CN108455976B - Sintered tabular corundum with low zirconium content and preparation method thereof - Google Patents

Sintered tabular corundum with low zirconium content and preparation method thereof Download PDF

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CN108455976B
CN108455976B CN201810016251.7A CN201810016251A CN108455976B CN 108455976 B CN108455976 B CN 108455976B CN 201810016251 A CN201810016251 A CN 201810016251A CN 108455976 B CN108455976 B CN 108455976B
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monoclinic zirconia
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陈要生
赵义
马铮
李媛媛
宋雅楠
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Zhejiang Zili Advanced Materials Co ltd
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    • 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
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
    • C04B35/101—Refractories from grain sized mixtures
    • C04B35/106—Refractories from grain sized mixtures containing zirconium oxide or zircon (ZrSiO4)
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5436—Particle size related information expressed by the size of the particles or aggregates thereof micrometer sized, i.e. from 1 to 100 micron
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/77—Density
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance

Abstract

The invention discloses a low-zirconium-content sintered tabular corundum and a preparation method thereof, wherein the preparation method comprises the following steps: mixing industrial alumina powder and monoclinic zirconia powder according to the mass ratio of 1: 0.05-0.16, grinding and balling sequentially, and firing at 1700-1800 ℃ for 2.5-3.5h to obtain the low-zirconium-content sintered tabular corundum. The particle size of the monoclinic zirconia powder is 2 mu m and/or 10 mu m. The sintered tabular corundum with low zirconium content prepared by the invention has the advantages of good thermal shock stability, simple preparation process and low cost, and is suitable for industrial production.

Description

Sintered tabular corundum with low zirconium content and preparation method thereof
Technical Field
The invention relates to the field of refractory materials, in particular to low-zirconium-content sintered tabular corundum and a preparation method thereof.
Background
The thermal shock stability is one of the most important performance indexes of the refractory material, particularly for products such as sliding plates or ladle bricks, the products are easy to crack and cannot be used continuously due to frequent severe temperature change, and the improvement of the thermal shock stability of the refractory material is the only solution.
In the prior art, the sintered tabular corundum has good thermal shock stability due to the fact that the crystal grains contain more closed micro-pores, but the use requirement cannot be met, and therefore, a plurality of refractory manufacturers can select to add part of electro-fused zirconia corundum to improve the thermal shock stability of the refractory.
However, the fused zirconia corundum has the following problems in the preparation process:
1) high energy consumption in the preparation process, ZrO2The addition amount is large and is generally higher than 20 wt%, so that the preparation cost of the material is higher;
2) ZrO in fused zirconia corundum2The crystal grains have a large size (generally 50 μm or more) and are unevenly distributed, and ZrO cannot be sufficiently expressed2The toughening effect of (1).
Disclosure of Invention
The invention provides a low-zirconium-content sintered tabular corundum, which has lower zirconium content, better thermal shock stability, low cost and simple preparation.
A method for preparing low-zirconium-content sintered tabular corundum comprises the following steps:
mixing industrial alumina powder and monoclinic zirconia powder according to the mass ratio of 1: 0.05-0.16, grinding and balling sequentially, and firing at 1700-1800 ℃ for 2.5-3.5h to obtain the low-zirconium-content sintered tabular corundum.
Compared with the plate-shaped corundum prepared by adopting an electric melting method in the prior art, the plate-shaped corundum prepared by adopting the sintering method has lower zirconium content and better thermal shock stability.
In the sintered tabular corundum, ZrO2Has a smaller grain size of corundum, ZrO2The crystal grains are uniformly distributed at the grain boundary position of the corundum crystal grains, the effect of micro-crack toughening is fully exerted, and the thermal shock stability of the sintered plate-shaped corundum is improved.
ZrO can be controlled by controlling the mass ratio and the firing temperature of the industrial alumina powder and the monoclinic zirconia powder2The size and the distribution uniformity of the crystal grains are improved, so that the thermal shock resistance of the sintered tabular corundum is improved, the sintered tabular corundum has higher fracture toughness, and the thermal shock stability of related products is further improved.
Preferably, the monoclinic zirconia powder has a particle size of 2 μm or 10 μm.
When the monoclinic zirconia powder has a fine particle size, the monoclinic zirconia powder is relatively easy to sinter in the sintering process, and the volume density is correspondingly improved; when the monoclinic zirconia powder has a coarse particle size, sintering is difficult in the sintering process.
In the present invention, monoclinic zirconia powder is used, and the particle size is optimized to ensure that ZrO in the sintered tabular corundum2The corundum crystal grains have small size and can be uniformly distributed at the grain boundary position of the corundum crystal grains, the size of the corundum crystal grains is moderate, the corundum crystal grains are controlled to be 30-50 mu m, when the corundum crystal grains are too large, the corundum crystal grains cannot play a role in improving the thermal shock stability, and when the corundum crystal grains are too small, the corundum wear-resisting property is easy to causeAnd the deterioration is made.
In the present invention, the particle diameter is a number average particle diameter unless otherwise specified.
Preferably, the monoclinic zirconia powder is formed by mixing 2-micron monoclinic zirconia powder and 10-micron monoclinic zirconia powder, and the mass ratio of the 2-micron monoclinic zirconia powder to the 10-micron monoclinic zirconia powder is 1: 0.5 to 1.
The method adopts the blending of monoclinic zirconia powder with two grain sizes, and can improve ZrO by adjusting the proportion of 2 mu m monoclinic zirconia powder and 10 mu m monoclinic zirconia powder2The distribution uniformity of the crystal grains at the grain boundary position of the corundum crystal grains and the growth size of the crystal grains are reasonably controlled.
Preferably, in the monoclinic zirconia powder of 2 μm, D501.8 to 2.3 μm, ZrO2The content is more than 99.0 percent; in 10 μm monoclinic zirconia powder, D50Is 10-15 μm, ZrO2The content is more than 98.5 percent.
Preferably, more than 90 wt% of the ground powder passes through a 325 mesh sieve.
After mixing the industrial alumina powder and the monoclinic zirconia powder, grinding for 1-2 hours to ensure that more than 90% of the ground powder can pass through a 325-mesh sieve (manufactured by Taylor). Namely, more than 90 percent of the ground powder has the particle size of less than 45 mu m by mass fraction.
Preferably, the balling adopts a two-step method, water is used as balling liquid during balling, and the using amount of the water is 18-22%.
In the invention, the salt balling liquid is not required to be introduced, water is directly adopted as the balling liquid, the corrosion to the pipeline is effectively avoided, the process operation is simple, the cost is low, and the method is suitable for large-scale production. The using amount of the water is 18-22% by mass fraction, and the balling liquid is continuously applied in the whole balling process.
Preferably, the pellets are baked after being dried twice, and the temperature of the first drying is
180-300 ℃, the temperature of the second drying is 550-650 ℃, and the moisture content of the dried balls is not more than 0.5%.
Preferably, in the industrial alumina powder, the mass percent of each component isRespectively, the following steps: al (Al)2O3≥98.0％，SiO2≤0.10％，CaO≤0.15％，Fe2O3≤0.1％，Na2O≤0.5％。
Preferably, the particle size of the industrial alumina powder is not more than 25 μm.
That is, the industrial alumina powder can pass through a 60-mesh screen. The grain size of the sintered corundum grains and ZrO can be controlled by controlling the grain diameter of the industrial alumina powder2The distribution uniformity of the crystal grains at the grain boundary position of the corundum crystal grains.
The invention also provides a low-zirconium-content sintered tabular corundum prepared by the preparation method.
The sintered tabular corundum obtained by the preparation method provided by the invention is detected as follows: the bulk density is 3.50-3.58g/cm3(ii) a Apparent porosity of 3.4-4.8%, water absorption of 1.0-1.9%, and Al2O3The grain size (i.e. corundum grain size) is 30-50 μm, and the optimal size is controlled to be 30-40 μm; ZrO (ZrO)2The grain size is 0.7-15 μm, and the optimal grain size is controlled to be 1.0-9 μm; the fracture toughness is 9.0-13.5 Mpa.m0.5。
The sintered tabular corundum with low zirconium content prepared by the invention has the advantages of good thermal shock stability, simple preparation process and low cost, and is suitable for industrial production.
Drawings
FIG. 1 is a micrograph of a low zirconium content sintered tabular corundum prepared in example 4 of the present invention.
Detailed Description
The invention is further described with reference to specific examples.
Examples 1 to 6
A method for preparing low-zirconium-content sintered tabular corundum comprises the following steps:
(1) the industrial alumina powder and the monoclinic zirconia powder are respectively placed in different bins, the bins are communicated into the ball mill through respective pipelines, and the feeding mass ratio of the industrial alumina powder and the monoclinic zirconia powder is shown in table 1.
Of technical aluminaThe main component is gamma-alumina, and the mass fractions of the components in the industrial alumina powder are respectively Al2O3≥98.0％、SiO2≤0.10％、CaO≤0.15％，Fe2O3≤0.1％，Na2O≤0.5％。
In Table 1, D in 2 μm monoclinic zirconia powder50＝1.8-2.3μm，ZrO2The mass fraction is more than 99.0 percent; in 10 μm monoclinic zirconia powder, D50＝10-15μm，ZrO2The mass fraction is more than 98.5 percent.
(2) The commercial alumina powder and the monoclinic zirconia powder were milled in a ball mill for the milling times shown in table 1.
(3) After the grinding, the ball was placed in a balling plate, and water was sprayed as a balling liquid in an amount shown in Table 1 to prepare 6 to 7mm master balls, and the master balls were fed into a balling cylinder to prepare green balls having a diameter of 23. + -. 2 mm.
(4) And (3) drying the green pellets for two times in sequence, wherein the temperature and the time of the two times of drying are shown in table 1, and the moisture content of the dried green pellets is less than 0.5%.
(5) And (3) sintering the dried green pellets in a high-temperature shaft kiln, wherein the sintering temperature and the sintering time are shown in table 1. And cooling along with the furnace, crushing, screening and packaging to obtain the sintered tabular corundum with low zirconium content.
TABLE 1
Figure BDA0001542042840000041
Figure BDA0001542042840000051
Comparative example 1
The preparation process flow of this example is the same as that of example 4, only the kind of zirconia added is changed, and the calcium oxide stabilized zirconia powder is introduced, and the specific adding ratio and parameters are shown in table 2.
The calcium oxide stabilized zirconia powder has the following relevant parameters:
calcium oxideStabilized zirconia powder, D50Is 10-15 μm, ZrO2The content is more than 94.0 percent, and the CaO content is 4.5 to 5.0 weight percent.
Comparative examples 2 to 3
The preparation process flow of the comparative examples 2 to 3 is consistent with that of the example 4, only the sintering temperature is changed, and the specific addition ratio and parameters are shown in the table 2.
Comparative examples 4 to 5
The preparation process flow of comparative examples 4-5 is the same as that of example 4, only the sintering time is changed, and the specific addition ratio and parameters are shown in table 2.
TABLE 2
Figure BDA0001542042840000052
Figure BDA0001542042840000061
Performance characterization
The results of the performance tests of the sintered plate-like corundum prepared in examples 1 to 6 and comparative examples 1 to 5 are shown in Table 3. In the sintered tabular corundum with low zirconium content prepared in each example, the mass percentages of the components are as follows: al (Al)2O3≥96.5％-97.5％，SiO2≤0.10％-0.15％，Fe2O3≤0.1-0.2％，Na2O≤0.2-0.4％，ZrO2≥2.5-3.5％。
TABLE 3
Figure BDA0001542042840000062
As can be seen from Table 3, the sintered tabular corundum with low zirconium content prepared by the present invention has a bulk density of 3.50 to 3.58g/cm3(ii) a Apparent porosity of 3.4-4.8%, water absorption of 1.0-1.9%, and Al2O3Grain size of 30-50 μm, ZrO2Grain size is 0.7-15 μm; fracture toughness of 9.0-13.5 Mpa.m0.5。
FIG. 1 shows an electron micrograph of example 4As can be seen from FIG. 1, the corundum grains have an average size of 30 to 40 μm and the white region is ZrO2Grain of ZrO2Grain size of 1.0-9 μm, ZrO2The grain size is uniform, and the ZrO2 grains are uniformly distributed at the combination of corundum grains and crystal grains.
Appropriate changes and modifications to the embodiments described above will become apparent to those skilled in the art from the disclosure and teachings of the foregoing description. Therefore, the present invention is not limited to the specific embodiments disclosed and described above, and some modifications and variations of the present invention should fall within the scope of the claims of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (7)

1. A preparation method of low-zirconium-content sintered tabular corundum is characterized by comprising the following steps:
mixing industrial alumina powder and monoclinic zirconia powder according to the mass ratio of 1: 0.05-0.16, grinding and balling sequentially, and then firing at 1700-1800 ℃ for 2.5-3.5h to obtain the low-zirconium-content sintered tabular corundum;
the particle size of the industrial alumina powder is not more than 25 mu m;
the particle size of the monoclinic zirconia powder is 2 μm and/or 10 μm;
the monoclinic zirconia powder is formed by mixing 2-micron monoclinic zirconia powder and 10-micron monoclinic zirconia powder, and the mass ratio of the 2-micron monoclinic zirconia powder to the 10-micron monoclinic zirconia powder is 1: 0.5 to 1.
2. The method for preparing a sintered tabular corundum having a low zirconium content according to claim 1, wherein D is the content of monoclinic zirconia powder having a particle size of 2 μm501.8 to 2.3 μm, ZrO2The content is more than 99.0 percent; in 10 μm monoclinic zirconia powder, D50Is 10-15 μm, ZrO2The content is more than 98.5 percent.
3. The method for producing a sintered tabular corundum with a low zirconium content according to claim 1, wherein 90% by weight or more of the ground powder passes through a 325-mesh sieve.
4. The method for preparing the sintered tabular corundum with low zirconium content according to claim 1, wherein the balling adopts a two-step method, water is used as balling liquid during balling, and the using amount of the water is 18-22%.
5. The method for preparing sintered tabular corundum with low zirconium content according to claim 1, wherein the sintering is carried out after the first drying at 180-300 ℃ and the second drying at 550-650 ℃, and the moisture content of the dried spheres is not more than 0.5%.
6. The method for preparing the sintered tabular corundum with low zirconium content according to claim 1, wherein the industrial alumina powder comprises the following components in percentage by mass: al (Al)2O3≥98.0％，SiO2≤0.10％，CaO≤0.15％，Fe2O3≤0.1％，Na2O≤0.5％。
7. A sintered tabular corundum with a low zirconium content, characterized by being prepared by the preparation method according to any one of claims 1 to 6.
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