CN104446512A - Composite sintering aids for BN-ZrO2-SiC composite material - Google Patents
Composite sintering aids for BN-ZrO2-SiC composite material Download PDFInfo
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- CN104446512A CN104446512A CN201310435315.4A CN201310435315A CN104446512A CN 104446512 A CN104446512 A CN 104446512A CN 201310435315 A CN201310435315 A CN 201310435315A CN 104446512 A CN104446512 A CN 104446512A
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Abstract
The invention relates to BN composite material preparation technologies and discloses composite sintering aids for a BN-ZrO2-SiC composite material. The composite sintering aids contain 1-4% of Al2O3 micropowder, 1-3% of CaCO3 fine powder and 1-3% of SiO2 micropowder; the composite sintering aids are applied to a BN composite material, wherein the content of BN in the composite material is 30-70%, the content of ZrO2 in the composite material is 20-60%, the content of SiC in the composite material is 5-30%, and the content of the sintering aids in the composite material is 2-10%. The three sintering aids form an Al2O3-CaCO3-SiO2 low-melting-point phase at high temperatures. According to the composite sintering aids disclosed by the invention, hot-pressed sintering is carried out by adopting the Al2O3 micropowder, the CaCO3 fine powder and the SiO2 micropowder, so as to produce the BN composite material, and then, a good sintering aiding effect can be achieved, so that the material is low in porosity, high in strength and excellent in comprehensive properties.
Description
Technical field
The present invention relates to a kind of manufacturing technology of BN matrix material, particularly relate to a kind of BN-ZrO
2the complex sintering aids of-SiC ceramic matrix composite material.
Background technology
BN(boron nitride) there are 4 kinds of crystal formations, wherein hexagonal AlN (h-BN) is normal pressure stable phase, adopts h-BN raw material production BN pottery so general.Hexagonal boron nitride (h-BN) has low thermal expansivity, high thermal conductivity and excellent heat-shock resistance.By hexagonal boron nitride and other stupalith compound, its heat-shock resistance can be improved, and the breaking strain of material can be improved.BN matrix material has BN-ZrO
2matrix material, BN-AlN matrix material, BN-match grand matrix material, BN-ZrO
2-SiC ceramic matrix composite material, BN-AlN-Si
3n
4matrix material etc.Boron nitride composite after sintering has good machining property, and precision is very high.
Boron nitride (h-BN) is a kind of laminate structure being similar to graphite, and every layer becomes hexagonal loop network alternately by B, atom N, covalent bonds between atom in layer, is the poor material of a kind of sintering activity, is difficult to obtain fine and close BN stupalith.So, the hot-pressing sintering method of pressure sintering under general employing high temperature, and add certain sintering aid, fine and close BN sintered compact could be obtained.According to documents and materials, in the process of carrying out hot pressed sintering BN pottery, mainly through adding B
2o
3, Y
2o
3, Si
3n
4, CaCO
3deng as sintering aid, to promote the cohesive action of h-BN interlayer, improve the compactness of stupalith, improve the sintering character of material.B
2o
3fusing point is low, just produces liquid phase at low temperatures, has good help nodulizing to BN material, but B
2o
3water absorbability is very strong, adds more B
2o
3the easy moisture absorption of BN material can be made to form boric acid, due to the decomposition of boric acid in high bake process, easily cause product surface to bubble.In addition, if add more B
2o
3agglutinant, not only the high temperature break resistant intensity of material is difficult to improve, and resistance to fouling can be affected.Y
2o
3the good sintering aid of stupalith, but expensive.Si
3n
4the nodulizing that helps do not have the former two good, and price is more expensive.CaCO
3although the charge is small, help nodulizing effect general to BN material.Because BN is difficult to sintering, suitable sintering aid is selected to be the key that BN matrix material obtains superperformance.
In recent years, the strip continuous casting technology of short route obtains and develops on a large scale very much.The core of thin strap continuous casting is, the casting roll of a pair opposite direction rotating and the molten bath of a pair side seal board formation continuous casting, distribute the mouth of a river and molten steel is injected molten bath, strip pulls out from the casting roll of opposite direction rotating, forms the strip product of several millimeters.Casting roll, side seal board and current distribution device (the distribution mouth of a river) are the three-major-items of thin strap continuous casting, are directly connected to the direct motion of thin band continuous casting technique and the quality of strip product.According to such working conditions, side seal board must have superior heat-shock resistance, good wear resistance, enough normal temperature and hot strength and good anti-molten steel washes away and aggressiveness.Based on so harsh service requirements, the more employing of side seal board is containing the stupalith of BN.Catheter is the key part in spray deposition processing, just as continous casting sprue, is a kind of functional refractory.During work, catheter is baked to 200 DEG C, pours into the molten steel of temperature more than 1600 DEG C.Whole reaction-injection moulding carries out in the encloses container of vacuum protection atmosphere.Catheter itself does not have baking condition, after baking of tundish, accepts the heat transfer of tundish, and the temperature of catheter just reaches 200 DEG C, and therefore catheter is subject to strong thermal shock effect.Molten steel is by catheter ejection at a high speed under stress, and catheter is subject to the strong souring of molten steel, is subject to washing away of high velocity air outside catheter simultaneously.Therefore, not only require catheter good thermal shock, desired strength is high again, and anti-molten steel washes away, and reaming is little.
Existing patent analyses.US Patent No. 2002/0104640A1 discloses in ceramic plate the patent adding Al.Think twin-roll thin strip continuous casting ceramic plate containing more than 9% Al, its normal temperature flexural strength is not less than 120MPa, more than flexural strength 65MPa when 1000 DEG C, hardness (Hv) 50 ~ 350, the thermal conductivity 8W/ (mK) of normal temperature ~ 1000 DEG C below, thermal shocking tolerance index R ' more than 800W/m, with the wetting property (contact angle θ) more than 120 ° of molten steel.Add Al and resist stainless erosional competency to improve side seal board.Utilize the side seal board that this ceramic plate is formed, can long-time continuous Cast Stainless Steel molten steel.
Japanese Patent JP8080170 thinks, forms for the material watering cast steel, stainless side seal board should be matrix by SiAlON ceramic (SIALON)/BN.The chemical composition of SiAlON ceramic is Si
6-
zalzOzN
8-z, wherein the scope of Z is 2 ~ 4.The content of BN is 0.5 ~ 50%.Such ceramic plate has good resistant to corrosion, chipping resistance performance.
The side seal board material of Japanese Patent JP8164452, except above-mentioned composition, also adds AlN, namely by SiAlON ceramic-BN-AlN.SiAlON ceramic chemical composition Si
6-
zalzOzN
8the content of to be the content of 2 ~ 4, BN be 0.5 ~ 59%, the AlN of the Z value in-z is 1 ~ 10%.
The side seal board material of Japanese Patent JP8243689 adds Mo, is namely made up of SiAlON ceramic-BN-Mo sill.The chemical composition Si of match dragon pottery
6-
zalzOzN
8the content of to be 2 ~ 4, BN be 0.5 ~ 50%, the Mo of the Z value in-z is still 1 ~ 10%.
Japanese Patent JP3999993 discloses thin-strip casting side sealing ceramic plate, and the formation of this ceramic plate is, with REAG phase 10-90 volume %, Sialon phase 5-50 volume %, BN phase 5-50 volume % are the twin-roll thin strip continuous casting side seal ceramic plate of feature.Mention and adopt amorphous phase 0-20 volume %, for the constitution element of amorphous phase, rare earth element, Al, Si, O, N element are better, inevitably containing some impurities.
US Patent No. 4885264 discloses hot pressed sintering BN, ZrO
2and SiC ceramic matrix composite material, for horizontal casting separating ring.Adopt interim bonding agent when only mentioning mixing, do not speak of and adopt which type of sintering aid.
US Patent No. 6667263B1 discloses hot pressed sintering BN, matches grand matrix material, for thin-strip casting side sealing plate.Sintering aid adopts MgO and Y
2o
3.
Ceramic composite disclosed in US Patent No. 2005/0288168A1 is: the BN of 10-40% mullite, 35-5%AlN and 20%.Add the sintering aid of less than 5%, adopt B
2o
3, CaO, MgO, CeO
2, Y
2o
3, boric acid, silicate composite, aluminous cement, kaolin, refractory glass material, resol, furane resin, pitch and their mixture.
Chinese patent CN102173792 " a kind of ceramic composite for thin-strip casting side sealing plate and preparation method thereof ", stupalith by volume mark is made up of the additive of the zirconium white of 20-70%, the boron nitride of 20-70% and 2-30%.Proposition additive is a kind of or wherein several combination in oxide compound, carbide, nitride, boride, metal simple-substance, inorganics simple substance.It is characterized in that oxide compound is a kind of or wherein several combination in silicon oxide, aluminum oxide, boron oxide, titanium oxide, yttrium oxide, ytterbium oxide, lanthanum trioxide; Carbide is a kind of or wherein several combination in silicon carbide, norbide, titanium carbide, zirconium carbide; Nitride is a kind of or wherein several combination in silicon nitride, aluminium nitride, titanium nitride, zirconium nitride; A kind of or wherein several combination in my titanium boride of boride, zirconium boride 99.5004323A8ure, hafnium boride, lanthanum boride; Metal simple-substance is a kind of or wherein several combination in aluminium, titanium, zirconium; Inorganics simple substance is a kind of or wherein several combination in pure boron, elemental silicon, simple substance carbon, elemental sulfur.Above-mentioned additive is exactly sintering aid, but such additive composition is very general not concrete, and addition scope is very large, allows people feel to feel at a loss.
The sintering aid of comprehensive above-mentioned patent documentation, some patent documentation adds metal, and a patent documentation specifically adopts MgO and Y
2o
3, other patent documentation or broadly explain, otherwise not mentioned.
Summary of the invention
The object of the present invention is to provide a kind of BN-ZrO
2the complex sintering aids of-SiC ceramic matrix composite material, this complex sintering aids adopts Al
2o
3micro mist, CaCO
3fine powder and SiO
2micro mist carrys out hot pressed sintering and produces BN matrix material, can reach good and help nodulizing, makes that material void content is low, intensity is high, high comprehensive performance.
In order to realize above-mentioned technical purpose, the present invention adopts following technical scheme:
A kind of BN-ZrO
2the complex sintering aids of-SiC ceramic matrix composite material, comprises Al
2o
3micro mist, CaCO
3fine powder and SiO
2micro mist, Al
2o
3micro mist 1-4%, CaCO
3fine powder 1-3%, SiO
2micro mist 1-3%; This complex sintering aids is used for BN matrix material, BN content 30-70%, ZrO in this matrix material
2content 20-60%, SiC content 5-30%, sintering aid content 2-10%.
Described Al
2o
3micro mist adopts the super-fine powder of purity more than 99%, and mean particle size is less than 5 μm.
Described CaCO
3adopt purity more than 99%, granularity is less than 320 object fine powders.
Described SiO
2the purity more than 94% of micro mist, mean particle size is less than 1 μm.
Described three sintering aids at high temperature form Al
2o
3-CaO-SiO
2low melting point phase.
Complex sintering aids of the present invention adopts Al
2o
3micro mist, CaCO
3fine powder and SiO
2micro mist carrys out hot pressed sintering and produces BN matrix material, and the complex sintering aids of employing unlike the prior art.While overcoming existing sintering aid shortcoming, can reach good and help nodulizing, make that material void content is low, intensity is high, high comprehensive performance.While BN matrix material has superior heat-shock resistance, there is good wear resistance and resistance to fouling.BN matrix material can be used for the continuous casting functional such as thin-strip casting side sealing plate, spray forming liquid delivery tube refractory materials.
The BN matrix material that complex sintering aids of the present invention is made, this BN matrix material mainly BN, ZrO
2with the matrix material of SiC.The advantage of BN is that thermal conductivity is high, and linear expansivity is little, good thermal shock, is a kind of high temperature solid lubricant, and BN product is easy to processing, and fusing point is higher, presents unreactiveness with molten metal, and shortcoming is that raw materials cost is high, hard-to-sinter.ZrO
2there is high rigidity, high strength, high tenacity, the physical and chemical performance that high wear resistance and chemical resistance etc. are excellent, there is very excellent anti-molten steel and the aggressiveness of slag, there is good heat-shock resistance.The BN-ZrO that both are combined
2matrix material, add some SiC simultaneously, make material have excellent heat-shock resistance, resistance to fouling, wear resistance and workability, be applicable to the high temperature resistant position that the working conditionss such as thin-strip casting side sealing plate, spray forming liquid delivery tube and continuous casting functional refractory materials are very harsh.
The manufacturing process of BN pottery has hot pressed sintering, chemical Vapor deposition process and pyrolysis method etc.Adopt hot-pressing sintering technique can to obtain close to theoretical density, void content close to the sintered compact of zero, easily obtain compact grained tissue and there is the product of excellent mechanical performances.
In order to the hot pressed sintering effect making BN matrix material reach good, the present invention adopts Al
2o
3micro mist, CaCO
3fine powder and SiO
2micro mist complex sintering aids.Al
2o
3micro mist adopts the super-fine powder of purity more than 99%, and mean particle size is less than 5 μm.CaCO
3adopt purity more than 99%, granularity is less than 320 object fine powders.SiO
2micro mist is the SiO produced when smelting ferrosilicon and industrial silicon
2and oxygen rapid oxidation in Si gas and air condensation and the ultra-fine siliceous powder body material of one formed.Adopt the silicon powder of purity more than 94%, have very high activity and very little granularity, mean particle size is less than 1 μm.SiO
2micro mist starts to occur liquid phase at 600 DEG C, can promote the sintering of material, Al at lesser temps
2o
3although micro mist fusing point is very high, micro mist is trickle, and specific surface area is large, active high, shows good to help nodulizing under high temperature.CaCO
3fine powder more than 900 DEG C is decomposed to form CaO, and CaO is to BN and ZrO
2have and certain help nodulizing.Meanwhile, three sintering aids at high temperature form Al
2o
3-CaO-SiO
2low melting point phase, lowest total of the melting point is 1300 DEG C, further acceleration of sintering.Al
2o
3micro mist, CaCO
3fine powder and SiO
2micro mist is generally applied at pottery, refractories industry, and wide material sources, price is not high.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
The main raw material of the embodiment of the present invention adopts hexagonal AlN, ZrO
2, SiC.BN makes material have excellent heat-shock resistance, ZrO
2improve the resistance to fouling of material, SiC improves the wear resistance of material.Sintering aid adopts Al
2o
3micro mist (purity 99.5%, granularity 2 μm), CaCO
3fine powder (purity 99%, granularity 500 order) and SiO
2micro mist (purity 96%, granularity 0.8 μm) composite assistant.Each material rate (weight percent), BN content 30-70%, ZrO
2content 20-60%, SiC content 5-30%, sintering aid content 2-10%.Raw material carries out ball milling mixing after weighing by proportioning.Abrading-ball adopts corundum ball, and abrading-ball is 2:1 with the ratio of raw material.Ball milling mixing time is no less than 40h.Mixed raw material loads graphite jig, carries out hot pressed sintering in a nitrogen atmosphere.Firing temperature 1650-1800 DEG C, pressure 13-25MPa.Product stripping after hot pressing furnace cooling, cuts into the general shape of product, is then finish-machined to the product meeting dimensional requirement further, last vacuum packaging after upper and lower surface polishes.
Following table lists the ratio of embodiment of the present invention main raw material and sintering aid and the performance of BN matrix material thereof.Wherein, material mixture ratio is all weight percentage.Can find out, embodiment all achieves good over-all properties, and comparative example adopts traditional single sintering aid, poor-performing, and wherein there is evil mind B2 sample inside, illustrates not fully sintered.
Examples and comparative examples of the present invention
* thermal shock test: 25 × 25 × 125 samples, 1200 DEG C air-cooled 5 times
Complex sintering aids of the present invention adopts Al
2o
3micro mist, CaCO
3fine powder and SiO
2micro mist carrys out hot pressed sintering and produces BN matrix material, by the acting in conjunction of micro mist sintering and liquid phase sintering under high temperature, makes material reach good sintering.The performance that material reaches, volume density 2.89g/cm
3above, apparent porosity less than 0.2%, more than compressive strength 293MPa, heat-shock resistance, 1200 DEG C air-cooled 5 times, material without distortion, cracking.The apparent porosity of BN matrix material is low, and density, intensity are high, high comprehensive performance, while BN matrix material has superior heat-shock resistance, also has good wear resistance and resistance to fouling.Complex sintering aids of the present invention overcomes the shortcoming of sintering aid in the past.
BN matrix material of the present invention can be used for the continuous casting functional such as thin-strip casting side sealing plate, spray forming liquid delivery tube refractory materials.
Claims (5)
1. a BN-ZrO
2the complex sintering aids of-SiC ceramic matrix composite material, is characterized in that: comprise Al
2o
3micro mist, CaCO
3fine powder and SiO
2micro mist, Al
2o
3micro mist 1-4%, CaCO
3fine powder 1-3%, SiO
2micro mist 1-3%; This complex sintering aids is used for BN matrix material, BN content 30-70%, ZrO in this matrix material
2content 20-60%, SiC content 5-30%, sintering aid content 2-10%.
2. BN-ZrO according to claim 1
2the complex sintering aids of-SiC ceramic matrix composite material, is characterized in that: described Al
2o
3micro mist adopts the super-fine powder of purity more than 99%, and mean particle size is less than 5 μm.
3. BN-ZrO according to claim 1
2the complex sintering aids of-SiC ceramic matrix composite material, is characterized in that: described CaCO
3adopt purity more than 99%, granularity is less than 320 object fine powders.
4. BN-ZrO according to claim 1
2the complex sintering aids of-SiC ceramic matrix composite material, is characterized in that: described SiO
2the purity more than 94% of micro mist, mean particle size is less than 1 μm.
5. BN-ZrO according to claim 1
2the complex sintering aids of-SiC ceramic matrix composite material, is characterized in that: described three sintering aids at high temperature form Al
2o
3-CaO-SiO
2low melting point phase.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198445A (en) * | 2015-10-21 | 2015-12-30 | 哈尔滨工业大学 | Boron nitride multi-phase ceramic side sealing plate and preparation method thereof |
| CN110066184A (en) * | 2019-06-14 | 2019-07-30 | 武汉科技大学 | A kind of boron nitride-base nozzle refractory material and preparation method thereof being used to prepare amorphous thin ribbon |
| CN110590336A (en) * | 2019-10-08 | 2019-12-20 | 河南鼎天新材料有限公司 | Inorganic powder material with self-healing sintering function and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1489988A (en) * | 2002-10-18 | 2004-04-21 | 中国科学院上海硅酸盐研究所 | Cheap machinable zirconium oxide ceramic dental repairing body and preparation thereof |
| CN101624285A (en) * | 2008-07-08 | 2010-01-13 | 比亚迪股份有限公司 | Composition for preparing zirconia ceramics and ceramics |
| CN101638317A (en) * | 2008-08-02 | 2010-02-03 | 比亚迪股份有限公司 | Fully stabilized zirconia ceramic material and preparation method thereof |
| CN102260078A (en) * | 2010-05-31 | 2011-11-30 | 比亚迪股份有限公司 | Zirconia ceramic and preparation method thereof |
| CN102795848A (en) * | 2012-08-02 | 2012-11-28 | 江苏锡阳研磨科技有限公司 | Low-temperature sintered zirconium silicate grinding ball and preparation method thereof |
| CN102964122A (en) * | 2012-11-23 | 2013-03-13 | 潮州三环（集团）股份有限公司 | Dielectric ceramic composite and manufacturing method of electronic element thereof |
-
2013
- 2013-09-24 CN CN201310435315.4A patent/CN104446512A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1489988A (en) * | 2002-10-18 | 2004-04-21 | 中国科学院上海硅酸盐研究所 | Cheap machinable zirconium oxide ceramic dental repairing body and preparation thereof |
| CN101624285A (en) * | 2008-07-08 | 2010-01-13 | 比亚迪股份有限公司 | Composition for preparing zirconia ceramics and ceramics |
| CN101638317A (en) * | 2008-08-02 | 2010-02-03 | 比亚迪股份有限公司 | Fully stabilized zirconia ceramic material and preparation method thereof |
| CN102260078A (en) * | 2010-05-31 | 2011-11-30 | 比亚迪股份有限公司 | Zirconia ceramic and preparation method thereof |
| CN102795848A (en) * | 2012-08-02 | 2012-11-28 | 江苏锡阳研磨科技有限公司 | Low-temperature sintered zirconium silicate grinding ball and preparation method thereof |
| CN102964122A (en) * | 2012-11-23 | 2013-03-13 | 潮州三环（集团）股份有限公司 | Dielectric ceramic composite and manufacturing method of electronic element thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105198445A (en) * | 2015-10-21 | 2015-12-30 | 哈尔滨工业大学 | Boron nitride multi-phase ceramic side sealing plate and preparation method thereof |
| CN110066184A (en) * | 2019-06-14 | 2019-07-30 | 武汉科技大学 | A kind of boron nitride-base nozzle refractory material and preparation method thereof being used to prepare amorphous thin ribbon |
| CN110590336A (en) * | 2019-10-08 | 2019-12-20 | 河南鼎天新材料有限公司 | Inorganic powder material with self-healing sintering function and preparation method and application thereof |
| CN110590336B (en) * | 2019-10-08 | 2021-10-19 | 河南鼎天新材料有限公司 | Inorganic powder material with self-healing sintering function and preparation method and application thereof |
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Application publication date: 20150325 |
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