CN1006886B - Silicone nitride/boron nitride composite and prepn. thereof - Google Patents
Silicone nitride/boron nitride composite and prepn. thereofInfo
- Publication number
- CN1006886B CN1006886B CN 87104774 CN87104774A CN1006886B CN 1006886 B CN1006886 B CN 1006886B CN 87104774 CN87104774 CN 87104774 CN 87104774 A CN87104774 A CN 87104774A CN 1006886 B CN1006886 B CN 1006886B
- Authority
- CN
- China
- Prior art keywords
- silicon nitride
- boron nitride
- hot pressing
- boron
- nitride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
- C04B35/593—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained by pressure sintering
Abstract
The present invention belongs to the field of high-temperature engineering ceramics of inorganic nonmetal material science. In the method of the present invention, a proper amount of dispersed phase silicon nitride powder is added in silicon nitride basal bodies, and through high-temperature hot pressing, the silicon nitride / boron nitride composite material is made; the thermal shock resistance (delta T is larger than 1200 DEG C), molten steel erosion resistance and machinability of the silicon nitride material are considerably improved, and the deliquescence of boron nitride sintered bodies is avoided. The horizontal continuous casting separating rings made from the material can be used for the horizontal continuous casting of different types of steel at the high temperature of 1500 DEG C to 1600 DEG C.
Description
The invention belongs to inorganic non-metallic materials science, high temperature engineering ceramics field.
It is simple that horizontal continuous casting technique has an apparatus and process, and slab quality is good, save energy, improve many advantages such as recovery rate of iron, obtained development faster in recent years abroad, as the cast company of West Germany, SUMITOMO CHEMICAL Iron And Steel Company etc. has all obtained suitable progress.At present, domestic many Iron And Steel Companies are also developing research to this technology, and begin to enter the stage of applying.
The pottery separating ring is one of key problem in technology of horizontal casting equipment, and it is positioned at the junction of tundish and crystallizer, and molten steel is flowed through the mouth of a river, separating ring to crystallizer from tundish.Separating ring is between the melting zone and solidification zone of molten steel, stands the thermal shocking of the about 1570 ℃ of left and right sides molten steel during casting, bears about 150 ℃ of-1570 ℃ of thermal stresses that the temperature difference produced in the casting process, and under being in the continuous erosion of molten steel and washing away.So general refractory materials is difficult to satisfy its service requirements.
At present, main both at home and abroad employing hot pressed boron is as the separating ring material, and result of use is also better, but boron nitride material cost of material is more expensive, and needs moisture protection in the storage and transport process, brings inconvenience to use.In addition, because the thermal conductivity of boron nitride material is bigger, casting technology and slab quality there is detrimentally affect.
Many superperformances such as silicon nitride ceramics is a kind of excellent high-temperature engineering ceramics, and it has high hard, high-strength, and chemical stability is good, but use as the separating ring material, anti-molten steel aggressiveness is relatively poor, and heat-shock resistance can not meet the demands, and causes the product performance instability.And profiled parts is difficult to carry out machining.
Reaction sintering Si
3N
4/ BN matrix material, because starting raw material and sintering mechanism are different with heat pressing process, thereby principal crystalline phase constitutes and the equal difference of material property in the final sintered compact.Reaction sintering has time reaction time long (giving sintering and reaction sintering time more than 150 hours), and the material void content is big, density is little, thereby intensity is lower, anti-molten steel aggressiveness is poor, work-ing life is shorter, anti-thermal shock strength retrogression's temperature lower (＜600 ℃) of while material, use easily produces and peels off, cracked phenomenon, causes the continuous casting process instability.
The purpose of material of the present invention is comprehensive Si
3N
4The advantage of material and BN material two aspects is improved Si
3N
4Fragility, the heat-shock resistance of pottery are lower, anti-molten steel corrodes relatively poor and more unmanageable shortcoming, also solve simultaneously general hot pressing BN engineering materials and BN composite sinter and be easy to moisture absorption decomposition, it is bigger to be difficult for keeping use and thermal conductivity, cause the temperature rise of continuous caster ternary point too high, make the unsettled shortcoming of continuous casting process, improve the preservation condition and the use properties of separating ring.
Material of the present invention has excellent high-temperature physics and chemical property, and its high temperature anti-thermal shock strength retrogression temperature (＞920 ℃) has very big raising than general structural ceramic material.This material also has excellent hot strength, and density is moderate, soaks into angle big (about about 120 ℃) with molten steel, so the anti-molten steel of material corrodes and abradability good (erosion rate＜0.8mm/ hour), has improved separating ring work-ing life greatly.The horizontal continuous casting steel separating ring that uses this material preparation to go out, can satisfy in the horizontal continuous casting process separating ring, have high-heat resistance shock resistant, can bear the requirement of about 1570 ℃ of-150 ℃ of thermal stress damages that the temperature difference produced and severe condition such as molten steel erosion, wearing and tearing such as anti-carbon steel, steel alloy and stainless steel.The thermal conductivity of this matrix material is lower simultaneously, make strand inside and outside crystallization uniform and delicate, avoided general hot pressing BN material thermal conductivity bigger, made the important control parameter-triple point temperature of continuous caster too high (higher about 300 ℃) and cause the shortcoming of the unstable even failure of continuous casting process than required value.Advantages such as this separating ring also has the tide of not being afraid of, working accuracy is higher, and assembling process is not fragile through industrialized level continuous casting certification test, reach the service requirements of industrialized level continuous casting fully.
The detailed description of the invention is:
(median size is less than 5 microns to use fine alpha-silicon nitride powders, α is greater than 80%) as the matrix powder raw material, use fine boron nitride powder (unstabilized monocline phase, median size is less than 5 microns) as compound disperse phase, from fine (median size is little 5 microns) alumina powder, the magnesium-aluminium spinel powder, Zirconium oxide powder, carbon dust, choose in the boron oxide powder a kind of to three kinds as sintering aid, according to silicon nitride matrix powder 55-90% weight ratio, boron nitride disperse phase 5～40% weight ratios, sintering aid 5～15% weight ratios are prepared burden, being dispersion medium with ethanol (or other organic solvent) adopts alumina balls (or silicon nitride ball in aluminum oxide ball milling (or be lined with other ball milling of the rubber liner), zirconia ball) mix grinding is 5～20 hours, after drying as the original powder of matrix material.
The original powder of above-mentioned matrix material is packed into behind the plumbago crucible, put into the hot pressing electric furnace, under the nonoxidizing atmosphere protection, induce to be heated to 1600～1800 ℃ of insulations 10～80 minutes, simultaneously sample is applied 100～400Kg/Cm
2Pressure, hot pressing becomes silicon nitride/boron nitride composite.
Utilize the present invention can the horizontal continuous casting steel of preparation garden base and square billet separating ring and other high temperature engineering ceramics parts.
Embodiment one:
According to 73% weight ratio alpha-silicon nitride powders (5 microns of median sizes, α phase 90%), 15% weight ratio boron nitride powder (3 microns of median sizes), 10% weight ratio alumina powder and 2% weight ratio B
2O
3The proportion ingredient of powder (3 microns of median sizes); with ethanol is dispersion medium; in the aluminum oxide ball milling, use the alumina balls mix grinding after 15 hours; place baking oven dry compound, more dried compound is packed in the plumbago crucible, crucible is put into the hot pressing electric furnace; feed nitrogen as protective atmosphere; be heated to 1700 ℃, be incubated 1 hour, simultaneously sample is applied 300Kg/Cm
2Pressure, hot pressing becomes silicon nitride/boron nitride composite goods.With the separating ring that this kind Composite Preparation goes out, high temperature resistant in the energy adaptation level continuous casting process to separating ring, anti-thermal shock, a harsh requirement such as anti-erosion.
Embodiment two:
Use the processing condition same with embodiment one, only changing proportioning raw materials is 65% alpha-silicon nitride powders, the boron nitride powder of 25% weight percent, the magnesium-aluminium spinel powder of 10% weight ratio, the matrix material separating ring of preparing through hot pressing can satisfy the performance requriements of horizontal casting to separating ring equally.
Claims (3)
1, the preparation method of a kind of silicon nitride/boron nitride composite sintered compact, it is characterized by alpha-silicon nitride powders with 55～90% weight ratios, the boron nitride powder of 5～40% weight ratios, the sintering aid of 5～15% weight ratios (comprising aluminum oxide, magnesium-aluminium spinel, zirconium white, boron oxide, powdered carbon) are that raw material is through mixing hot pressing.
2, as the preparation method of right 1 described silicon nitride/boron nitride composite sintered compact, its composite character is to be dispersion medium mix grinding 5～20 hours in ball milling with ethanol (or other organic solvents), drying.
3, as the preparation method of right 1 described silicon nitride/boron nitride composite sintered compact; its heat pressing process is characterized as its mixed back raw material; pack in the plumbago crucible; put into the hot pressing electric furnace; under protection of inert gas; be heated to 1600～1800 ℃, be incubated 10～80 minutes, simultaneously sample is applied 100～400kg/cm
2Pressure hot pressing form.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87104774 CN1006886B (en) | 1987-07-06 | 1987-07-06 | Silicone nitride/boron nitride composite and prepn. thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87104774 CN1006886B (en) | 1987-07-06 | 1987-07-06 | Silicone nitride/boron nitride composite and prepn. thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1030402A CN1030402A (en) | 1989-01-18 |
| CN1006886B true CN1006886B (en) | 1990-02-21 |
Family
ID=4815008
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87104774 Expired CN1006886B (en) | 1987-07-06 | 1987-07-06 | Silicone nitride/boron nitride composite and prepn. thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1006886B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112337C (en) * | 1999-05-28 | 2003-06-25 | 清华大学 | Preparation of silicon nitride-based composite material with superhigh tenacity |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060457C (en) * | 1997-02-03 | 2001-01-10 | 汪宁 | Composite porcelain containing hexagonal boron nitride and preparation method thereof |
| CN102170716B (en) * | 2010-12-09 | 2013-01-30 | 江苏华盛精细陶瓷科技有限公司 | Method for manufacturing silicon nitride heating body |
| CN103570370B (en) * | 2013-11-14 | 2017-05-17 | 武汉钢铁(集团)公司 | Hot-pressed ceramic refractory material for thin-strip continuous casting side sealing plate and preparation method of hot-pressed ceramic refractory material |
| CN106278283A (en) * | 2016-08-04 | 2017-01-04 | 长兴鑫宇耐火材料有限公司 | A kind of step sintering prepares the method for boron nitride ceramic material |
| CN107721434A (en) * | 2017-11-14 | 2018-02-23 | 苏州科茂电子材料科技有限公司 | Suitable for the piezo-electric ceramic composite material preparation method of transformer |
| CN108395257B (en) * | 2018-05-18 | 2021-04-02 | 哈尔滨工业大学 | Silicon nitride-based composite material and preparation method thereof |
| CN117229066A (en) * | 2019-01-31 | 2023-12-15 | 电化株式会社 | Ceramic sintered body, method for producing same, and nozzle member |
| CN111302810B (en) * | 2020-03-09 | 2021-04-16 | 中国科学院上海硅酸盐研究所 | Low-noise silicon nitride ceramic-based friction material and preparation method and application thereof |
| CN111548168A (en) * | 2020-05-13 | 2020-08-18 | 金华市德裕精密陶瓷科技有限公司 | Ceramic material formula of precision part and preparation method thereof |
| CN113929472A (en) * | 2021-11-24 | 2022-01-14 | 福州赛瑞特新材料技术开发有限公司 | Preparation method of composite boron nitride ceramic nozzle |
-
1987
- 1987-07-06 CN CN 87104774 patent/CN1006886B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1112337C (en) * | 1999-05-28 | 2003-06-25 | 清华大学 | Preparation of silicon nitride-based composite material with superhigh tenacity |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1030402A (en) | 1989-01-18 |
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