CN103936437A - Casting-molded large-scale nitride-combined silicon carbide product - Google Patents
Casting-molded large-scale nitride-combined silicon carbide product Download PDFInfo
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- CN103936437A CN103936437A CN201410116796.7A CN201410116796A CN103936437A CN 103936437 A CN103936437 A CN 103936437A CN 201410116796 A CN201410116796 A CN 201410116796A CN 103936437 A CN103936437 A CN 103936437A
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- silicon
- silicon carbide
- powder
- carbide
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Abstract
The invention relates to a casting-molded large-scale nitride-combined silicon carbide product. The product employs silicon carbide particles and powder, silicon carbide micro powder, silicon dioxide micro powder, alumina micro powder, active magnesium oxide and a water reducer as powder materials, employs silica sol as a binder and is molded by employing vibration casting. A molded blank is subjected to maintenance, drying, and high-temperature nitridation processing in nitrogent, so that the nitride-combined silicon carbide product is prepared. By reacting silicon dioxide and silicon carbide in the materials with nitrogen at the conditions of high temperature and nitrogen, silicon nitride is generated and other nitrides are further generated, and thus the combination strength is generated. The products helps to solve the problems and the disadvantages that conventional nitride-combined silicon carbide products generated through nitridation of silicon powder is high in cost and relatively easily have residual silicon, large-scale products cannot be produced, and the like. According to the technical scheme, the large-scale nitride-combined silicon carbide product can be produced and has the advantages of low cost, excellent performances and the like, the prepared silicon carbide product is capable of replacing conventional Si3N4-combined, Si2N2O-combined and Sialon-combined silicon carbide and being applied to fields of steel industry blast furnace air ports and blast furnace cooling wall cast-in bricks, nonferrous metals industry aluminium electrolytic tanks and the like.
Description
Technical field
The invention belongs to technical field of inorganic nonmetallic materials.Be specifically related to the large-scale nitride combined silicon carbide goods of a kind of casting, can solve and existingly generate nitride by silica flour and be inadequate, can prepare large-scale nitride combined silicon carbide goods, the alternative existing Si of prepared silicon carbide articles
3n
4, Si
2n
2o, Sialon silicon carbide, be applied to the field such as steel industry blast-furnace tuyere and blast furnace cooling wall laying brick, coloured industry aluminium cell.
Background technology
Nitride combined silicon carbide goods are with Si
3n
4, Si
2n
2single-phase or the multiphase nitride such as O, Sialon and AlN is the silicon carbide high grade refractory in conjunction with phase.It has acted on many excellent properties of nitride and carbofrax material, has that hot strength is high, thermal conductivity is high, thermal expansivity is low, thermal shock resistance is good, alkali resistant erosion performance is good, an advantage such as the strong and wear resistance at elevated temperature of the liquation erosional competency such as anti-slag and zinc-aluminium copper-lead is good.At present, multiple nitride combined silicon carbide goods have all obtained industrial application, as a kind of novel high-temperature material, have application prospect very widely at aspects such as smelting iron and steel, non-ferrous metal metallurgy, ceramic industries.
Si
3n
4, Sialon, Si
2n
2the covalent linkage compounds such as O are all engineering ceramic materials of excellent performance, and these synthetic materials are need be under high temperature inert or neutral atmosphere condition could sintering good.At present, with Si
3n
4, Sialon and Si
2n
2o synthesis material directly, as in conjunction with phase raw material, is prepared and is produced Nitride union silicon carbide fire-proof material, fails to obtain actual applying because production cost is high.Nitride combined silicon carbide goods all adopt reaction sintering method preparation substantially now, and its technological principle is: in the industrial silicon carbide materials of certain particle size composition, add respectively appropriate Si powder, Si and SiO
2fine powder, Si and Al
2o
3fine powder and other admixture, through mixing, after moulding in high-purity N
2in atmosphere, carry out reaction sintering in 1400 ~ 1600 DEG C, in sintering process by following chemical reaction:
3Si?+?2N
2?=?Si
3N
4
3Si?+?SiO
2?+?2N
2?=?2Si
2N
2O
Si
3N
4?+?SiO
2?=?2Si
2N
2O
(6-Z)Si
3N
4?+?Z(Al
2O
3?+?AlN)?=?3Si
6-ZAl
ZO
ZN
8-Z
The Si that reaction generates
3n
4, Si
2n
2o or Sialon, by silicon-carbide particle mortise, give goods multiple premium properties.
It is the key link that current nitride combined silicon carbide goods produce bonding strength that silica flour nitridation in situ generates silicon nitride.Along with the continuous nitrogenize of silica flour, in material, void content reduction, air vent aperture reduce.Silicon powder nitride is thermopositive reaction, and the slightly improper local temperature that easily causes of nitridation process control is too high, makes silica flour fusing stop up pore.Above-mentioned two aspect effects make the nitrogenize of goods inside very difficult.Therefore, the technology controlling and process that adopts silica flour nitridation in situ to produce nitride combined silicon carbide material is had relatively high expectations, and it is complete that dimensional thickness is difficult to nitrogenize more than 250mm, easily occurs residual silicon and affects product performance.Above shortcoming makes existing silica flour nitridation in situ technique cannot prepare the nitride combined silicon carbide goods of large-size.
Summary of the invention
For the problems referred to above, the present invention proposes the large-scale nitride combined silicon carbide goods of a kind of casting, the present invention can prepare large size, special-shaped refractory materials, and cost is low, excellent performance.
Object of the present invention is achieved through the following technical solutions: the large-scale nitride combined silicon carbide goods of described casting are to be raw material by silicon-carbide particle and fine powder, silicon carbide micro-powder, fine silica powder and alumina powder, additional activated magnesia, water reducer and silicon sol composition; Described activated magnesia chemical composition requires MgO >=92.0%, tap density≤0.1g/ml;
In the present invention, the weight percent of each raw material is:
Silicon-carbide particle 70～76%
Carbide fine powder 14～20%
Silicon carbide micro-powder 4～8%
Fine silica powder 2～5%
Alumina powder 0.5～1.5%
Activated magnesia is additional, and add-on is the 0.03-0.06% of raw material gross weight
Water reducer is additional, and add-on is the 0.05-0.12% of raw material gross weight
Silicon sol is additional;
The gross weight of described goods raw material is 100%.
The chemical composition of silicon-carbide particle described in the present invention and fine powder requires as SiC >=95%.The size range of silicon-carbide particle is 3 ~ 0.088mm, and carbide fine powder size range is 0.044 ~ 0.020mm.Described silicon carbide micro-powder Chemical Composition requires SiC >=94.0%, and granularity requirements is less than 5 μ m.
Described fine silica powder Chemical Composition requires SiO
2>=95.0%, particle diameter requires≤1 μ m.Described alumina powder chemical composition requires Al
2o
3>=99.0%, particle diameter requires≤5 μ m.
Described water reducer refers to the polyethylene glycol type water reducer CASTMENT FS-20 that BASF Aktiengesellschaft produces.
Described silicon sol is alkaline sodium type silicon sol, SiO
2content range is 20-31%, preferentially selects SiO
2content is the silicon sol of 24-26%.
Above-mentioned particle and powder are proportionally prepared burden, after fully mixing, add silicon sol, silicon sol add-on is controlled 60 ~ 90% according to vibrational flow value.Adopt the moulding of vibrating casting method.After moulding base substrate through maintenance, dry after, high-temperature ammonolysis processing in nitrogen, treatment temp is 1350 ~ 1500 DEG C, the treatment time, according to product size adjustment, makes this nitride combined silicon carbide goods.
Principle of the present invention is: under high temperature, in material, silicon sol dehydration generates nanometer grade silica, nano silicon is evenly wrapped in silicon-carbide particle and fine powder surface, under high temperature and condition of nitrogen gas, in material, silicon-dioxide and silicon carbide reaction in－situ generate silicon nitride, and its reaction equation is as follows:
2SiC+?SiO
2?+?2N
2?=?Si
3N
4?+?2CO
Generated in-situ Si
3n
4and SiO
2solid solution generates Si
2n
2o, and aluminum oxide reaction generates Sialon.The nitride that reaction generates is evenly distributed in whole material, matrix and aggregate is combined closely, thereby the performance such as hot strength of goods is greatly improved.
The present invention has the following advantages:
1, avoided existing silicon powder nitride to generate the mode of silicon nitride, do not needed to add expensive silica flour, solved that conventional nitride combined silicon carbide product cost is high, generating process control requirement is high, be prone to residual silicon and can not produce massive article problem.Invention is passed through in material, between silicon-dioxide, silicon carbide and nitrogen, to react and generate silicon nitride under high temperature nitrogen condition, and further generates other nitride, thereby produces bonding strength.Silicon-dioxide used, sic raw material fusing point are higher, do not have liquid phase and produce under temperature of reaction, can not stop up channel of nitrogen, can be used for producing large-scale nitride combined silicon carbide goods.
2, the present invention adopts casting, and silicon sol used is in conjunction with belonging to non-cement articulated system.Avoid conventional nitride low-temperature binder that combined silicon carbide product adds to introduce the detrimentally affect of impurity, avoided traditional casting aluminous cement bonding agent at high temperature to generate the detrimentally affect of eutectic.After the water evaporation that silicon sol is introduced, in mould material, form and be communicated with pore, provide nitrogen to enter the passage of material internal.The silicon-dioxide that silicon sol is introduced is evenly distributed on silicon-carbide particle, fine powder and micro mist surface, has increased the contact area of silicon-dioxide and silicon carbide, is more conducive to high-temperature ammonolysis reaction.While burning till in nitrogen, a small amount of impurity-sodium oxide volatilization that makes silicon sol introduce because oxygen partial pressure is lower, makes the further sublimate of material.
3, silicon sol solidifies generation blank strength by adjusting its pH value or introducing alkaline-earth metal ions conventionally.Compared with introducing alkaline-earth metal ions, adjust the curing base substrate of pH value and only depend on silicon-dioxide Coagulating binding each other, low being difficult to of intensity meets the requirements such as carrying, makes material internal in the operation process before the bakings such as form removal easily produce defect, increased the scrap rate of material.It is higher that alkaline-earth metal ions solidifies blank strength, but Ca
2+or Mg
2+be unfavorable for material at high temperature performance Deng the introducing of foreign ion.The present invention has added the activated magnesia that granularity is tiny, specific surface area is large, the Mg that utilizes its aquation to generate
2+by silicon sol and fine silica powder surface-Si-O
-group is joined to one another, and makes material solidification and have higher blank strength high.The magnesium nitride gas that magnesium oxide, magnesium hydroxide and nitrogen reaction under high temperature in base substrate generates, is conducive to material nitrogenize, and has reduced foreign matter content in silicon carbide articles.
4, compound silicon carbide micro-powder, fine silica powder and the alumina powder of adding, has optimized the size composition of mould material matrix, the flowing property while having improved moulding.The specific surface area that fine silica powder and silicon carbide micro-powder are higher is conducive to the generation of nitride.Add appropriate alumina powder to promote original position to generate the different growth of nitride, improved the mechanical property of silicon carbide articles.
Embodiment
Illustrate enforcement of the present invention and feature below, but the present invention is not limited to following embodiment.
Embodiment 1: feed composition and proportioning (mass percent) they are silicon-carbide particle 75.5%, carbide fine powder 14%, silicon carbide micro-powder 8%, fine silica powder 2%, alumina powder 0.5%, activated magnesia (additional) 0.06%, water reducer (additional) 0.07%.
Embodiment 2: feed composition and proportioning (mass percent) they are silicon-carbide particle 70%, carbide fine powder 17.5%, silicon carbide micro-powder 6%, fine silica powder 5%, alumina powder 1.5%, activated magnesia (additional) 0.03%, water reducer (additional) 0.12%.
Embodiment 3: feed composition and proportioning (mass percent) they are silicon-carbide particle 74%, carbide fine powder 16%, silicon carbide micro-powder 5.5%, fine silica powder 4%, alumina powder 0.5%, activated magnesia (additional) 0.04%, water reducer (additional) 0.08%.
Embodiment 4: feed composition and proportioning (mass percent) they are silicon-carbide particle 76%, carbide fine powder 15.5%, silicon carbide micro-powder 5%, fine silica powder 3%, alumina powder 0.5%, activated magnesia (additional) 0.05%, water reducer (additional) 0.05%.
Embodiment 5: feed composition and proportioning (mass percent) they are silicon-carbide particle 70%, carbide fine powder 20%, silicon carbide micro-powder 4%, fine silica powder 5%, alumina powder 1%, activated magnesia (additional) 0.03%, water reducer (additional) 0.1%.
After above-mentioned particle and powder are proportionally fully mixed, add SiO
2content is 25% alkaline sodium type silicon sol, adjusts respectively the mass percent that its vibrational flow value accounts for powder at silicon sol that 60 ~ 90%, embodiment, 1 ~ embodiment 5 adds and is respectively: 6.7%, 7.2%, 6.4%, 6.0% and 7.0%.After adding silicon sol, fully mix, silicon sol is wrapped in around particle and powder uniformly.Add vibration limit in limit in mould to feed in raw material in the material mixing, mould material is filled in whole mould uniformly.After moulding, base substrate is after maintenance, drying, and high-temperature ammonolysis processing in nitrogen, makes this nitride combined silicon carbide goods.
Claims (5)
1. the large-scale nitride combined silicon carbide goods of casting, is characterized in that described goods are is raw material by silicon-carbide particle and fine powder, silicon carbide micro-powder, fine silica powder and alumina powder, additional activated magnesia, water reducer and silicon sol composition; Described activated magnesia chemical composition requires MgO >=92.0%, tap density≤0.1g/ml; Above-mentioned particle and powder are proportionally prepared burden, after fully mixing, add silicon sol, silicon sol add-on is controlled 60 ~ 90% according to vibrational flow value; Adopt the moulding of vibrating casting method; Base substrate after moulding through maintenance, dry after, high-temperature ammonolysis processing in nitrogen, treatment temp is 1350 ~ 1500 DEG C, makes nitride combined silicon carbide goods;
In the present invention, the weight percent of each raw material is:
Silicon-carbide particle 70～76%
Carbide fine powder 14～20%
Silicon carbide micro-powder 4～8%
Fine silica powder 2～5%
Alumina powder 0.5～1.5%
Activated magnesia is additional, and add-on is the 0.03-0.06% of raw material gross weight
Water reducer is additional, and add-on is the 0.05-0.12% of raw material gross weight
Silicon sol is additional;
The gross weight of described goods raw material is 100%.
2. the large-scale nitride combined silicon carbide goods of a kind of casting according to claim 1, is characterized in that: the chemical composition of described silicon-carbide particle and fine powder requires as SiC >=95%; The size range of silicon-carbide particle is 3 ~ 0.088mm, and carbide fine powder size range is 0.044 ~ 0.020mm; Described silicon carbide micro-powder Chemical Composition requires SiC >=94.0%, and granularity requirements is less than 5 μ m.
3. the large-scale nitride combined silicon carbide goods of a kind of casting according to claim 1, is characterized in that: described fine silica powder Chemical Composition requires SiO
2>=95.0%, particle diameter requires≤1 μ m; Described alumina powder chemical composition requires Al
2o
3>=99.0%, particle diameter requires≤5 μ m.
4. the large-scale nitride combined silicon carbide goods of a kind of casting according to claim 1, is characterized in that: described water reducer is the polyethylene glycol type water reducer CASTMENT FS-20 that BASF Aktiengesellschaft produces.
5. the large-scale nitride combined silicon carbide goods of a kind of casting according to claim 1, is characterized in that: described silicon sol is alkaline sodium type silicon sol, SiO
2content range is 20-31%, preferentially selects SiO
2content is the silicon sol of 24-26%.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106045522A (en) * | 2015-06-27 | 2016-10-26 | 湖北神雾热能技术有限公司 | Nonmetal material tray for refuse pyrolysis furnace rotating bed and preparation method thereof |
| CN110423118A (en) * | 2019-07-24 | 2019-11-08 | 洛阳市科创绿色建材研究院 | A kind of copper chute composite ceramics phase antiseep wear-resisting material produced with polycrystalline silicon wastes |
| CN112794703A (en) * | 2021-02-20 | 2021-05-14 | 中冶武汉冶金建筑研究院有限公司 | High-aluminum self-flow castable and preparation method thereof |
| CN112830772A (en) * | 2021-01-22 | 2021-05-25 | 中冶武汉冶金建筑研究院有限公司 | Submicron silica micropowder combined iron runner castable and preparation method thereof |
| CN113121240A (en) * | 2021-04-23 | 2021-07-16 | 中钢集团洛阳耐火材料研究院有限公司 | Preparation method of high-wear-resistance nitride-combined silicon carbide composite ceramic overcurrent part |
| CN113698218A (en) * | 2021-10-29 | 2021-11-26 | 北京利尔高温材料股份有限公司 | Tundish cover castable and preparation method thereof |
| CN114163254A (en) * | 2022-02-11 | 2022-03-11 | 北京利尔高温材料股份有限公司 | Blast furnace iron tap channel main channel castable |
| CN116178025A (en) * | 2023-03-24 | 2023-05-30 | 长兴兴鹰新型耐火建材有限公司 | High-strength light explosion-proof castable |
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| CN101823892A (en) * | 2010-04-29 | 2010-09-08 | 河南科技大学 | Cement-free in-situ silicon nitride combined silicon carbide prefabricated member and preparation method thereof |
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Patent Citations (2)
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| CN101823892A (en) * | 2010-04-29 | 2010-09-08 | 河南科技大学 | Cement-free in-situ silicon nitride combined silicon carbide prefabricated member and preparation method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106045522A (en) * | 2015-06-27 | 2016-10-26 | 湖北神雾热能技术有限公司 | Nonmetal material tray for refuse pyrolysis furnace rotating bed and preparation method thereof |
| CN110423118A (en) * | 2019-07-24 | 2019-11-08 | 洛阳市科创绿色建材研究院 | A kind of copper chute composite ceramics phase antiseep wear-resisting material produced with polycrystalline silicon wastes |
| CN112830772A (en) * | 2021-01-22 | 2021-05-25 | 中冶武汉冶金建筑研究院有限公司 | Submicron silica micropowder combined iron runner castable and preparation method thereof |
| CN112794703A (en) * | 2021-02-20 | 2021-05-14 | 中冶武汉冶金建筑研究院有限公司 | High-aluminum self-flow castable and preparation method thereof |
| CN113121240A (en) * | 2021-04-23 | 2021-07-16 | 中钢集团洛阳耐火材料研究院有限公司 | Preparation method of high-wear-resistance nitride-combined silicon carbide composite ceramic overcurrent part |
| CN113698218A (en) * | 2021-10-29 | 2021-11-26 | 北京利尔高温材料股份有限公司 | Tundish cover castable and preparation method thereof |
| CN114163254A (en) * | 2022-02-11 | 2022-03-11 | 北京利尔高温材料股份有限公司 | Blast furnace iron tap channel main channel castable |
| CN114163254B (en) * | 2022-02-11 | 2022-04-26 | 北京利尔高温材料股份有限公司 | Blast furnace iron tap channel main channel castable |
| CN116178025A (en) * | 2023-03-24 | 2023-05-30 | 长兴兴鹰新型耐火建材有限公司 | High-strength light explosion-proof castable |
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