CN1223550C - Sialon combined fireproof material containing aluminum silicon alloy - Google Patents
Sialon combined fireproof material containing aluminum silicon alloy Download PDFInfo
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- CN1223550C CN1223550C CN 02137290 CN02137290A CN1223550C CN 1223550 C CN1223550 C CN 1223550C CN 02137290 CN02137290 CN 02137290 CN 02137290 A CN02137290 A CN 02137290A CN 1223550 C CN1223550 C CN 1223550C
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- fine powder
- sialon
- silicon alloy
- aluminum silicon
- corundum
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Abstract
The present invention provides a sialon combined fireproofing material containing aluminum silicon alloys. The fireproofing material contains 60 to 75% of corundum skeletal material, 10 to 20% of corundum fine powder, 5 to 15% of aluminum silicon alloy fine powder, 1.5 to 5% of clay and 5 to 12% of aluminum oxide fine powder, wherein the aluminum silicon alloy fine powder is prepared by processing metallic aluminum and metallic silicon through mixture, preparation, fusion or sintering. The aluminum silicon alloy fine powder is used in the fireproofing material, which is helpful to quickly generate sialon combined phases in the process of the sintering of sialon combined corundum bricks and improve the bonding strength of the sialon combined phases and the brown corundum skeletal material. The sintering temperature of the sialon combined fireproofing material is reduced to about 1430 DEG C from the conventional temperature above 1500 DEG C, which is helpful to enhance the fracture resistance toughness of the fireproofing material and enhance the resistance capability of high temperature heat stress damage to the fireproofing material.
Description
Technical field
The present invention relates to a kind of Sialon combined fireproof material.
Background technology
G.Ervin found the practicality of SiC-AlN sosoloid as far back as 1970 and applies for a patent first.
Early seventies, the researchist of Britain and Japan finds an Al
2O
3Join Si
3N
4In carry out hot pressing, at Si
3N
4Lattice in the Al of solid solution
2O
3Can reach 60～70% (weight), and find the Si in this sosoloid
3N
4Siliciumatom and N atom and respectively by the displacement of Al atom and Sauerstoffatom, formed a new system of Si-Al-O-N, and with their the order called after Sialon (Sialon) of first letter.
Jacques.P.R. proposed a kind of in high-melting-point raw materials such as corundum, mullite, zirconium mullite, magnesia by add 23～90% granularity less than the metallic silicon power of 150 μ m, 9～62% granularity less than the sintering oxidation aluminium powder of 20 μ m, 0～24% granularity less than the metallic aluminium powder of 80 μ m, 3～45% granularity greater than the boron nitride of 100m and crystalline flake graphite, 0～3% clay; under 1300～1600 ℃ of nitrogen protections, preparation is mainly used in the method for the Sialon combined fire-resistant material of ladle slide plate etc.
With AlN and Si
3N
4Deng being raw material or using metallic aluminium that Pure Silicon Metal and alumina raw material etc. the at high temperature basic synthetic method of synthetic beta-Sialon phase have had a large amount of reports.Aforesaid method has had the theory of comparative maturity in the fine structure pottery, but at fire resisting material field, adopting above-mentioned synthetic method to still have is worth further improved place.Particularly in the overhaul or new construction of large blast furnace,, use large size refractory brick to become an inevitable trend in order to reduce construction period significantly.Adopt the standard specifications of 230 * 115 * 65mm can't satisfy the requirement of using and constructing, suggestion adopts the above specification of 415 * 200 * 154mm to become developing direction.Because above-mentioned big specification blast furnace has increased about 7.5 times with the volume of refractory brick than standard square.In suitability for industrialized production beta-Sialon combined corundum brick, will have to increase considerably firing temperature and prolong soaking time, even so, how guaranteeing in the control of the industrialization firing process of reality does not have unreacted metal aluminium and Pure Silicon Metal in the centre of the refractory brick of big specification, and how guaranteeing can to generate equally distributed beta-Sialon in the centre of the refractory brick of big specification still has the optimization of many leftover problem products for further aspect equating.
Summary of the invention
The object of the present invention is to provide a kind of Sialon combined fireproof material, improving Sialon in conjunction with mutually and the bonding strength between the brown corundum aggregate, and help to increase the anti-fracture toughness property of refractory materials, improve the high temperature resistance thermal stress damage ability of refractory materials.
We can find according to the synthesis technique of at present a large amount of Sialon phases and test-results: when using highly purified AlN, Al
2O
3And Si
3N
4During for the raw material of Sialon combined corundum brick, the growing amount of Sialon phase is subjected to Al and O atom to Si
3N
4The control of the rate of diffusion in 4 lattices if take can shorten someway the diffusion length of Al and O atom, undoubtedly can promote the generation of Sialon phase.For this reason the present inventor proposed to synthesize in advance a kind of on chemical constitution with generate the Sialon duplicate aluminum silicon alloy that requires mutually and rely on metallic aluminium atom and the mixed uniformly favourable condition of Pure Silicon Metal atom on atomic scale in the aluminum silicon alloy, then in the nitridation process of aluminum silicon alloy, correspondingly be formed on mixed uniformly aluminium nitride and silicon nitride on the molecular scale.
Sialon combined fireproof material of the present invention, its raw material contain following composition (weight percent):
Aggregate 60～75%
Fine powder 10～20%
Aluminum silicon alloy fine powder 5～15%
Aluminum oxide fine powder 5～12%
Clay 1.5～5%
Wherein, described aggregate is corundum or silicon nitride or mullite; Described fine powder is corundum or silicon nitride or mullite;
Described aluminum silicon alloy fine powder is to be formed by metallic aluminium and Pure Silicon Metal mixed melting or sintering; The metallic aluminium in the described aluminum silicon alloy fine powder and the proportioning of Pure Silicon Metal are to determine that in conjunction with Z coefficient mutually the Z coefficient is 1.0～4.0 according to predetermined Sialon, and the weight percent of metallic aluminium and Pure Silicon Metal is: Si:60～94%, Al:6.0～40%.
Described aluminum silicon alloy fine powder, clay, aluminum oxide fine powder are the 180-320 order.
Described aluminum silicon alloy fine powder in the preparation, adding has that to account for weight alloy per-cent be that 30～60% aluminum oxide fine powder is as stopping composition.
Described aluminum silicon alloy fine powder in the preparation, adding has that to account for weight alloy per-cent be 1～10% silicon nitride fine powder.
Reaction mechanism of the present invention
For the ease of explaining, preestablish following assumed condition:
(1) when with single metal silicon fine powder and metallic aluminium during as the raw material of synthetic beta-Sialon, the particle diameter of Pure Silicon Metal/metallic aluminium fine powder is 200 orders or 0.074mm;
(2) volumetric expansion in nitridation process of Pure Silicon Metal and metallic aluminium is not temporarily calculated.
According to above-mentioned assumed condition, at high temperature reaction generates Si with nitrogen when Pure Silicon Metal
3N
4The time, this means that the longest straight line diffusion length from the surface to the silicon nitride core of the aluminium nitride aluminium atom that is arranged in silicon nitride resultant particle outside surface is 3.7 * 10
5, when using aluminum silicon alloy as synthesis material, because Pure Silicon Metal and metallic aluminium are in the dispersion level on the atomic scale, when Z=2.0 to 4.0, the atomic quantity of Pure Silicon Metal and metallic aluminium is than greatly in 6: 1 to 1.5: 1 scope.This also means simultaneously Si
3N
4Compare greatly about 2: 1 to 0.75: 1 with the molecular amounts of AlN, be not difficult to find from the aforementioned calculation value: as synthesizing aluminium nitride and two kinds of resultants of silicon nitride that Sialon needs mutually, at the beginning of generating, be in good molecular level admixture, when with aluminium nitride molecule that the silicon nitride molecule contacts in aluminium atom when in the lattice of silicon nitride, spreading, its unidirectional straight line diffusion length no longer has been 3.7 * 10
5About , in fact be contracted to the following (β-Si of 10
3N
4Lattice parameter.A=760.8pm, c=291.1pm, α=108.0 °, remarks: 1Pm=10
-12M, 1 =10
-10M), reduction magnification is 10
4About.Therefore the aluminium atom is under suitable temperature condition, the needed time of diffusion will shorten greatly in the silicon nitride lattice, thereby make the speed of response of whole system be greatly improved, or can keep under the common speed of response condition, reduce temperature of reaction significantly, so that save energy, or reduction is simplified firing process etc. to the requirement of calcination equipment.For example in the present invention, when with temperature of reaction when about 1500 ℃ of routine are reduced to 1430 ℃, although reduction along with temperature of reaction, velocity of diffusion between the reactant will obviously descend, but, because the rapid decline of diffusion length between the reactant, and the positive-effect cause is far longer than the negative effect that the decline owing to velocity of diffusion causes because diffusion length descends, even therefore under lower temperature of reaction condition, use aluminum silicon alloy still can synthesize beta-Sialon rapidly in conjunction with phase.
Fig. 1 is conventional Sialon phase generation model, its aspect of model is: reaction generates silicon nitride and aluminium nitride with nitrogen separately for Pure Silicon Metal and metallic aluminium, and then and batching in aluminum oxide fine powder reaction, under the temperature about 1500 ℃, the Si-Al-O-N atom finally generates the Sialon phase through diffusion mutually for a long time.
Fig. 2 is the model that aluminum silicon alloy of the present invention generates the Sialon phase, in above-mentioned reaction process, at first reaction generates aluminium nitride to the metallic aluminium atom with nitrogen, because inevitably volumetric expansion in the aluminium nitride generative process, in aluminum silicon alloy, will cause corresponding volumetric expansion and short texture, and not participate in the aluminium nitride Buddhist monk who has generated and form a rapid diffusion passage between the Pure Silicon Metal of reaction.That is the surface that nitrogen-atoms will be with comparalive ease arrives the Pure Silicon Metal atom by the passage between aluminium nitride and the Pure Silicon Metal generates silicon nitride.In addition owing to the generation of aluminium nitride prior to silicon nitride, therefore, can not have continuous and fine and close silicon nitride product layer in the final nitrogenize product of aluminum silicon alloy, silicon nitride will form mixolimnion with 2: 1 to 0.75: 1 molecule ratio or carry out diffusion-sintering to Sialon component development mutually at the same time with aluminium nitride.
Characteristics of the present invention are as follows:
(1) according to different Z value requirements, at high temperature synthetic special-purpose in advance aluminum silicon alloy makes the atom in the Pure Silicon Metal and two kinds of metallic elements of metallic aluminium in the aluminum silicon alloy be in the mixed-level of atomic scale.Then aluminum silicon alloy is joined in the corundum raw material, as the wedding agent of synthetic beta-Sialon combined corundum brick.
(2) volumetric expansion of aluminum silicon alloy in nitridation process has very obvious effects to the nitrogenize that promotes Pure Silicon Metal.
(3) between aluminium nitride and Pure Silicon Metal, set up a nitrogen-atoms rapid diffusion passage, helped carrying out fast of nitrogenize.
(4) use aluminum silicon alloy to compare with the powder mix that uses Pure Silicon Metal/metallic aluminium, the straight line diffusion length between the Si-Al-O-N atom might dwindle 10
4Doubly, thus greatly promoted the generation of beta-Sialon phase.
(5) contain the grain-size that the silicon nitride crystal seed of appropriate amount can refinement beta-Sialon phase in the aluminum silicon alloy, and help the quick nitrogenize of Pure Silicon Metal.
Therefore in the sintering process of product of the present invention, its firing temperature can being reduced to about 1430 ℃ more than 1500 ℃ from routine.Indexs such as the compressive strength of brick body and folding strength improve more than 30% than conventional products in addition, owing in wood invention, introduced the aluminum silicon alloy fine powder, therefore help in the sintering process of Sialon combined corundum brick, to generate fast Silaon in conjunction with mutually and improve Silon in conjunction with mutually and the bonding strength between the brown corundum aggregate.And help to increase the anti-fracture toughness property of refractory materials, improve the high temperature resistance thermal stress damage ability of refractory materials.Be specially adapted to use at body of heater and the furnace bosh position of life at the iron-smelting blast furnace more than 20 years.
Description of drawings
Fig. 1 is the conventional generation model figure of Sialon in conjunction with phase.
Fig. 2 generates model diagram mutually for the Sialon combination of aluminum silicon alloy of the present invention.
Embodiment
Describe in further detail below in conjunction with specific embodiment:
Embodiment 1.
The Sialon combined corundum brick that contains aluminum silicon alloy of the present invention is by brown corundum aggregate, brown corundum fine powder, and clay, aluminum oxide fine powder and aluminum silicon alloy fine powder combine according to following weight per-cent:
Palm fibre corundum aggregate: 70%
The palm fibre corundum fine powder: 10.5%, the 180-320 order
The aluminum silicon alloy fine powder: 9.5%, the 180-320 order
The Guangxi clay: 2%, the 180-320 order
Aluminum oxide fine powder: 8%, the 180-320 order
The preparation method of aluminum silicon alloy fine powder: when pressing Z=1, Si:93.98%, mixed fusion or the sintering of Al:6.02%.
The preparation method of Sialon combined corundum brick: according to a conventional method, after the raw material mixing, moulding is carried out sintering afterwards and is made product of the present invention.
Embodiment 2.
Sialon combined corundum brick with the preparation of aluminum silicon alloy method of the present invention is by brown corundum aggregate, brown corundum fine powder, and clay, aluminum oxide fine powder and aluminum silicon alloy fine powder combine according to following weight per-cent:
Palm fibre corundum aggregate: 65%
The palm fibre corundum fine powder: 17.25%, the 180-320 order
The aluminum silicon alloy fine powder: 9.25%, the 180-320 order
The Guangxi clay: 2%, the 180-320 order
Aluminum oxide fine powder: 6.5%, 180～320 orders
The preparation method of aluminum silicon alloy fine powder: when pressing Z=3, Si:75.75%, mixed fusion or the sintering of Al:24.25%.
The preparation method of Sialon combined corundum brick: with embodiment 1.
Embodiment 3
Sialon combined corundum brick with the preparation of aluminum silicon alloy method of the present invention is by brown corundum aggregate, brown corundum fine powder, and clay, aluminum oxide fine powder and aluminum silicon alloy fine powder combine according to following weight per-cent:
Palm fibre corundum aggregate: 68.5%
Palm fibre corundum fine powder: 10%, 180～320 orders
Aluminum silicon alloy fine powder: 10.8%, 180～320 orders
Guangxi clay: 2%, 180～320 orders
Aluminum oxide fine powder: 8.7%, the 180-320 order
The preparation method of aluminum silicon alloy fine powder: when pressing Z=4, Si:60.95%, mixed preparation fusion or the sintering of Al:39.05%.
The preparation method of Sialon combined corundum brick: with embodiment 1.
Claims (4)
1. Sialon combined fireproof material, its raw material contains following composition (weight percent):
Aggregate 60～75%
Fine powder 10～20%
Aluminum silicon alloy fine powder 5～15%
Aluminum oxide fine powder 5～12%
Clay 1.5～5%
Wherein, described aggregate is corundum or silicon nitride or mullite; Fine powder is corundum or silicon nitride or mullite; Described aluminum silicon alloy fine powder is to be formed by metallic aluminium and Pure Silicon Metal mixed melting or sintering; The metallic aluminium in the described aluminum silicon alloy fine powder and the proportioning of Pure Silicon Metal are to determine that in conjunction with Z coefficient mutually the Z coefficient is 1.0～4.0 according to predetermined Sialon, and the weight percent of metallic aluminium and Pure Silicon Metal is: Si:60-94%, Al:6.0～40%.
2. Sialon combined fireproof material as claimed in claim 1 is characterized in that, described aluminum silicon alloy fine powder, clay, aluminum oxide fine powder are the 180-320 order.
3. Sialon combined fireproof material as claimed in claim 1 is characterized in that: described aluminum silicon alloy fine powder in the preparation, adding has that to account for weight alloy per-cent be that 30～60% aluminum oxide fine powder is as stopping composition.
4. Sialon combined fireproof material as claimed in claim 1 is characterized in that: described aluminum silicon alloy fine powder in the preparation, adding has that to account for weight alloy per-cent be 1～10% silicon nitride fine powder.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02137290 CN1223550C (en) | 2002-09-29 | 2002-09-29 | Sialon combined fireproof material containing aluminum silicon alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02137290 CN1223550C (en) | 2002-09-29 | 2002-09-29 | Sialon combined fireproof material containing aluminum silicon alloy |
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|---|---|
| CN1485300A CN1485300A (en) | 2004-03-31 |
| CN1223550C true CN1223550C (en) | 2005-10-19 |
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| CN 02137290 Expired - Fee Related CN1223550C (en) | 2002-09-29 | 2002-09-29 | Sialon combined fireproof material containing aluminum silicon alloy |
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Families Citing this family (13)
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| CN1300057C (en) * | 2004-08-25 | 2007-02-14 | 武汉科技大学 | Refractory Sialon corundum brick material for blast flurnace and its prepn process |
| CN101747062A (en) * | 2008-11-27 | 2010-06-23 | 郑州东方三力耐火材料有限公司 | Ladle upper nozzle brick for steelmaking |
| CN101747063B (en) * | 2008-11-27 | 2013-03-06 | 郑州东方三力耐火材料有限公司 | Aluminium-magnesia carbon brick and preparation method thereof |
| CN101747065A (en) * | 2008-11-29 | 2010-06-23 | 郑州东方三力耐火材料有限公司 | Magnesia carbon brick and preparation method thereof |
| CN102674852A (en) * | 2012-05-10 | 2012-09-19 | 中国钢研科技集团有限公司 | Preparation method of tundish working lining |
| WO2015058723A1 (en) * | 2013-10-25 | 2015-04-30 | 李明建 | Preparation method of blast furnace or iron runner sialon lining |
| CN103553669B (en) * | 2013-10-25 | 2015-03-11 | 巩义市时创新材料孵化器有限公司 | Method for preparing Sialon material inside blast furnace |
| CN105272297B (en) * | 2015-10-28 | 2017-04-26 | 河南科技大学 | Fe-Sialon-corundum composite refractory material and preparation method thereof |
| CN108727043A (en) * | 2018-06-11 | 2018-11-02 | 武汉科技大学 | A kind of low-carbon aluminum-carbon refractory material and preparation method thereof with multidimensional enhancing |
| CN113461432A (en) * | 2021-07-28 | 2021-10-01 | 巩义市芙豪冶金材料有限公司 | Anti-scouring anhydrous stemming |
| CN115611643A (en) * | 2022-09-02 | 2023-01-17 | 五冶集团上海有限公司 | Novel prefabricated block for chute pillar of dry quenching furnace and preparation method thereof |
| CN115636679B (en) * | 2022-11-03 | 2023-08-11 | 中钢洛耐科技股份有限公司 | Sialon corundum mullite for firing electronic ceramic kiln |
| CN116199503B (en) * | 2023-01-31 | 2024-04-12 | 马鞍山利尔开元新材料有限公司 | Al is added 2 O 3 -Si 3 N 4 Composite powder sliding plate brick, composite sliding plate brick and preparation method thereof |
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