CN1210222C - Synthesized compound sillimanite products and preparation method thereof - Google Patents
Synthesized compound sillimanite products and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a synthetic compounding sillimanite product. The synthetic compounding sillimanite product is a compounding body which uses mullite crystal phase as a main material and uses corundum phase and vycor glass as auxiliary materials. The present invention is composed of the following materials according to the proportion by weight: 28 to 32% of alpha-alumine powder, 8 to 12% of plate-shaped corundum granules, 7 to 10% of silicon dioxide powder, 38 to 42% of mullite aggregate, 8 to 14% of mullite powder and 0.2 to 0.8% of fused magnesia powder. The synthetic compounding sillimanite product is prpared by a gelatin forming method that simplex premixing liquid is prepared firstly; after miropowder material balls are added into the simplex premixing liquid to be milled into slurry, aggregate, an initiating agent and a defoaming agent are added into the slurry to be stirred and uniformly to prepare suspensoid; finally, the suspensoid is injected into a mould to be solidified and shaped. The synthetic compounding sillimanite product has the advantages of big volume density, low apparent porosity, good thermal stability, long service life, no preheating need and direct use; in addition, the service life of the synthetic compounding sillimanite product is 1.5 to 2 times as long as that of a traditional sillimanite product. The preparation method of the present invention is scientific and reasonable and is easy to implement, and effectively guarantees the product quality.
Description
Technical Field
The invention relates to a synthetic composite sillimanite product anda preparation method thereof, belonging to the technical field of refractory materials.
Background
Along with the continuous development of market demands and technologies, the refractory materials are greatly improved, and favorable progress is made. The sillimanite product as a special refractory material has wider application space, and is applied to the glass industry, the electronic component industry and the magnetic material industry in many cases. However, the following problems still exist with the current sillimanite products: the volume density is small and is 2.15-2.25 g/cm3It is difficult to achieve 2.3g/cm3The apparent porosity is high, 25-28%, and large bubbles with the diameter of phi 2-phi 8mm exist, although some manufacturers adopt a vacuum pumping technology, only a part of bubbles with the diameter of phi more than 3mm are eliminated, and bubbles with the diameter of phi less than 2mm are difficult to eliminate; the thermal stability is poor, preheating treatment is needed when the device is used, the device is complicated and inconvenient, and the service life is directly influenced. Summarizing the situation for many years, the reason is mainly found in the aspects of material selection, material proportioning and forming, such as material selection requirement, material proportioning, traditional grouting and compression molding, and therefore, the improvement on the product quality from multiple aspects is needed.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the invention provides a synthetic composite sillimanite product with large volume density, low apparent porosity, good thermal stability and long service life, and also provides a preparation method whichis scientific, reasonable, easy to implement and beneficial to ensuring the product quality.
The synthetic composite sillimanite product comprises the following crystalline phases in percentage by weight:
76-82% of mullite crystal phase, 5-9% of corundum and 10-15% of high silica glass phase. The product forms a complex with mullite crystal phase as the main component and corundum phase and high silica glass as the secondary component.
The weight percentage of the ingredients of the product is as follows:
α -28-32% of alumina powder, 8-12% of tabular corundum particles, 7-10% of silica powder, 38-42% of mullite aggregate, 8-14% of mullite powder and 0.2-0.8% of fused magnesia powder.
The ingredients have the following requirements:
α -alumina, industrial grade α -alumina;
plate corundum: industrial first-grade product plate corundum;
silicon dioxide: SiO 22≥96％；
Mullite: al (Al)2O3≥48％、Fe2O3≤0.8％、K2O+Na2O≤0.5％、CaO+MgO≤0.8％、Al2O3+SiO2≥98％。
The preparation method comprises the steps of proportioning, forming and sintering, wherein the weight composition of the granules of the proportioning is as follows:
micro powder material:
α -alumina powder, 3-9% of powder with the particle diameter d less than or equal to 1um
The particle diameter d of the powder is less than or equal to 9um and is more than 1um, and the powder is 9-26 percent
16-30 percent of powder with the particlesize d less than or equal to 20um and less than 9um
16-30 percent of powder with the particle size d less than or equal to 32um and less than 20um
The particle size d of the powder with the particle size of more than 32um and less than or equal to 44um is 9-26 percent
9-23% of powder with particle size d less than or equal to 88um and more than 44 um;
the silicon dioxide powder is powder with the particle size d less than or equal to 1 um;
the mullite powder is a powder with the particle size d less than or equal to 88 um;
the fused magnesia powder is as follows: powder with particle size d less than or equal to 88um and less than or equal to 44 um;
aggregate:
the plate-shaped corundum particles are: powder with the particle size d of less than or equal to 0.4mm and less than or equal to 0.1 mm;
mullite aggregate: 25 to 50 percent of granular material with the grain diameter d being more than 0.4mm and less than or equal to 0.8mm
25 to 50 percent of granular material with the grain diameter d of more than 0.8mm and less than or equal to 1.2mm
12-38% of granules with the particle size d being larger than 1.2mm and smaller than or equal to 1.6 mm;
the preparation method has the advantages that the ingredient gradation is reasonable, the larger volume density and the lower apparent porosity can be ensured, special microstructures such as crack bifurcation, particle pinning and the like can be formed in a final product, the generation and the expansion of large cracks are hindered, and the excellent product stability is ensured.
The forming mode adopts a gel forming method:
(1) preparing a monomer premix;
(2) adding the micro-powder, performing ball milling for pulping, adding the aggregate, the initiator and the defoaming agent, and stirring and mixing uniformly to prepare a suspension;
(3) and injecting the suspension into a mold for curing and forming.
The Gel forming method is a new forming process recently introduced, namely a ceramic precision forming technology originated from Gel-casting (Gel-casting) in the united states. The process utilizes the characteristic of three-dimensional network gel formed by polymerization reaction of organic monomers to ensure that the ceramic suspension is solidified in situ into a ceramic body after being injected into a mould. The method adopts a metal mould or other non-porous mould which is not water-tight, and is characterized in that: the blank body has uniform structure, high green body strength and convenient processing, can realize near net size forming, is widely applied to the manufacture of special ceramics and refractory material products, and the details of the conditions are not repeated. The present invention is only explained in detail for some modified cases.
Preparing a monomer premix: acrylamide and sodium polyacrylate with the molecular weight of 7000-10000 are dissolved in water to prepare the monomer premix, the raw materials are easy to obtain, and the obtained premix has good performance. The proportion of the materials for preparation is respectively as follows: the weight of the acrylamide is 0.3-0.8% of that of the micro powder, and the weight of the sodium polyacrylate is 0.6-1.2% of that of the micro powder.
Other control parameters are as follows:
the selected initiator is potassium persulfate, and the using amount of the initiator is 0.3-0.8% of the weight of the micro powder; the defoaming agent is tributyl phosphate, and the using amount of the defoaming agent is 0.8-1.5% of the weight of the micro powder. The method has the advantages of no need of a catalyst, defoaming agent, no need of vacuumizing, convenience in operation and low cost, and particularly has more remarkable effect in industrial production.
The raw materials used in the present invention are directly available.
The forming and curing temperature is 40-80 ℃, and the curing time is 60-180 minutes.
The firing temperature of the product is 1420-1480 ℃, and the highest temperature is kept for 18-22 hours.
Because the forming adopts organic monomers, the main task of the initial stage of the sintering is to remove organic matters, namely, the degreasing process is mainly carried out at the temperature of below 500 ℃, and the sintering control is as follows:
8-12 hours below 80 ℃; 16-20 hours at 80-110 ℃;
12-16 hours at 110-160 ℃; 12-16 hours at 160-200 ℃;
8-12 hours at 200-260 ℃; 8-12 hours at 260-300 ℃;
12-16 hours at 300-380 ℃; 12-16 hours at 380-460 ℃;
460-500 ℃ for 12-16 hours.
The high-temperature sintering reaction of the sintering engineering comprises the following steps:
other process operating requirements, like conventional firing of refractory materials, are not repeated.
The sillimanite product of the invention is detected to have the following technical indexes:
Al2O363-70% of Fe2O3Less than1 percent and the volume density of the powder is 2.4 to 2.6g/cm3The apparent porosity is 11-18%, the refractoriness under load is 1560 ℃, and the thermal stability is as follows: 1100 deg.CWater cooling at-20 deg.c and no crack for 8 times.
The sillimanite product of the invention has large volume density, low apparent porosity, good thermal stability and long service life, does not need preheating and can be directly used, and the service life of the sillimanite product is 1.5 to 2 times of that of the traditional sillimanite product. The product of the invention is made into a charging barrel, a punch and a bowl of a feeding machine of a glass kiln, and good product performance is fully verified in practical application. The preparation method is scientific and reasonable, is easy to implement and effectively ensures the product quality.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
the synthetic composite sillimanite product comprises the following crystalline phases in percentage by weight:
79% of mullite crystal phase, 8% of corundum and 13% of high silica glass phase.
The weight percentage of the ingredients is as follows:
α -30% of alumina powder, 10% of tabular corundum particles, 8% of silica powder, 40% of mullite aggregate, 12% of mullite powder and 0.5% of fused magnesia powder.
The ingredients have the following requirements:
α -alumina, industrial grade α -alumina;
plate corundum: industrial first-grade product plate corundum;
silicon dioxide: SiO 22≥96％；
Mullite: al (Al)2O3≥48％、Fe2O3≤0.8％、K2O+Na2O≤0.5％、CaO+MgO≤0.8％、Al2O3+SiO2≥98％。
The preparation method comprises the steps of proportioning, forming and sintering, wherein the weight composition of the granules of the proportioning is as follows:
micro powder material:
α -alumina powder, powder with particle diameter d less than or equal to 1um 7%
The particle diameter d of the powder is less than or equal to 9um and is more than 1um and less than or equal to 17 percent
The particle diameter d of the powder is less than or equal to 20um and is less than 9um and less than or equal to 23 percent
20um is more than 20um and 23 percent of powder with the particle size d less than or equal to 32um
The particle size d of the powder with the particle size of more than 32um and less than or equal to 44um is 16 percent
14 percent of powder with the particle size d being more than 44um and less than or equal to 88 um;
the silicon dioxide powder is powder with the particle size d less than or equal to 1 um;
the mullite powder is a powder with the particle size d less than or equal to 88 um;
the fused magnesia powder is as follows: powder with particle size d less than or equal to 88um and less than or equal to 44 um;
aggregate:
the plate-shaped corundum particles are: powder with the particle size d of less than or equal to 0.4mm and less than or equal to 0.1 mm;
mullite aggregate: 38 percent of granules with the grain diameter d less than or equal to 0.8mm and less than 0.4mm
38 percent of granular material with the grain diameter d less than or equal to 1.2mm and less than 0.8mm
24 percent of granules with the grain diameter d being more than 1.2mm and less than or equal to 1.6 mm;
the forming mode adopts a gel forming method:
(1) preparing a monomer premix;
(2) adding the micro-powder, performing ball milling for pulping, adding the aggregate, the initiator and the defoaming agent, and stirring and mixing uniformly to prepare a suspension;
(3) and injecting the suspension into a mold for curing and forming.
The monomer premix is prepared by dissolving acrylamide and sodium polyacrylate with the molecular weight of 7000-10000 in water, wherein the acrylamide in the ingredients of the premix is 0.5 percent of the weight of the micro-powder, and the sodium polyacrylate is 0.9 percent of the weight of the micro-powder. The initiator is potassium persulfate, the defoaming agent is tributyl phosphate, and the dosage of the initiator is 0.5 percent and 1 percent of the weight of the micro-powder respectively.
And (3) molding by using a metal mold, wherein the molding curing temperature is 40-60 ℃, and the curing time is 80-90 minutes. And (4) sintering the formed product after machining and finishing treatment.
The firing temperature of the product is 1430-1470 ℃, and the temperature is kept for 20 hours. In the firing process, the degreasing process is carried out below 500 ℃, and the firing control is as follows: 10 hours below 80 ℃; 18 hours at 80-110 ℃;
14 hours at 110-160 ℃; 13 hours at 160-200 ℃;
10 hours at 200-260 ℃; 10 hours at 260-300 ℃;
13 hours at 300-380 ℃; 14 hours at 380-460 ℃;
460-500 ℃ for 14 hours.
Example 2
The synthetic composite sillimanite product comprises the following crystalline phases in percentage by weight:
80% of mullite crystal phase, 7% of corundum and 13% of high silica glass phase.
The weight percentage of the ingredients is as follows:
α -29% of alumina powder, 11% of tabular corundum particles, 9% of silicon dioxide powder, 39% of mullite aggregate, 11.6% of mullite powder and 0.4% of added fused magnesia powder.
The weight gradation of the particles of the ingredients is as follows:
micro powder material:
α -alumina powder, powder with particle diameter d less than or equal to 1um 8%
The particle diameter d of the powder is more than 1um and less than or equal to 9um, and 15 percent
The particle size d of the powder is less than or equal to 20um and is less than 9um and less than or equal to 20um, and 22 percent
20um is more than 20um and the particle size d is less than or equal to 32um and 25 percent
The particle size d of the powder is more than 32um and less than or equal to 44um and 18 percent
12 percent of powder with the particle size d being more than 44um and less than or equal to 88 um;
aggregate:
mullite aggregate: 33 percent of granular material with the grain diameter d less than or equal to 0.8mm and less than 0.4mm
42 percent of granular material with the grain diameter d less than or equal to 1.2mm and more than 0.8mm
25 percent of granules with the particle size d being more than 1.2mm and less than or equal to 1.6 mm;
in the ingredients of the premix, acrylamide accounts for 0.6 percent of the weight of the micro-powder, and sodium polyacrylate with the molecular weight of 7000-10000 accounts for 0.8 percent of the weight of the micro-powder. The initiator is potassium persulfate, and the using amount of the initiator is 0.4 percent of the weight of the micro powder; the defoaming agent is tributyl phosphate, and the dosage of the defoaming agent is 1.1 percent of the weight of the micro-powder.
The curing temperature is 50-60 ℃, and the curing time is 90-100 minutes. The firing temperature of the product is 1440-1470 ℃, and the temperature is kept for 19 hours.
The degreasing process is mainly carried out below 500 ℃, and the firing is controlled as follows:
11 hours below 80 ℃; 18 hours at 80-110 ℃;
14 hours at 110-160 ℃; 14 hours at 160-200 ℃;
10 hours at 200-260 ℃; 9 hours at 260-300 ℃;
12 hours at 300-380 ℃; 13 hours at 380-460 ℃;
460-500 ℃ for 13 hours.
Otherwise, the same procedure as in example 1 was repeated.
Example 3
The synthetic composite sillimanite product comprises the following crystalline phases in percentage by weight:
77% of mullite crystal phase, 9% of corundum and 14% of high silica glass phase.
The other process parameters are respectively as follows:
the weight percentage of the ingredients is as follows:
α -30% of alumina powder, 10% of tabular corundum particles, 8.4% of silicon dioxide powder, 40% of mullite aggregate, 11% of mullite powder and 0.7% of added fused magnesia powder.
The weight gradation of the particles of the ingredients is as follows:
micro powder material:
α -alumina powder, powder with particle diameter d less than or equal to 1um 6%
Powder with particle size of 1um less than or equal to 20 percent and particle size d less than or equal to 9um
The particle diameter d of the powder is less than or equal to 20um and is less than 9um and less than or equal to 17 percent
20um is more than 20um and the powder with the particle size d less than or equal to 32um is 22 percent
The particle size d of the powder with the particle size of more than 32um and less than or equal to 44um is 16 percent
19 percent of powder with the particle size d less than or equal to 88um and more than 44 um;
aggregate:
mullite aggregate: 43 percent of granules with the grain diameter d less than or equal to 0.8mm and less than 0.4mm
34 percent of granules with the grain diameter d less than or equal to 1.2mm and more than 0.8mm
23 percent of granular material with the grain diameter d being more than 1.2mm and less than or equal to 1.6 mm;
in the ingredients of the premix, acrylamide accounts for 0.7 percent of the weight of the micro-powder, and sodium polyacrylate with the molecularweight of 7000-10000 accounts for 1.1 percent of the weight of the micro-powder. The initiator is potassium persulfate, and the using amount of the initiator is 0.7 percent of the weight of the micro powder; the defoaming agent is tributyl phosphate, and the dosage of the defoaming agent is 1.3 percent of the weight of the micro-powder.
Otherwise, the same procedure as in example 1 was repeated.
Claims (7)
1. A synthetic composite sillimanite product characterized in that it comprises the following crystalline phases in weight percent:
76-82% of mullite crystal phase, 5-9% of corundum and 10-15% of high silica glass phase;
the components by weight percentage of the material are α -alumina powder 28-32%, tabular corundum particles 8-12%, silica powder 7-10%, mullite aggregate 38-42%, mullite powder 8-14%, and fused magnesia powder 0.2-0.8%.
2. The synthetic composite sillimanite product according to claim 1, characterized in that the ingredients have the following requirements:
α -alumina, industrial grade α -alumina;
plate corundum: industrial first-grade product plate corundum;
silicon dioxide: SiO 22≥96％；
Mullite: al (Al)2O3≥48％、Fe2O3≤0.8％、K2O+Na2O≤0.5％、CaO+MgO≤0.8％、Al2O3+SiO2≥98％。
3. A method of producing a synthetic composite sillimanite product according to claim 1 or 2, comprising batching, shaping, firing, characterized in that the grain weight composition of the batching is:
micro powder material:
α -alumina powder, 3-9% of powder with the particle diameter d less than or equal to 1um
The particle diameter d of the powder is less than or equal to 9um and is more than 1um, and the powder is 9-26 percent
16-30 percent of powder with the particle size d less than or equal to 20um and less than 9um
16-30 percent of powder with the particle size d less than or equal to 32um and less than 20um
The particle size d of the powder with the particle size of more than 32um and less than or equal to 44um is 9-26 percent
9-23% of powder with particle size d less than or equal to 88um and more than 44 um;
the silicon dioxide powder is powder with the particle size d less than or equal to 1 um;
the mullite powder is a powder with the particle size d less than or equal to 88 um;
the fused magnesia powder is as follows: powder with particle size d less than or equal to 88um and less than or equal to 44 um;
aggregate:
the plate-shaped corundum particles are: powder with the particle size d of less than or equal to 0.4mm and less than or equal to 0.1 mm;
mullite aggregate: 25 to 50 percent of granular material with the grain diameter d being more than 0.4mm and less than or equal to 0.8mm
25 to 50 percent of granular material with the grain diameter d of more than 0.8mm and less than or equal to 1.2mm
12-38% of granules with the particle size d being larger than 1.2mm and smaller than or equal to 1.6 mm;
the forming mode adopts a gel forming method:
(1) dissolving acrylamide and sodium polyacrylate with the molecular weight of 7000-10000 in water to prepare a monomer premix;
(2) adding the micropowder, performing ball milling and pulping, adding aggregate, a potassium persulfate initiator with the amount of 0.3-0.8% of the weight of the micropowder, and a tributyl phosphate antifoaming agent with the amount of 0.8-1.5% of the weight of the micropowder, and uniformly stirring and mixing to obtain a suspension;
(3) and injecting the suspension into a mold for curing and forming.
4. The method as claimed in claim 3, wherein the amount of acrylamide in the mixture is 0.3-0.8 wt% of the fine powder, and the amount of sodium polyacrylate with a molecular weight of 7000-10000 is 0.6-1.2 wt% of the fine powder.
5. The method of claim 4, wherein the curing temperature is 40-80 ℃ and the curing time is 60-180 minutes.
6. The method of claim 5, wherein the firing temperature of the product is 1420-1480 ℃.
7. The method of claim 6, wherein the de-esterification process is performed at a temperature below 500 ℃, and the firing is controlled to:
8-12 hours below 80 ℃; 16-20 hours at 80-110 ℃;
12-16 hours at 110-160 ℃; 12-16 hours at 160-200 ℃;
8-12 hours at 200-260 ℃; 8-12 hours at 260-300 ℃;
12-16 hours at 300-380 ℃; 12-16 hours at 380-460 ℃;
460-500 ℃ for 12-16 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02135484 CN1210222C (en) | 2002-09-18 | 2002-09-18 | Synthesized compound sillimanite products and preparation method thereof |
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|---|---|---|---|
| CN 02135484 CN1210222C (en) | 2002-09-18 | 2002-09-18 | Synthesized compound sillimanite products and preparation method thereof |
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| CN1483702A CN1483702A (en) | 2004-03-24 |
| CN1210222C true CN1210222C (en) | 2005-07-13 |
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| CN108018585A (en) * | 2018-01-09 | 2018-05-11 | 范龙飞 | A kind of metal texture plate electroforming mould and method |
| CN116573925B (en) * | 2023-05-18 | 2024-05-10 | 中国科学院过程工程研究所 | Ceramic heat-insulating tile and preparation method and application thereof |
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