CN101323524A - Preparation of oriented hole silicon carbide porous ceramic - Google Patents
Preparation of oriented hole silicon carbide porous ceramic Download PDFInfo
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- CN101323524A CN101323524A CNA2008100179707A CN200810017970A CN101323524A CN 101323524 A CN101323524 A CN 101323524A CN A2008100179707 A CNA2008100179707 A CN A2008100179707A CN 200810017970 A CN200810017970 A CN 200810017970A CN 101323524 A CN101323524 A CN 101323524A
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Abstract
The invention discloses a preparation method of a porous silicon-carbide ceramic provided with oriented pores. Firstly, according to weight percentage, 0 to 30 percent of carbon powder, 0 to 50 percent of silicon powder and 0 to 60 percent of silica are added into the 10 to 100 percent of the basic material of silicon-carbide; wherein, the granularity of the silicon-carbide is W3.5 to P220, and one granularity or two granularities are adopted for graduation; then the equally mixed materials are processed through powder accumulation or normal ceramic forming process to obtain a green compact which is put into a graphite crucible or a saggar; the graphite crucible or saggar is placed into a vacuum sintering furnace provided with a temperature field with a temperature grade from 15 to 30 DEG C/cm, and then the temperature is raised to 1900 to 2500 DEG C in an argon environment and with pressure of 0.2 to 1 multipliedby 10 <5>Pa, and the insulation work for the graphite crucible or saggar is preserved for 0.5 to 3 hours; finally the temperature naturally falls down under air protection and the sintered body is taken out, namely, the recrystallization porous silicon-carbide ceramic provided with oriented pores is obtained.
Description
Technical field
The present invention relates to a kind of preparation method of recrystallized silicon carbide porous ceramics of the directional arrangement pore structure that can be used as filtering product or support of the catalyst etc.
Background technology
Thyrite has and is only second to adamantine hardness, high thermal conductivity, low relatively thermal expansivity, excellent thermal shock resistance and creep resisting ability, hot strength and wear resisting property are good, the chemical stability height is insoluble in the general acid and mixing acid, does not react with ebullient hydrochloric acid, sulfuric acid, hydrofluoric acid.Silicon carbide also has characteristic of semiconductor, has the characteristics of negative temperature coefficient.Therefore, it has wide practical use at the industrial circle relevant with thermal technology, burning, chemical industry, environmental protection etc. as a kind of pyroceramic of excellent performance.
Porous ceramics be a kind of through high temperature burn till, have in the sintered compact communicate with each other in a large number and with the connect ceramic material of pore passage structure of material surface.Can be widely used in fields such as melted metal filtering, support of the catalyst, purifying vehicle exhaust and absorbing sound and lowering noise field and transmitter, biomaterial, space material.The material of present existing porous ceramics mostly is oxide ceramics, but oxide ceramics at hardness and wear resistance, thermal conduction and heat-shock resistance, erosion resistance, and the electroconductibility aspect is difficult to compare with silicon carbide ceramics.In many special application scenarios new technical requirements has been proposed the porous ceramic film material performance.These advantages that require to be had with carbofrax material itself are mated very much.Developed at present the car tail-gas filter of business-like porous silicon carbide ceramic material, and high-temperature metal melt casting strainer.
The boring technique of existing porous silicon carbide ceramic is mainly by adding carbon dust, starch, and various organism colloid is as pore-forming material; Perhaps adopt timber, urethane foam as porous (foam) masterplate; Perhaps select resin, the resin+silicon carbide of high solid carbon content for use, perhaps resin+silica flour is shaped, and forms porous body as presoma through Pintsch process.The sintering of porous SiC pottery then forms the mutually bonding silicon carbide of low melting point by adding oxide compound when high temperature; Perhaps add silicon (also can add in base substrate) when sintering, original silicon carbide in the silicon carbide bonding base substrate that the reaction of gas phase or liquid-phase silicone and carbon forms during sintering perhaps directly generates silicon carbide porous body.
Adopt pore-forming material, foaming or template pore-creating, not only need to select suitable pore-forming material, whipping agent and template, the removal of pore-forming material, whipping agent or template simultaneously need be carried out under oxidizing condition mostly, cause the oxidation of sic raw material particulate easily, therefore be used for the preparation of oxide combined silicon carbide porous ceramics more.Silicon carbide inherent excellent properties can not be not fully exerted.
In the reaction sintering preparation process, reaction generates the volumetric expansion of silicon carbide, and perhaps excess reactant (for example Pure Silicon Metal) is difficult to obtain the material of high porosity to the filling of base substrate hole, and the use temperature of material is restricted simultaneously.The air hole structure of the porous that prior art makes (foam) silicon carbide ceramics is random orientation, the relevant performance isotropic of material.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method with carborundum porous ceramics of directional arrangement pore structure, this method need not to add pore-forming material and sintering second mutually, only need to obtain the carborundum porous ceramics sintered compact by control to high temperature recrystallization sintering process, it wherein between the silicon-carbide particle the pure silicon carbide combination that recrystallization process forms, and silicon-carbide particle aligns by preferred orientation, forms a kind of pore structure that aligns at intergranule simultaneously.
For reaching above purpose, the present invention takes following technical scheme to be achieved:
A kind of preparation method of directional hole carborundum porous ceramics comprises the steps:
The first step by weight percentage, adds carbon dust 0～30%, silica flour 0～50%, silica powder 0～60% in basic raw material silicon carbide 10～100%; Wherein carborundum granularity is W3.5～P220, adopts a kind of granularity or two kinds of grain size distributions;
In second step, the batching composition that adopts powder accumulation or ceramic conventional forming technology to mix is made green compact, places plumbago crucible or saggar;
The 3rd step, crucible or saggar put into have the vacuum atmosphere sintering oven that thermograde is 15～30 ℃/cm temperature field, be 0.5 * 10 at pressure
4～1 * 10
5Be warming up to 1900～2500 ℃ under the argon gas condition of Pa, be incubated 0.5-3 hour;
In the 4th step, sintered compact is taken out in cooling cooling naturally under the gas shield in the 3rd step, obtains having the recrystallized silicon carbide porous ceramics of directional arrangement pore structure.
In the such scheme, described silicon carbide adopts the method for two kinds of grain size distributions to be, granularity is that silicon carbide and the granularity of P120 is that the ratio of the silicon carbide weight of P180 is 4/6 or 3/7 or 6/4; Granularity is that silicon carbide and the granularity of P60 is that the ratio of the silicon carbide weight of P120 is 4/6; Granularity is that silicon carbide and the granularity of W14 is that the ratio of the silicon carbide weight of W3.5 is 4/6.Described thermograde along become in the body of heater vertically to or radial distribution.Described powder accumulation is ram-jolt in the plumbago crucible of the profile product that requires of directly packing into after the batching composition is mixed or the saggar.
Ultimate principle of the present invention is to utilize silicon carbide 1900-2500 ℃ of decomposition reaction that is taken place down, to decomposition, distillation, gas phase transmission, and to the control of gas phase crystallisation process again, realize the directed recrystallization sintering between the silicon-carbide particle, form directed perforate or hollow shape radially or the recrystallized silicon carbide porous ceramics of axial aperture structure.
Compared with prior art, the invention has the beneficial effects as follows:
1. adopt the temperature field (vertical or radial temperature field) with thermograde in sintering oven, the evaporation-cohesion direction of may command silicon carbide when high temperature sintering obtains at recrystallized silicon carbide porous ceramic articles axial or radial directed arrangement open-celled structure.
2. pass through the granularity and the grating of choose reasonable silicon carbide, and the add-on of other component; Can obtain the recrystallized silicon carbide porous ceramic articles that aligns open-celled structure of different void content, aperture size requirement.
3. the control of atmosphere pressures when passing through to sintering, the evaporation-cohesion speed when adjusting the silicon carbide high temperature sintering, adjustable adjusting to the void content and the pore size of the recrystallized silicon carbide porous ceramic articles of arranging open-celled structure.
4. the control of green density when using wedding agent shaping base substrate, or the control of pine dress base substrate ram-jolt density when not using wedding agent, but also auxiliary adjustment aligns the void content and the aperture size of the recrystallized silicon carbide porous ceramic articles of open-celled structure.
The crystalline structure for preparing resulting carborundum porous ceramics is pure α-phase silicon carbide, combination between the crystal realizes by recrystallize, the pore direction can according to sintering oven temperature field thermograde vertically or radial directed distribute, directivity with height can obtain the carborundum porous ceramics of 2 microns～2 millimeters of void content 30-70%, aperture size.Its physical and chemical performance is stable, can satisfy specific service requirements, for example as propping material or other functional materials of permeable membrane, has the use temperature wide ranges, the advantage that Application Areas is wide.
Description of drawings
The present invention is described in further detail below in conjunction with drawings and the specific embodiments.
Fig. 1 is the tissue of sample 3-1 of embodiments of the invention 3 and the microstructure form of pore.Wherein Fig. 1 (a) and (b) are respectively the Photomicrograph of different amplification.As can be seen from Figure 1, the microstructure of porous ceramics of the present invention is made up of the bar-shaped pore and the silicon-carbide particle that align, and the basic uniformity of inside and outside tissue, and the connection between the silicon-carbide particle is tight.
Embodiment
The present invention has been 8 embodiment altogether, and the raw material composition of embodiment 1～8 is listed in table 1.
The raw material of table 1 porous silicon carbide ceramic of the present invention is formed (WT%)
According to the prescription of table 1 embodiment 1～8, add ceramic typical binders in the raw material, the resol that also can use high solid carbon content uses conventional manufacturing process as tackiness agent, and raw material, tackiness agent are mixed; Make the green compact of different densities; Put into plumbago crucible or saggar after the drying; Also can not use tackiness agent, the direct ram-jolt of the powder that mixes is packed into to have in the plumbago crucible or saggar of the profile product that requires.Crucible or saggar are put into the high-temperature vacuum atmosphere sintering furnace, and the design by heating element and body of heater causes vertical or radial thermograde in the body of heater; Sintering oven can adopt resistive heating, also can adopt induction heating mode, also can use general high-temperature vacuum atmosphere sintering furnace, notes the shove charge position, so that crucible is in 15～30 ℃ thermograde space.0.5 * 10
4～1 * 10
5Be warming up to 1900-2500 ℃ under the argon gas condition of Pa, be incubated 0.5-3 hour, cooling cooling naturally under gas shield at last; Obtain having the high temperature recrystallization porous silicon carbide sintered compact of directional arrangement pore structure.Each embodiment all prepares two samples, totally ten six samples, its specifically be shaped and sintering process parameter referring to table 2.
Table 2 porous silicon carbide ceramic of the present invention is shaped and sintering process parameter
Embodiment 1～8 carborundum porous ceramics sample that high temperature of the present invention is fired into, the gentle SX-2700 scanning electron microscope in operational analysis sky has been measured the void content of sample respectively, and pore aligns effect, the results are shown in table 3.
The pore parameter of table 3 carborundum porous ceramics sample of the present invention
Claims (6)
1. the preparation method of an oriented hole silicon carbide porous ceramic is characterized in that, comprises the steps:
The first step by weight percentage, adds carbon dust 0～30%, silica flour 0～50%, silica powder 0～60% in basic raw material silicon carbide 10～100%; Wherein carborundum granularity is W3.5～P220, adopts a kind of granularity or two kinds of grain size distributions;
In second step, the batching composition that adopts powder accumulation or conventional ceramics forming technology to mix is made green compact, places plumbago crucible or saggar;
The 3rd step, crucible or saggar put into have the vacuum atmosphere sintering oven that thermograde is 15～30 ℃/cm temperature field, be 0.5 * 10 at pressure
4～1 * 10
5Be warming up to 1900～2500 ℃ under the argon gas condition of Pa, be incubated 0.5～3 hour;
In the 4th step, sintered compact is taken out in cooling cooling naturally under the gas shield in the 3rd step, obtains having the recrystallized silicon carbide porous ceramics of directional arrangement pore structure.
2. the preparation method of oriented hole silicon carbide porous ceramic according to claim 1, it is characterized in that described silicon carbide adopts the method for two kinds of grain size distributions to be: granularity is that silicon carbide and the granularity of P120 is that the ratio of the silicon carbide weight of P180 is 4/6 or 3/7 or 6/4.
3. the preparation method who aligns the perforate carborundum porous ceramics according to claim 1 is characterized in that, described silicon carbide adopts the method for two kinds of grain size distributions to be: granularity is that silicon carbide and the granularity of P60 is that the ratio of the silicon carbide weight of P120 is 4/6.
4. the preparation method who aligns the perforate carborundum porous ceramics according to claim 1 is characterized in that, described silicon carbide adopts the method for two kinds of grain size distributions to be: granularity is that silicon carbide and the granularity of W14 is that the ratio of the silicon carbide weight of W3.5 is 4/6.
5. the preparation method of oriented hole silicon carbide porous ceramic according to claim 1 is characterized in that, described thermograde along become in the body of heater vertically to or radial distribution.
6. the preparation method of oriented hole silicon carbide porous ceramic according to claim 1 is characterized in that, described powder accumulation is that batching is formed ram-jolt in the plumbago crucible of the profile product that requires of directly packing into after mixing or the saggar.
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| CN102391012A (en) * | 2011-08-02 | 2012-03-28 | 西安交通大学 | Method for preparing recrystallized silicon carbide porous ceramic by combining carbothermic reduction |
| CN102417366A (en) * | 2011-08-30 | 2012-04-18 | 北京理工大学 | Pore gradient silicon carbide porous ceramic and preparation method thereof |
| CN102515800A (en) * | 2011-12-20 | 2012-06-27 | 叶乐 | Microporous graphite silicon carbide brick |
| CN101654376B (en) * | 2009-08-26 | 2012-11-28 | 武汉科技大学 | Porous light heat-insulation and heat-preservation material and preparation method thereof |
| CN103939509A (en) * | 2014-04-22 | 2014-07-23 | 浙江天乐新材料科技有限公司 | Al/Sic and Cu/Sic composite material friction pair used for railway vehicle and manufacturing method thereof |
| CN105254322A (en) * | 2015-11-04 | 2016-01-20 | 陕西科技大学 | Preparation method of oriented porous SiC ceramic with crystal boundary containing metal phases |
| CN105272264A (en) * | 2015-11-04 | 2016-01-27 | 陕西科技大学 | Method for preparing compound co-continuous phase SiC/Si composite material |
| CN106007720A (en) * | 2016-05-11 | 2016-10-12 | 陕西固勤材料技术有限公司 | Silicon carbide composite zero-valent iron porous ceramics for sewage treatment and preparing method |
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| CN107382364A (en) * | 2017-06-30 | 2017-11-24 | 长兴泓矿炉料有限公司 | A kind of light weight low-loss carborundum series refractory material and preparation method thereof |
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| CN101654376B (en) * | 2009-08-26 | 2012-11-28 | 武汉科技大学 | Porous light heat-insulation and heat-preservation material and preparation method thereof |
| CN102391012A (en) * | 2011-08-02 | 2012-03-28 | 西安交通大学 | Method for preparing recrystallized silicon carbide porous ceramic by combining carbothermic reduction |
| CN102417366A (en) * | 2011-08-30 | 2012-04-18 | 北京理工大学 | Pore gradient silicon carbide porous ceramic and preparation method thereof |
| CN102417366B (en) * | 2011-08-30 | 2013-08-07 | 北京理工大学 | Pore gradient silicon carbide porous ceramic and preparation method thereof |
| CN102515800A (en) * | 2011-12-20 | 2012-06-27 | 叶乐 | Microporous graphite silicon carbide brick |
| CN103939509A (en) * | 2014-04-22 | 2014-07-23 | 浙江天乐新材料科技有限公司 | Al/Sic and Cu/Sic composite material friction pair used for railway vehicle and manufacturing method thereof |
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| CN107382364A (en) * | 2017-06-30 | 2017-11-24 | 长兴泓矿炉料有限公司 | A kind of light weight low-loss carborundum series refractory material and preparation method thereof |
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| CN115956064A (en) * | 2020-09-07 | 2023-04-11 | 日本碍子株式会社 | Refractory material |
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| CN112851394B (en) * | 2021-02-03 | 2022-04-12 | 潍坊工商职业学院 | Preparation method of porous silicon carbide ceramic |
| CN115340385A (en) * | 2022-08-30 | 2022-11-15 | 武汉工程大学 | Micron-aperture silicon carbide porous ceramic with controllable aperture and preparation method thereof |
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