CN104058754A - Beta-SiC/Si2N2O complex phase combined SiC kiln furniture and preparation method - Google Patents

Beta-SiC/Si2N2O complex phase combined SiC kiln furniture and preparation method Download PDF

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CN104058754A
CN104058754A CN201410225264.7A CN201410225264A CN104058754A CN 104058754 A CN104058754 A CN 104058754A CN 201410225264 A CN201410225264 A CN 201410225264A CN 104058754 A CN104058754 A CN 104058754A
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polycrystalline silicon
complex phase
conjunction
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CN104058754B (en
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王婷
李勇
孙加林
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Beijing University of Technology
University of Science and Technology Beijing USTB
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University of Science and Technology Beijing USTB
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Abstract

The invention discloses a beta-SiC/Si2N2O complex phase combined SiC kiln furniture and a preparation method, belonging to the field of fireproof materials. Raw materials comprise silicon carbonate, metallic Si, a polycrystalline silicon waste material as well as waste pulping liquor which is 2%-6% of the raw materials in total content and is used as a binding agent. During production, various raw materials are weighed in proportion and mixed to obtain a pug material, and the pug material is compression-molded, dried for 24-28 hours at the temperature of 110+/-10 DEG C and then sintered at the temperature of 1200-1500 DEG C under a carbon-buried condition. The product has the following excellent physical performance indexes: apparent porosity being 9% to 22%, volume density being 2.3g/cm<3> to 2.9g/cm<3>, compression strength at normal temperature being 60MPa to 200MPa, rupture strength at normal temperature being 20MPa to 75MPa, good oxidation resistance and good thermal shock resistance. In the method disclosed by the invention, the polycrystalline silicon waste material is taken as the raw material, and a carbon-buried sintering mode is adopted to simplify the production process, so the production cost of the SiC kiln furniture is lowered, the recycle of the polycrystalline silicon waste material is realized as well, and the waste of resources and environmental pollution are reduced.

Description

β-SiC/Si 2n 2o complex phase is in conjunction with SiC kiln furnitures and preparation method
Technical field
The present invention relates to a kind of β-SiC/Si of fire resisting material field 2n 2o complex phase is in conjunction with SiC kiln furnitures and preparation method.
Background technology
Kiln furnitures are a kind of high grade refractories, and its quality has extremely important impact to the quality of burnt product and energy consumption.Along with applying of ceramic industry quick sintering technology of ultra, the loop cycle that kiln furnitures use is shorter and shorter, working conditions is more harsh, and an urgent demand kiln furniture material improves constantly its normal temperature, hot strength and heat-shock resistance, to meet the needs of ceramic industry quick sintering technology of ultra development.Silicon carbide series refractory material is obtained development and application because having the premium propertiess such as high thermal conductivity, low thermal expansivity, good high-temperature behavior and heat-shock resistance by extensive kiln furnitures as ceramic kiln.
SiC has very strong covalent linkage characteristic, is difficult to sintering under general processing condition, conventionally need add sintering aid or the parcel by second-phase (in conjunction with phase) to obtain fine and close silicon carbide sintering block.β-SiC and Si 2n 2o is well in conjunction with phase, has very excellent performance, SiC particle can be combined, and promotes its density, improves the physicochemical property of SiC kiln furnitures.β-SiC hot strength is high, has stronger creep resistance, alkali-resistivity, oxidation-resistance; Si 2n 2o has and Si 3n 4similar performance, but its oxidation-resistance and heat-shock resistance are better than Si 3n 4.Therefore, simultaneously with Si 2n 2o and β-SiC, for the SiC goods in conjunction with phase have higher normal temperature, hot strength and good heat-shock resistance, are being better than Si aspect kiln furnitures 3n 4with the goods of silicate in conjunction with phase.The researchs such as Liu Chunxia show Si 2n 2o is better than Si in conjunction with the heat-shock resistance of SiC sample 3n 4in conjunction with SiC sample.Japan has realized Si 2n 2the suitability for industrialized production of O silicon carbide kiln furnitures, but domestic still in developmental stage.Accelerate long lifetime β-SiC/Si 2n 2o complex phase has urgent demand in conjunction with the development of SiC high-quality kiln furnitures.At present domestic and international Si 2n 2the production of O silicon carbide kiln furnitures is mainly passed through with SiC, SiO 2micro mist, silica flour, clay are that raw material burns till and makes at high-temperature ammonolysis kiln, and the performance of material is still needed and further improved and improve, and has the drawbacks such as production cost is high, energy consumption is large, processing condition are complicated, expensive.
In recent years, the energy, information industry are flourish, as the polysilicon market of main raw material, also constantly expand thereupon.But polysilicon can be used after need to cutting into silicon chip.At cutting process, because cutter damage becomes the crystalline silicon that has 50%~52% into silicon powder, enter cutting slurry, cause cutting efficiency to reduce, finally cutting slip inefficacy becomes slug, causes the wasting of resources and environmental pollution, to enterprise, has brought huge pressure.Therefore generally adopt at present silicon carbide as cutting abrasive material, cut and in slug, mainly contain HIGH-PURITY SILICON, polyoxyethylene glycol (dispersion agent), silicon carbide and a small amount of metal, but silicon and silicon carbide are in physics and chemistry less, the separation difficulty of difference in nature.Therefore Pure Silicon Metal and silicon carbide, how to recycle cost-effectively in cutting waste material are current problem demanding prompt solutions.
Summary of the invention
The present invention is intended to the performance requirement to kiln furniture material according to ceramic industry at present, overcomes existing Si 2n 2the defects such as improvement that O silicon carbide kiln furnitures production cost is high, energy consumption is large, processing condition are complicated, performance is still needed, make full use of β-SiC and Si 2n 2the performance characteristics of O, has proposed a kind of β-SiC/Si that polycrystalline silicon wastes is raw material of take 2n 2o complex phase, in conjunction with SiC kiln furnitures and preparation method, has not only improved the performance of kiln furnitures, has reduced the production cost of kiln furnitures, has also realized the comprehensive recycling of polycrystalline silicon wastes, has reduced the wasting of resources and environmental pollution.
Technical solution of the present invention:
(1). raw material forms and mass ratio: by weight percentage, 25-55% particle diameter is the SiC particle of 3-1mm, 10-25% particle diameter is 1-0.2mmSiC particle, 5-25% particle diameter≤0.088mmSiC fine powder, 0-25% metal Si, 5-30% polycrystalline silicon wastes, the spent pulping liquor of additional above-mentioned raw materials total amount 2-6% is as bonding agent.In described silicon carbide, SiC content is greater than 98%; In described metal Si, Si content is greater than 98%, and granularity is≤0.088mm; The granularity of described polycrystalline silicon wastes is discrete distribution, and between 1um and 240um, mean particle size is 20um ± 10um; In polycrystalline silicon wastes, contents of free si is 25-60%, carborundum content is 25-60%, alumina content is 3-7%, metal Fe content is 1-5%, CaO content is less than 0.5%, it is 0.5-3% that MgO content is less than 1%, PEG (polyoxyethylene glycol, English full name polyethylene glycol) content.
(2). burden process: take various raw materials by proportioning, will be in advance load weighted SiC thick, in two kinds of granulated aggregates mix to pour in wheel roller and further mix, after 3~5min, stop stirring, pour half that weighs in advance the bonding agent prepare into wheel roller, open again switch and stir 5min, make bonding agent be evenly distributed on particle surface; Then load weighted SiC fine powder, polycrystalline silicon wastes are poured into wheel roller and stirred 5min, more remaining bonding agent is all poured into and wherein continued to stir 8~12min, stop stirring.
(3). molding procedure: the raw material mixing is pressed into firebrick billet with vibrating forming machine or friction press.
(4). baking operation: the firebrick billet of forming is put into 110 ± 10 ℃ of dry 24-48h of moisture eliminator, control moisture content below 0.5%.
(5). firing process: the adobe making is buried under carbon condition and burnt till and prepare β-SiC/Si at 1200-1500 ℃ 2n 2o complex phase is in conjunction with SiC refractory materials.
Compared with prior art, feature of the present invention and positively effect:
1. the present invention adopts and to bury carbon process for calcining and prepared β-SiC/Si 2n 2o complex phase is in conjunction with SiC kiln furnitures.With original nitridation sintered comparing, simplified technique, reduced production cost.
2. product of the present invention is with β-SiC and Si 2n 2o is in conjunction with phase, is closely wrapped in around SiC particle, has improved the density of material.β-SiC hot strength is high, has stronger creep resistance, alkali-resistivity, oxidation-resistance; Si 2n 2o has and Si 3n 4similar performance, but its oxidation-resistance and heat-shock resistance are better than Si 3n 4.Product combines both performance advantages, has higher normal temperature, hot strength and good oxidation-resistance and thermal shock resistance.
3. the present invention, using polycrystalline silicon cut waste as raw material, replaces all or part of industrial silicon carbide and metallic silicon power, and in realizing under the condition of not separating silicon carbide and Pure Silicon Metal, the recycling of polycrystalline silicon wastes, had both reduced β-SiC/Si 2n 2o complex phase, in conjunction with the preparation cost of SiC kiln furnitures, has reduced again the waste of resource and the pollution of environment.
4. in the polycrystalline silicon cut waste that the present invention adopts, contain a small amount of PEG, at moulding and initial stage of sintering, can play the effect of bonding agent, improve filling properties and the processability of raw material, with spent pulping liquor, replace original resol to use, improved the raw-material feature of environmental protection.
5. the polycrystalline silicon cut waste granularity that the present invention adopts is discrete distribution, is conducive to raw-material grain composition, improves the density of material.Free silica granularity in polycrystalline silicon wastes is little, and surface-area is large, and reactive behavior is large, while existing with industrial silica fume simultaneously, and CO, the N of energy preferentially and in atmosphere 2rapid reaction, forms gradient reaction step by step, optimizes the structure of material.
6. product of the present invention has good physical performance index.Apparent porosity 9-22%, volume density 2.3-2.9g/cm 3, cold crushing strength 60-200MPa, strength at normal temperature 20-75Mpa, there is good oxidation-resistance and heat-shock resistance.
7. the requirement of the aspect such as kiln furnitures product of the present invention can meet ceramic industry intensity is high, heat-shock resistance is strong, oxidation-resistance is strong, and production technique is relatively simple, production cost is low, market potential is large, is suitable for applying, and will have good economic and social benefit.
Embodiment
Embodiment 1:
A kind of β-SiC/Si 2n 2o complex phase is in conjunction with SiC kiln furnitures and preparation method thereof, and by weight percentage, raw material consists of: the SiC particle 45% of particle diameter 3-1mm, particle diameter 1-0.2mmSiC particle 15%, particle diameter≤0.088mmSiC fine powder 13%, Industrial Metal silica flour 17%, polycrystalline silicon wastes 10%, additional 3% spent pulping liquor.
(1). batching: take various raw materials by proportioning, will be in advance load weighted SiC thick, in two kinds of granulated aggregates mix to pour in wheel roller and further mix, after 3~5min, stop stirring, by the bonding agent that weighing prepares in advance, half pours wheel roller into, open again switch and stir 5min, make bonding agent be evenly distributed on particle surface; Then load weighted SiC fine powder, polycrystalline silicon wastes are poured into wheel roller and stirred 5min, more remaining bonding agent is all poured into and wherein continued to stir 8min, stop stirring.
(2). moulding: the raw material mixing is pressed into firebrick billet with vibrating forming machine or friction press.
(3). dry: the refractory brick of forming is put into 110 ℃ of dry 48h of moisture eliminator, control moisture content below 0.5%.
(4). burn till: the adobe making is buried under carbon condition and burnt till and prepare β-SiC/Si at 1450 ℃ 2n 2o complex phase is in conjunction with SiC refractory materials.
The physical and chemical index of products obtained therefrom is: apparent porosity 15%, volume density 2.65g/cm 3, cold crushing strength 168MPa, strength at normal temperature 65MPa, heat-shock resistance, oxidation-resistance are all better.
Embodiment 2:
Raw material forms identical with embodiment 1, and production technique and example 1 are basic identical, and difference is: sintering temperature is 1500 ℃.
The performance index of products obtained therefrom are: apparent porosity 16%, volume density 2.61g/cm 3, cold crushing strength 157MPa, high temperature break resistant intensity 56MPa, its heat-shock resistance, oxidation-resistance are all better.

Claims (3)

1. a β-SiC/Si 2n 2o complex phase is in conjunction with SiC kiln furnitures, it is characterized in that: raw material by weight percentage consists of the SiC particle that 25-55% particle diameter is 3-1mm, 10-25% particle diameter is 1-0.2mmSiC particle, 5-25% particle diameter≤0.088mmSiC fine powder, 0-25% metal Si, 5-30% polycrystalline silicon wastes, the spent pulping liquor of additional above-mentioned raw materials total amount 2-6% is as bonding agent.
2. β-SiC/Si according to claim 1 2n 2o complex phase, in conjunction with SiC kiln furnitures, is characterized in that: in described silicon carbide, SiC content is greater than 98%; In metal Si, Si content is greater than 98%, and particle diameter is≤0.088mm; The granularity of described polycrystalline silicon wastes is discrete distribution, between 1um and 240um, mean particle size is 20um ± 10um, in polycrystalline silicon wastes, contents of free si is 25-60%, and carborundum content is 25-60%, and alumina content is 3-7%, metal Fe content is 1-5%, CaO content is less than 0.5%, MgO content, and to be less than 1%, PEG content be 0.5-3%.
3. β-SiC/Si as claimed in claim 1 or 2 2n 2o complex phase, in conjunction with the preparation method of SiC kiln furnitures, is characterized in that: preparation method comprises the following steps:
A. by proportioning, take various raw materials, will be in advance load weighted SiC thick, in two kinds of granulated aggregates mix to pour in wheel roller and further mix, after 3~5min, stop stirring, pour half that weighs in advance the bonding agent prepare into wheel roller, open again switch and stir 5min, make bonding agent be evenly distributed on particle surface; Then load weighted SiC fine powder, polycrystalline silicon wastes are poured into wheel roller and stirred 5min, more remaining bonding agent is all poured into and wherein continued to stir 8-12min, stop stirring;
B. the raw material mixing is pressed into firebrick billet with vibrating forming machine or friction press;
C. the firebrick billet of forming is put into 110 ± 10 ℃ of dry 24-48h of moisture eliminator, controlled moisture content below 0.5%;
D. the adobe making is buried under carbon condition and burnt till and prepare β-SiC/Si at 1200-1500 ℃ 2n 2o complex phase is in conjunction with SiC refractory brick.
CN201410225264.7A 2014-05-26 2014-05-26 β-SiC/Si2N2O complex phase is in conjunction with SiC kiln furnitures and preparation method Expired - Fee Related CN104058754B (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104313678A (en) * 2014-10-14 2015-01-28 武汉科技大学 Whisker-like SiC/Si3N4/Si2N2O composite powder and preparation method thereof
CN106431431A (en) * 2016-08-31 2017-02-22 江苏诺明高温材料股份有限公司 In-situ generating method for Si2N2O ceramic bonding phases in aluminum-carbon fireproof material with carbon thermal reduction method
CN106966732A (en) * 2017-03-09 2017-07-21 平顶山学院 A kind of fine powder silicon carbide ceramics and preparation method thereof
CN108275969A (en) * 2018-01-31 2018-07-13 景德镇陶瓷大学 It is a kind of to utilize the mullite silicon carbide whisker composite ceramic material and preparation method thereof that natural minerals are raw material
CN109293373A (en) * 2018-10-23 2019-02-01 河南省衡锐佳新材料科技有限公司 A kind of preparation of environment-friendly silicon-based additive and the application method in refractory material
CN110981510A (en) * 2019-12-18 2020-04-10 宜兴市丁山耐火器材有限公司 Silicon oxynitride and silicon carbide combined refractory brick and preparation method thereof

Citations (2)

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CN101602607A (en) * 2009-06-21 2009-12-16 贾剑光 Cement kiln preheaters complex nitride based on silicon carbide link plate and method for cooking
CN102275925A (en) * 2011-06-09 2011-12-14 东北大学 Method for sintering silicon carbide through crystalline silicon cutting waste material nitridation reaction

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101602607A (en) * 2009-06-21 2009-12-16 贾剑光 Cement kiln preheaters complex nitride based on silicon carbide link plate and method for cooking
CN102275925A (en) * 2011-06-09 2011-12-14 东北大学 Method for sintering silicon carbide through crystalline silicon cutting waste material nitridation reaction

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104313678A (en) * 2014-10-14 2015-01-28 武汉科技大学 Whisker-like SiC/Si3N4/Si2N2O composite powder and preparation method thereof
CN104313678B (en) * 2014-10-14 2017-04-26 武汉科技大学 Whisker-like SiC/Si3N4/Si2N2O composite powder and preparation method thereof
CN106431431A (en) * 2016-08-31 2017-02-22 江苏诺明高温材料股份有限公司 In-situ generating method for Si2N2O ceramic bonding phases in aluminum-carbon fireproof material with carbon thermal reduction method
CN106966732A (en) * 2017-03-09 2017-07-21 平顶山学院 A kind of fine powder silicon carbide ceramics and preparation method thereof
CN108275969A (en) * 2018-01-31 2018-07-13 景德镇陶瓷大学 It is a kind of to utilize the mullite silicon carbide whisker composite ceramic material and preparation method thereof that natural minerals are raw material
CN108275969B (en) * 2018-01-31 2020-04-07 景德镇陶瓷大学 Mullite-silicon carbide whisker composite ceramic material taking natural minerals as raw materials and preparation method thereof
CN109293373A (en) * 2018-10-23 2019-02-01 河南省衡锐佳新材料科技有限公司 A kind of preparation of environment-friendly silicon-based additive and the application method in refractory material
CN109293373B (en) * 2018-10-23 2021-05-28 河南省衡锐佳新材料科技有限公司 Preparation of environment-friendly silicon-based additive and application method of environment-friendly silicon-based additive in refractory material
CN110981510A (en) * 2019-12-18 2020-04-10 宜兴市丁山耐火器材有限公司 Silicon oxynitride and silicon carbide combined refractory brick and preparation method thereof

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