Method for preparing ZrN-Al2O3-ZrO2 multiphase ceramic material by aluminum nitride-zirconium dioxide reactive sintering

A technology of zirconia and aluminum nitride, applied in the field of high-temperature ceramic materials, can solve problems such as unfavorable billet quality, damage to key continuous casting equipment, and deterioration of erosion resistance

Inactive Publication Date: 2014-05-14
NORTH CHINA UNIVERSITY OF SCIENCE AND TECHNOLOGY
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  • Abstract
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  • Application Information

AI Technical Summary

Problems solved by technology

[0004] As a high-temperature structural material, although ZrO 2 The material has been widely used, but because of ZrO 2 The volume effect of crystal transformation is large, and the thermal conductivity is small (about 0.36-1.27W m -1 ·K -1 ), high coefficient of thermal expansion (α=8~11×10 -6 / °C), its poor thermal shock resistance is still an urgent problem to be solved.
For example, during metallurgical continuous casting and pouring steel, the zirconia sizing nozzle undergoes a high-temperature sudden change from 800°C (preheating temperature) to about 1650°C (molten steel temperature). Such harsh thermal shock conditions can easily cause the zirconia sizing nozzle to Thermal shock cracking occurs, which deteriorates the erosion resistance of the sizing nozzle to molten steel, and greatly reduces the service life of the zirconia sizing nozzle, and even interrupts the continuous casting process due to abnormal changes in the hole diameter, resulting in excessive flow of molten steel, or steel breakout , or damage the key continuous casting equipment "mold"
For this reason, Shandong Laiwu Iron and Steel Co., Ltd. has developed a domestically initiated and internationally leading continuous casting tundish pouring sizing nozzle quick replacement device, and proposed a continuous casting tundish sizing nozzle rapid replacement technology for continuous flow, which is used to solve the problem of oxidation. The service life of zirconium nozzle is short, the tundish is replaced frequently, there is a large amount of molten steel injection, the loss of cutting head and tail of continuous casting blank is large, and the casting speed is too fast due to the erosion of nozzle in the later stage of casting, which is not good for the quality of casting blank and may cause leakage. Problems such as steel accidents
Although this measure relieved the impediment brought by the short life of the zirconia nozzle to the rapid development of high-efficiency continuous casting technology, it did not fundamentally solve the inapplicability of the current sizing nozzle material to the existing high-efficiency rapid continuous casting process The problem

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0018] Ingredients composition: 90% monoclinic zirconia with particle size ≤0.1μm, median particle size d 50 = 10% aluminum nitride with a particle size of 5 μm, and 1.5% calcium fluoride with a particle size ≤ 10 μm (additional).

[0019] First, mix monoclinic zirconia fine powder, aluminum nitride fine powder, and calcium fluoride fine powder according to the measured ratio, dry mix for 3 minutes, add an appropriate amount of absolute ethanol to form a flowable viscous slurry, wet The method mixed 4 hours; The slurry after the wet method was mixed was filtered to remove ethanol, then in the state of constantly stirring, gradually adding mass percentage is about 12% (mass percentage, extra) of rosin ethanol solution of 10% in the mixed powder, After continuing to stir and mix for 10 minutes, the material was trapped under sealed conditions, and a blank for pressure molding was obtained after 4 hours of material trapping. The uniformly mixed and trapped billet is formed into ...

Embodiment 2

[0023] Ingredients composition: 85% monoclinic zirconia with particle size ≤ 0.1 μm, median particle size d 50 = 15% of aluminum nitride of 5 μm, 1.5% of zirconium diboride with particle size ≤ 10 μm (additional).

[0024] First, mix the monoclinic zirconia fine powder, aluminum nitride fine powder, and zirconium diboride fine powder according to the metering ratio, dry mix for 3 minutes, and then add an appropriate amount of absolute ethanol to form a flowable viscous slurry. Wet mixing for 4 hours; the slurry after wet mixing was filtered to remove ethanol, and then in the state of constant stirring, gradually add about 12% (mass percentage, extra) of rosin ethanol solution with a mass percentage of 10% in the mixed powder , Continue to stir and mix for 10 minutes and trap the material under sealed conditions, and obtain a blank for pressure molding after 4 hours of trapping the material. The uniformly mixed and trapped billet is formed into a green body by a hydraulic pres...

Embodiment 3

[0028] Ingredients composition: 80% monoclinic zirconia with particle size ≤0.1μm, median particle size d 50 = 20% of aluminum nitride of 5 μm, 1.5% of aluminum disilicide with particle size ≤ 10 μm (additional).

[0029] First, monoclinic zirconia fine powder, aluminum nitride fine powder, and molybdenum disilicide fine powder are mixed according to the measured ratio, and after 2 minutes of dry mixing, an appropriate amount of absolute ethanol is added to form a flowable viscous slurry. Mixing method for 4 hours; The slurry after wet mixing was filtered to remove ethanol, and then in the state of constant stirring, gradually adding mass percentage was about 12% (mass percentage, extra) of rosin ethanol solution of 10% in the mixed powder, After continuing to stir and mix for 10 minutes, trap the material under sealed conditions, and obtain a blank for pressure molding after trapping the material for 3 hours. The uniformly mixed and trapped billet is formed into a green body...

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Abstract

The invention relates to a method for preparing a ZrN-aluminum nitride2O3-ZrO2 multiphase ceramic material by aluminum nitride-zirconium dioxide reactive sintering, belonging to the field of high-temperature ceramic materials. The multiphase material is prepared from the following raw materials in percentage by mass: 5-40% of aluminum nitride fine powder, 60-95% of monoclinic zirconium dioxide fine powder, and 1-1.5% of sintering accelerator (CaF2 or ZrB2 or MoSi2) fine powder (additional). The method comprises the following steps: dryly mixing the raw materials, adding anhydrous ethanol, and wetly mixing; removing ethanol from the slurry, adding a rosin ethanol solution, stirring, and standing in a sealed environment to obtain a blank; and molding the blank, drying, and keeping the temperature at 1400 DEG C for 6-8 hours in a dynamic nitrogen atmosphere to obtain the ZrN-Al2O3-ZrO2 multiphase ceramic material. The multiphase material has the advantages of high soaking capacity, small thermal expansion coefficient and favorable thermal shock resistance, is assisted by a microcrack toughening mechanism, and can provide a novel high-temperature ceramic material for the fields of steel and non-ferrous metallurgy, construction materials, electronics and the like.

Description

technical field [0001] The invention belongs to the field of high-temperature ceramic materials, in particular to the preparation of ZrN-Al by reaction sintering of aluminum nitride-zirconia 2 o 3 -ZrO 2 Methods for Composite Materials. Background technique [0002] ZrO 2 It has many excellent characteristics such as high melting point (2700°C), good chemical stability, high hardness, and is not easy to be wetted and eroded by metal solution. It is a high-temperature material that has attracted much attention. But due to ZrO 2 There are three crystal forms with different densities (cubic zirconia c-ZrO 2 6.27g / cm 3 , tetragonal zirconia t-ZrO 2 6.10g / cm 3 and monoclinic zirconia m-ZrO 2 5.68g / cm 3 ), in the temperature range from room temperature to 2700 °C, ZrO 2 m-ZrO 2 →t-ZrO 2 →c-ZrO 2 Crystal transformation, temperature drop ZrO 2 reverse transformation occurs, and in ZrO 2 When the crystal transformation occurs, it is accompanied by a large volume effe...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C04B35/48C04B35/622
Inventor 卜景龙王榕林张利芳王志发蔡艳张健
Owner NORTH CHINA UNIVERSITY OF SCIENCE AND TECHNOLOGY
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