CN1255354C - High-temperature ceramic refractory material and its manufacturing method - Google Patents
High-temperature ceramic refractory material and its manufacturing method Download PDFInfo
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- CN1255354C CN1255354C CN 02136175 CN02136175A CN1255354C CN 1255354 C CN1255354 C CN 1255354C CN 02136175 CN02136175 CN 02136175 CN 02136175 A CN02136175 A CN 02136175A CN 1255354 C CN1255354 C CN 1255354C
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- boron nitride
- corundum
- refractory material
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Abstract
The present invention relates to a fire-proof material of a high-temperature ceramic and a manufacturing method thereof. The manufacturing method comprises the following steps that celon bulge combining sand compounded by corundum and boron nitride is synthesized firstly; next, the sand compounded by the corundum and the boron nitride in different grades is added by a binding agent to form pug material which is molded in a press mode, and the pug material is fired at the high temperature in the atmosphere filled with N2 and/or NH3. The fire-proof material has the final chemical components of 50 to 68% of Al2O3, 5 to 18% of BN, 5 to 7% of ZrO2, 3 to 7% of SiO2, 1 to 5% of Y2O3 and 5 to 10% of C. The final phase of the fire-proof material has the components of 40 to 70% of corundum phase, 5 to 20% of hexagon boron nitride, 10 to 20% of celon bulge and 5 to 20% of amorphous carbon coupling phase. Thus, the various properties of the material is homogenized fully, the abrasion-proof index of the material is controlled to a maximum limit at the point which approaches to the abrasion-proof index of a copper rolling material, and the mechanical property under the high temperature is kept to be unchanged. Simultaneously, a side seal plate has the advantages of easy and optimized manufacturing process, and cost reduction.
Description
Technical field
The present invention relates to the ceramic subject, particularly high temperature engineering ceramics field.
Background technology
One-heating forming is the target that the metallargist dreams of.Twin-roll thin strip continuous casting is a nearly continuous casting process at a kind of nearly end.Strip caster is formed the molten bath by two water cooled rolls and a pair of side shields that rotate in opposite directions, annotates molten steel with submerged nozzle in the molten bath, and molten steel is in the surface solidification of two rollers, and solidified shell directly forms made-up belt by two water cooled rolls pressings; Side seal technology and side seal board are one of core technologies of thin strap continuous casting.Thin strap continuous casting processing requirement side seal board high-temperature ceramic refractory material has excellent comprehensive performances, must satisfy following the requirement:
(1) have good thermal shock resistance, heat distortion amount is little;
(2) good mechanical performance intensity, toughness under the high temperature;
(3) refractory steel aggressiveness is strong;
(4) good heat-insulating property, poor with the molten steel wetting property;
(5) material has suitable anti-wear energy.
In the specification sheets of Chinese patent 91107479.1, a kind of side seal board that is made of two-layer matrix material is provided, its basic unit is that thermal conductivity is low, again the high aluminium lamination refractory materials of clay matter, fused quartz matter and lightweight of certain intensity, surface layer to be arranged be that thickness is high fine and close glass-ceramic or the enamel of 0.5-3mm.Although this way has solved material cold problem of molten steel at molten steel, two roller and side seal board three calmodulin binding domain CaMs from principle, but high fine and close glass-ceramic or enamel hardness of surface layer is too high, very easily make the copper coin wearing and tearing of two roller end faces, thus the work-ing life of the two rollers of influence.In the utility model patent of Chinese patent 98229485.9, mention the side seal board material that uses and be boron nitride.But boron nitride material intensity is low, and wear resisting property is poor.Especially boron nitride is easy to oxidation under hot conditions, and therefore single use boron nitride effect is unsatisfactory.
Chinese patent 95194684.6 has been invented a kind of strip caster and has been used the side.This side comprises a metal frame and a non-metallic plates.This non-metallic plates is made up of two portions, and a part is the friction zone that contacts with two rollers, and another part is and melts the middle section that steel contacts.Its friction zone is made up of a kind of boron nitride material of 15% of containing at least.And the friction zone is made up of several elements that splice mutually.Molten steel zone is preferably carbon bonded pottery.The shortcoming of this patent is, side seal board different zones material coefficient of thermal expansion performance difference is big, easily crack at bonding surface, and side seal board manufacturing process complexity.
Chinese patent CN1092053A has announced that a kind of match swells (SIALON) combined silicon carbide refractory ceramic material.This material can be a purpose with the contour warm nature of the heat shock resistance that improves carbofrax material, and it is grand in conjunction with phase to introduce match in carborundum refractory.It is characterized in that forming SIALON in conjunction with phase with clay mineral such as kaolin and charcoal source.Chinese patent CN1091116A has announced a kind of based on zirconium corundum, mullite and boron nitride matrix material, its objective is comprehensive malleableize and reinforcement by based on zirconium corundum, mullite material and boron nitride material, obtaining a kind of is respectively that base-material and boron nitride are compound and be two kinds of matrix materials of base-material and based on zirconium corundum, mullite compound with the boron nitride with the zircon corundum.It is characterized by and carry out high temperature sintering after above-mentioned raw materials directly is mixed, this is too high in conjunction with the matrix material synthesis temperature of phase with pottery directly, is difficult to preparation.
As seen, if side seal material wear-resistant performance is too high, in use the side seal material copper roller that will wear and tear causes the copper roller to damage, and influences the work-ing life of copper roller or causes bleed-out.If side seal material wear-resistant performance is poor, then in use the copper roller will the wear-side closure material, forms groove on side seal board, causes bleed-out and influences the Cast Strip quality of edges, goes out burr etc. as limit, Cast Strip minister, causes waste product.
Summary of the invention
The objective of the invention is to seek suitable pyroceramic side seal board refractory materials of a kind of over-all properties complementary, economy and the method for making this material, can improve the mechanical behavior under high temperature and the antioxidant property of boron nitride material, improve the heat-shock resistance and the machinability of corundum material, make the manufacturing process and the cost optimization and simple of side seal board simultaneously, cost reduces.
The present invention is achieved in that high-temperature ceramic refractory material, and its chemical ingredients is: Al
2O
350～68%, BN 5～18%, ZrO
25～7%, SiO
23～7%, Y
2O
31～5%, C 5～10%; Its phase composite is 40～70% corundum phase, 5～20% hexagonal boron nitride, 10～20% match grand mutually with 5～20% decolorizing carbon in conjunction with mutually; More than be weight percentage.
The manufacture method of above-mentioned materials is as follows:
A) corundum, boron nitride are mixed by the design proportioning and add sintering aid and dispersion medium, behind the mix grinding as raw material;
B) with the forming under the pressure of raw material, make waste base at 100～200Mpa;
C) waste base is inserted logical N
2And/or NH
3Atmosphere in, burn till and be incubated 8～24 hours under 1450～1600 ℃ the temperature, obtain complex sand;
D) with complex sand by different grade demand fragmentations, and with resol or pitch with itself and α-Al
2O
3, boron nitride, metallic silicon power, kaolin stir by the design proportioning and be mixed, and makes pug, at the forming under the pressure of 100～200Mpa;
E) at logical N
2And/or NH
3Atmosphere in, burnt till through 6～40 hours under 1150 ℃～1600 ℃ temperature;
Wherein, described sintering aid is C, Si, α-Al
2O
3, ZrO
2, SiO
2With a kind of or several combinations in the kaolin.
Described dispersion medium is a dehydrated alcohol.
Step b) and d) described pressure forming employing machine press or etc. static pressure.
In sintering process, a part of carbon in the binding agent forms carbon in conjunction with network, and another part carbon passes through carbothermic reduction reaction:
, formation Z value is 1～4 Si
6-zAl
zO
zN
8～z match is grand in conjunction with phase.
In conjunction with original two big class material advantages, and the combination of matrix material carried out preferably mutually.The grand bonded corundum boron nitride material of selected match is as the principal crystalline phase of side seal material.In matrix and main crystal phase material, introduce boron nitride simultaneously with carbon and Sai Long two-phase bonded mode, fully all every performance of formed material.
Embodiment
Embodiment 1:
By 55% corundum, 15% boron nitride, 10% zirconium white, 10% kaolin, other sintering aid (all being weight percentage) batch mixing of 10%, with the dehydrated alcohol is dispersion medium, mix grinding is 10 hours in the alumina balls grinding machine, in metal die, use mechanical pressing under the pressure with 150Mpa after the discharging, make waste base.The waste base that suppresses is inserted logical N
2The high temperature kiln roasting of atmosphere.Firing temperature is 1500 ℃, is incubated 20 hours.The complex sand that burns till is stand-by by different grade demand fragmentations, screening.
Complex sand broken, that screening is good is prepared burden by maximum critical granularity 3mm, and wherein complex sand 75%, α-Al
2O
35%, boron nitride 3%, metallic silicon power 2%, kaolin 5%, in conjunction with phenolic resin adhesive 10%, carry out batch mixing after, in mould with the pressure forming of 150Mpa.After 120 ℃ of oven dry, under 1450 ℃ of conditions, burn till.Obtain a kind of match grand and carbon two-phase bonded corundum boron nitride ceramic material and goods behind the naturally cooling.
The weight percent of the main chemical compositions of the finished product is as follows:
| Al 2O 3 | BN | ZrO 2 | SiO 2 | Y 2O 3 | C |
| 65.8 | 7.0 | 6.1 | 5.4 | 3.5 | 5.0 |
Embodiment 2:
By 55% corundum, 15% boron nitride, 10% zirconium white, 10% kaolin, other sintering aid (all being weight percentage) batch mixing of 10%, with the dehydrated alcohol is dispersion medium, mix grinding is 8 hours in the alumina balls grinding machine, in metal die, use isostatic pressing under the pressure with 100Mpa after the discharging, make waste base.The waste base that suppresses is inserted logical N
2And NH
3The high temperature kiln roasting of atmosphere.Firing temperature is 1500 ℃, is incubated 24 hours.The complex sand that burns till is stand-by by different grade demand fragmentations, screening.
Complex sand broken, that screening is good is prepared burden by maximum critical granularity 3mm, and wherein complex sand 75%, α-Al
2O
35%, boron nitride 3%, metallic silicon power 2%, kaolin 5%, in conjunction with phenolic resin adhesive 10%, carry out batch mixing after, in mould with the pressure forming of 150Mpa.After 120 ℃ of oven dry, under 1450 ℃ of conditions, burn till.Obtain a kind of match grand and carbon two-phase bonded corundum boron nitride ceramic material and goods behind the naturally cooling.
The weight percent of the main chemical compositions of the finished product is as follows:
| Al 2O 3 | BN | ZrO 2 | SiO 2 | Y 2O 3 | C |
| 68.0 | 5.0 | 5.0 | 7.0 | 1.0 | 8.4 |
Embodiment 3:
By 55% corundum, 15% boron nitride, 10% zirconium white, 10% kaolin, other sintering aid (all being weight percentage) batch mixing of 10%, with the dehydrated alcohol is dispersion medium, mix grinding is 12 hours in the alumina balls grinding machine, after the discharging in metal die to press or isostatic pressing with machine under the pressure of 200Mpa, make waste base.The waste base that suppresses is inserted the high temperature kiln roasting of the atmosphere of logical NH3.Firing temperature is 1500 ℃, is incubated 8 hours.The complex sand that burns till is stand-by by different grade demand fragmentations, screening.
Complex sand broken, that screening is good is prepared burden by maximum critical granularity 3mm, and wherein complex sand 75%, α-A1
2O
35%, boron nitride 3%, metallic silicon power 2%, kaolin 5%, in conjunction with phenolic resin adhesive 10%, carry out batch mixing after, in mould with the pressure forming of 150Mpa.After 140 ℃ of oven dry, under 1450 ℃ of conditions, burn till.Obtain a kind of match grand and carbon two-phase bonded corundum boron nitride ceramic material and goods behind the naturally cooling.
The weight percent of the main chemical compositions of the finished product is as follows:
| Al 2O 3 | BN | ZrO 2 | SiO 2 | Y 2O 3 | C |
| 50.0 | 18.0 | 7.0 | 3.0 | 5.0 | 10.0 |
Embodiment 4:
By 55% corundum, 15% boron nitride, 10% zirconium white, 10% kaolin, other sintering aid (all being weight percentage) batch mixing of 10%, with the dehydrated alcohol is dispersion medium, mix grinding is 11 hours in the alumina balls grinding machine, in metal die, use mechanical pressing under the pressure with 140Mpa after the discharging, make waste base.The waste base that suppresses is inserted logical N
2And NH
3The high temperature kiln roasting of atmosphere.Firing temperature is 1500 ℃, is incubated 16 hours.The complex sand that burns till is stand-by by different grade demand fragmentations, screening.
Complex sand broken, that screening is good is prepared burden by maximum critical granularity 3mm, and wherein complex sand 75%, α-Al
2O
35%, boron nitride 3%, metallic silicon power 2%, kaolin 5%, bound bitumen binding agent 10%, carry out batch mixing after, in mould with the pressure forming of 150Mpa.After 140 ℃ of oven dry, under 1450 ℃ of conditions, burn till.Obtain a kind of match grand and carbon two-phase bonded corundum boron nitride ceramic material and goods behind the naturally cooling.
The weight percent of the main chemical compositions of the finished product is as follows:
| Al 2O 3 | BN | ZrO 2 | SiO 2 | Y 2O 3 | C |
| 50.0 | 18.0 | 7.0 | 6.8 | 5.0 | 9.5 |
The resulting final material of the foregoing description and original material are compared test find, both are at thermal shock resistance, heat distortion amount, and mechanical property intensity under the hot conditions and refractory steel aggressiveness aspect are all very approaching.And the hardness of original material particulate material is higher, and the copper roller that in use weares and teares easily causes the copper roller to damage, and influences the work-ing life of copper roller or causes bleed-out.The prepared material of the embodiment of the invention has isostatic, suitable anti-wear energy, thereby has improved the mechanical behavior under high temperature and the antioxidant property of boron nitride material, improves the heat-shock resistance and the machinability of corundum material.
Claims (7)
1. a high-temperature ceramic refractory material is characterized in that, its chemical ingredients is:
Al
2O
3 50～68％
BN 5～18％
ZrO
2 5～7％
SiO
2 3～7％
Y
2O
3 1～5％
C 5～10％；
Its phase composite is 40～70% corundum phase, 5～20% hexagonal boron nitride phase, 10～20% match grand mutually with 5～20% decolorizing carbon in conjunction with mutually; More than be weight percentage.
2. high-temperature ceramic refractory material as claimed in claim 1 is characterized in that, described boron nitride ratio is 15%, by weight percentage.
3. the manufacture method of a high-temperature ceramic refractory material as claimed in claim 1 or 2 is characterized in that, manufacturing step is as follows:
A) corundum, boron nitride are mixed by the design proportioning and add sintering aid and dispersion medium, behind the mix grinding as raw material;
B) with the forming under the pressure of raw material, make waste base at 100～200Mpa;
C) waste base is inserted logical N
2And/or NH
3Atmosphere in, burn till and be incubated 8～24 hours under 1450～1600 ℃ the temperature, obtain complex sand;
D) with complex sand by different grade demand fragmentations, and with resol or pitch with itself and α-Al
2O
3, boron nitride, metallic silicon power, kaolin be by design proportioning stirring and evenly mixing, makes pug, at the forming under the pressure of 100～200Mpa;
E) at logical N
2And/or NH
3Atmosphere in, burnt till through 6～40 hours under 1150 ℃～1600 ℃ temperature;
Wherein, described sintering aid is C, Si, α-Al
2O
3, ZrO
2, SiO
2With a kind of or several combinations in the kaolin.
4. the manufacture method of high-temperature ceramic refractory material as claimed in claim 3 is characterized in that, described dispersion medium is a dehydrated alcohol.
5. the manufacture method of high-temperature ceramic refractory material as claimed in claim 3 is characterized in that, described mix grinding is in the corundum ball mill, and the mix grinding time is 8～12 hours.
6. the manufacture method of high-temperature ceramic refractory material as claimed in claim 3 is characterized in that, step b) and d) described pressure forming employing machine press or etc. static pressure.
7. the manufacture method of high-temperature ceramic refractory material as claimed in claim 3 is characterized in that, in sintering process, a part of carbon in the binding agent forms carbon in conjunction with network, and another part carbon passes through carbothermic reduction reaction:
, formation Z value is 1～4 Si
6-zAl
zO
zN
8～zSai Long is in conjunction with phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02136175 CN1255354C (en) | 2002-07-24 | 2002-07-24 | High-temperature ceramic refractory material and its manufacturing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02136175 CN1255354C (en) | 2002-07-24 | 2002-07-24 | High-temperature ceramic refractory material and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1470473A CN1470473A (en) | 2004-01-28 |
| CN1255354C true CN1255354C (en) | 2006-05-10 |
Family
ID=34146338
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02136175 Expired - Fee Related CN1255354C (en) | 2002-07-24 | 2002-07-24 | High-temperature ceramic refractory material and its manufacturing method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101583804B (en) * | 2006-12-20 | 2012-07-11 | Ntn株式会社 | Rolling bearing, hub unit, rolling member, universal joint, torque transmission member for universal joint, and process for producing the same |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1293015C (en) * | 2004-04-14 | 2007-01-03 | 哈尔滨工业大学 | Process for preparing high temperature texture ceramic material SiBONC |
| CN1300058C (en) * | 2004-08-25 | 2007-02-14 | 武汉科技大学 | Sailon corundum refractory material for permeable ladle stopper and its prepn process |
| CN101381241B (en) * | 2008-10-16 | 2011-06-15 | 武汉科技大学 | Porous breathable refractory materials for upper nozzle and production method thereof |
| CN101798232B (en) * | 2009-12-22 | 2012-09-26 | 山东宇佳新材料有限公司 | Preparation method of Sialon-carbofrax-corundum composite refractory material |
| CN102161082B (en) * | 2010-02-23 | 2013-10-30 | 上海柯瑞冶金炉料有限公司 | Side sealing plate for thin-belt continuous casting and manufacturing method |
| CN103803951B (en) * | 2013-12-23 | 2016-08-17 | 苏州宏泉高压电容器有限公司 | A kind of ceramic material and preparation method thereof |
| CN104710181A (en) * | 2015-02-11 | 2015-06-17 | 安徽华通铸业有限公司 | Insulating refractory for vacuum casting aluminum alloy casting |
| CN105113705A (en) * | 2015-08-06 | 2015-12-02 | 安徽铭源新型建材科技有限公司 | Heat-insulating wear-resistant inner wallboard |
-
2002
- 2002-07-24 CN CN 02136175 patent/CN1255354C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101583804B (en) * | 2006-12-20 | 2012-07-11 | Ntn株式会社 | Rolling bearing, hub unit, rolling member, universal joint, torque transmission member for universal joint, and process for producing the same |
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| Publication number | Publication date |
|---|---|
| CN1470473A (en) | 2004-01-28 |
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Granted publication date: 20060510 Termination date: 20130724 |