30 DEG C/min, be incubated 7 minutes, obtain based on β phase, the nitride porous Si composite ceramic that β phase and α phase coexist.
Performance: adopting three-point bending method to record curved bending strength is 44.6MPa, and the ventilate rate that Archimedes's drainage is surveyed is 58.9%.
Embodiment 6
1. be 70%Si by massfraction 3n 4, 10%Al 2o 3, 20% starch powder put into agate jar, add the dehydrated alcohol grinding 2h of above-mentioned raw materials quality 1.5 times, obtained slip, is placed in electric drying oven with forced convection and dries 6h at 80 DEG C by slurry; 100 mesh sieves crossed by material after oven dry;
2. add the PVA that concentration is 5% in powder after sizing, put into ceramic mixer mixing 20min, obtain compound;
3. by compound compression molding under 6MPa, base substrate is obtained;
4. base substrate is placed in air furnace and carries out binder removal, be raised to 250 DEG C with the temperature rise rate of 2 DEG C/min, then be warmed up to 550 DEG C with 1 DEG C/min temperature rise rate, after 550 DEG C of insulation 2h, naturally cool to room temperature;
5. the base substrate after binder removal is placed in SPS sintering oven and carries out Fast Sintering, and condition is that vacuum tightness is less than 10Pa, sintering pressure 5MPa; Be warming up to 1000 DEG C with the temperature rise rate of 100 DEG C/min, then be heated to 1600 DEG C with the temperature rise rate of 30 DEG C/min, be incubated 7 minutes, obtain based on β phase, the nitride porous Si composite ceramic that β phase and α phase coexist.
Performance: adopting three-point bending method to record curved bending strength is 49.4MPa, and the ventilate rate that Archimedes's drainage is surveyed is 48.2%.

Claims (6)

1. discharge plasma sintering prepares the method for porous silicon nitride, it is characterized in that: comprise the following steps:
1. by Si 3n 4powder, sintering aid, pore-forming material put into agate ball milling, then add dehydrated alcohol grinding 2h, and obtained slip, is placed in electric drying oven with forced convection and dries 5h ~ 8h at 70 DEG C ~ 90 DEG C by slurry; 100 object sieves crossed by material after oven dry;
2. add binding agent in powder after sizing, put into ceramic mixer and carry out batch mixing, obtain compound;
3. by compound compression molding, base substrate is obtained;
4. base substrate is placed in air furnace and carries out binder removal, binder removal process is from room temperature to 550 DEG C, temperature rise rate is 1 DEG C/and min ~ 3 DEG C/min, after being incubated 2h after arriving 550 DEG C, naturally cool to room temperature;
5. the base substrate after binder removal is placed in Fast Sintering in SPS sintering oven, and condition is that vacuum tightness is less than 10Pa, and sintering pressure is less than 6MPa; Be heated to 1000 DEG C with the temperature rise rate of 70 ~ 110 DEG C/min, then be heated to 1400 ~ 1600 DEG C with the temperature rise rate of 20 ~ 40 DEG C/min, be incubated 5 ~ 10 minutes, obtain based on β phase, the nitride porous Si composite ceramic that β phase and α phase coexist.
2. discharge plasma sintering according to claim 1 prepares the method for porous silicon nitride, it is characterized in that: step 1. in, Si 3n 4the mass ratio of powder, sintering aid, pore-forming material is (65 ~ 85): (4 ~ 12): (10 ~ 30); Dehydrated alcohol is 1.5 ~ 1.2 times of above-mentioned raw materials quality.
3. discharge plasma sintering according to claim 1 prepares the method for porous silicon nitride, it is characterized in that: step 3. in, compression molding pressure is 6 ~ 10MPa.
4. discharge plasma sintering according to claim 1 prepares the method for porous silicon nitride, it is characterized in that: described Si 3n 4powder particle size is 0.5 ~ 10 μm, purity is 88% ~ 97%.
5. discharge plasma sintering according to claim 1 prepares the method for porous silicon nitride, it is characterized in that: described sintering aid is MgO, Al 2o 3, Y 2o 3wherein one or more.
6. discharge plasma sintering according to claim 1 prepares the method for porous silicon nitride, it is characterized in that: described binding agent is the PVA of concentration 5%.
CN201410535921.8A 2014-09-28 2014-09-28 Method for preparing porous silicon nitride by spark plasma sintering Pending CN105439620A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105734332A (en) * 2016-04-29 2016-07-06 合肥工业大学 Preparation method for porous tungsten bulk material with uniform and controllable pores
CN107522329A (en) * 2017-08-18 2017-12-29 巢湖市俊业渔具有限公司 Sewage water treatment method during a kind of fishing net makes
CN109095443A (en) * 2018-10-22 2018-12-28 青岛瓷兴新材料有限公司 A kind of method that liquid phase auxiliary combustion is synthetically prepared high purity silicon nitride silicon powder
CN109734455A (en) * 2018-06-08 2019-05-10 河北高富氮化硅材料有限公司 A method of preparing porous silicon nitride ceramic
CN113563088A (en) * 2021-07-30 2021-10-29 淄博国创中心先进车用材料技术创新中心 Porous silicon nitride ceramic component and method for producing same

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105734332A (en) * 2016-04-29 2016-07-06 合肥工业大学 Preparation method for porous tungsten bulk material with uniform and controllable pores
CN107522329A (en) * 2017-08-18 2017-12-29 巢湖市俊业渔具有限公司 Sewage water treatment method during a kind of fishing net makes
CN107522329B (en) * 2017-08-18 2020-12-08 阜阳颍知网络信息科技有限公司 Sewage treatment method in fishing net manufacturing
CN109734455A (en) * 2018-06-08 2019-05-10 河北高富氮化硅材料有限公司 A method of preparing porous silicon nitride ceramic
CN109095443A (en) * 2018-10-22 2018-12-28 青岛瓷兴新材料有限公司 A kind of method that liquid phase auxiliary combustion is synthetically prepared high purity silicon nitride silicon powder
CN109095443B (en) * 2018-10-22 2021-05-28 青岛瓷兴新材料有限公司 Method for preparing high-purity silicon nitride powder by liquid-phase auxiliary combustion synthesis
CN113563088A (en) * 2021-07-30 2021-10-29 淄博国创中心先进车用材料技术创新中心 Porous silicon nitride ceramic component and method for producing same
CN113563088B (en) * 2021-07-30 2023-06-13 淄博国创中心先进车用材料技术创新中心 Porous silicon nitride ceramic part and manufacturing method thereof

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