CN106927818B - Rapid low-cost preparation method of black zirconia ceramic - Google Patents

Rapid low-cost preparation method of black zirconia ceramic Download PDF

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CN106927818B
CN106927818B CN201710158058.2A CN201710158058A CN106927818B CN 106927818 B CN106927818 B CN 106927818B CN 201710158058 A CN201710158058 A CN 201710158058A CN 106927818 B CN106927818 B CN 106927818B
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black zirconia
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CN106927818A (en
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刘长青
张露月
李旭
伍媛婷
王秀峰
刘虎林
张新孟
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Shaanxi University of Science and Technology
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Abstract

The invention relates to a ceramic material and a preparation method thereof, in particular to a rapid low-cost preparation method of black zirconia ceramic, which adopts a liquid phase method to prepare a precursor solution, so that coloring ions and zirconium atoms are uniformly mixed at an atomic level, a coprecipitation method is further utilized to obtain a precursor complex intermediate, black zirconia raw material powder is obtained through low-temperature heat treatment, and the black zirconia ceramic product is obtained through pressing and sintering; the colorant atoms and zirconium atoms are uniformly mixed in the solution at the atomic level, so that the problem of uneven coloring of black zirconia is avoided, and meanwhile, simple copper ions are adopted as the colorant, so that the toxic action of cobalt, chromium, titanium, manganese and the like on a human body is avoided.

Description

Rapid low-cost preparation method of black zirconia ceramic
Technical Field
The invention belongs to the technical field of ceramic materials, and particularly relates to a rapid low-cost preparation method of black zirconia ceramic.
Background
The zirconium dioxide has excellent mechanics, thermal and electrical properties, and has unique phase change effect and high-temperature oxygen ion conduction phenomenon, so that the zirconium dioxide is widely used in the fields of high-temperature structural materials, fuel cells and the like. The black zirconia ceramic material has the characteristics of excellent mechanical property, pure color, metallic luster, lower radiation property and the like, becomes a novel material for high-grade decoration, such as high-grade home decoration artware, watch chains, television curtain wall decoration materials and the like, and has wide market prospect.
At present, the preparation of the black zirconia ceramics mainly adopts the following method: (1) and carrying out blackening treatment on the zirconia ceramic by utilizing a vacuum atmosphere, a reducing atmosphere or an inert atmosphere. The method has strict requirements on equipment and high production cost, and is difficult to prepare the black ceramic product with a complex shape; (2) adding coloring oxides of iron, cobalt, chromium, titanium, manganese and the like into the zirconia powder, uniformly mixing the materials, and obtaining the black zirconia ceramic through molding and sintering. The method has the advantages of difficulty in realizing uniform mixing of the pigment and the zirconia, complex preparation process, strict requirements on the content of the pigment and the sintering temperature, high raw material cost, potential problems of heavy metal leakage, radiation and the like.
In addition, with the increasing importance of people on ecological environment in recent years, the preparation process of the material is required to be low in cost (low in sintering temperature, simplified in process and the like), free of pollution and wide in selected sources as far as possible.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a rapid low-cost preparation method of black zirconia ceramics, which has the advantages of simple preparation process, strong operability and low cost.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for preparing black zirconia ceramics quickly and with low cost comprises preparing precursor solution by liquid phase method, mixing coloring ions and zirconium atoms uniformly at atomic level, obtaining precursor complex by coprecipitation method, obtaining black zirconia raw material powder by low temperature heat treatment, pressing, and sintering to obtain black zirconia ceramic product.
The coloring ions are copper, zirconium hydroxide and copper nitrate are used as raw materials, the copper nitrate provides coloring ions, and the zirconium hydroxide provides zirconium atoms.
The molar ratio of the zirconium hydroxide to the copper nitrate is 1: 1-3: 1, distilled water is adopted to prepare Zr (OH)4-CuNO3Adjusting the pH value of the precursor solution to 7-10 by ammonia water, and heating in a thermostatic water bath at 60-90 ℃ for 0.5-1.5 hours to obtain a precursor complex.
And carrying out suction filtration, impurity removal, drying and grinding on the precursor complex to obtain precursor powder, and carrying out heat treatment on the precursor powder at the temperature of 500-800 ℃ for 1-2 hours to obtain black zirconia raw material powder.
And pressing and molding the black zirconia raw material powder, and sintering at the temperature of 900-1500 ℃ for 1-2 hours to obtain the black zirconia ceramic product.
Compared with the prior art, the invention has the beneficial effects that:
1) because the copper ion colorant and zirconium atoms are uniformly mixed in the solution at the atomic level, the problem of nonuniform coloring of black zirconium oxide is avoided.
2) Simple copper ions are adopted as a coloring agent, so that the toxic action of cobalt, chromium, titanium, manganese and the like on a human body is avoided.
3) Preparing a precursor solution by adopting a liquid phase method, enabling coloring ions and zirconium atoms to achieve uniform mixing at an atomic level, further obtaining a precursor complex by utilizing a coprecipitation method, and obtaining black zirconia raw material powder by low-temperature heat treatment.
4) The preparation process of the raw material powder is simple, the raw material cost is low, no pollution is caused, the operability is strong, the activity of the obtained raw material powder is high, the sintering temperature is low, and the defects of high requirements on equipment and sintering temperature, complex preparation process, high production cost and the like in the conventional preparation method are overcome.
Drawings
FIG. 1 shows black zirconia ceramic articles prepared in examples 1 to 3.
FIG. 2 is a microscopic morphology view of black zirconia prepared in examples 1 to 3.
Fig. 3 is an XRD pattern of black zirconia prepared in examples 1-3.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the drawings and examples. The technical solution of the present invention is not limited to the following embodiments, but includes any combination of the embodiments.
Example 1
A rapid and low-cost preparation method of black zirconia ceramics is realized according to the following steps:
(1) with Zr (OH)4And CuNO3Preparing Zr (OH) from distilled water as a raw material4-CuNO3Precursor solution of Zr (OH)4With CuNO3The mass ratio of (1): 1.
(2) adjusting the pH value of the precursor solution in the step 1 to 9 by using ammonia water, and heating in a constant-temperature water bath at 60 ℃ for 1.5 hours to obtain a precursor complex;
(3) carrying out suction filtration, impurity removal, drying and grinding on the precursor complex obtained in the step 2 to obtain precursor powder;
(4) carrying out heat treatment on the precursor powder obtained in the step 3 at 600 ℃ for 1 hour to obtain black zirconia raw material powder;
(5) and (4) performing cold static pressure forming on the black zirconia raw material powder obtained in the step (4), and sintering at 900 ℃ for 2 hours to obtain the black zirconia ceramic product.
Example 2
A rapid and low-cost preparation method of black zirconia ceramics is realized according to the following steps:
(1) with Zr (OH)4And CuNO3Preparing Zr (OH) from distilled water as a raw material4-CuNO3Precursor solution; zr (OH)4With CuNO3The mass ratio of (1): 1.5.
(2) adjusting the pH value of the precursor solution in the step 1 to be 8 by adopting ammonia water, and heating the solution in a constant-temperature water bath at the temperature of 80 ℃ for 1.5 hours to obtain a precursor complex;
(3) carrying out suction filtration, impurity removal, drying and grinding on the precursor complex obtained in the step 2 to obtain precursor powder;
(4) carrying out heat treatment on the precursor powder obtained in the step 3 at 600 ℃ for 2 hours to obtain black zirconia raw material powder;
(5) and (4) performing cold static pressure forming on the black zirconia raw material powder obtained in the step (4), and sintering at 1200 ℃ for 1.5 hours to obtain the black zirconia ceramic product.
Example 3
A rapid and low-cost preparation method of black zirconia ceramics is realized according to the following steps:
(1) with Zr (OH)4And CuNO3Preparing Zr (OH) from distilled water as a raw material4-CuNO3Precursor solution; zr (OH)4With CuNO3The mass ratio of (1): 2.
(2) adjusting the pH value of the precursor solution in the step 1 to 7-10 by using ammonia water, and heating in a constant-temperature water bath at 90 ℃ for 1 hour to obtain a precursor complex;
(3) carrying out suction filtration, impurity removal, drying and grinding on the precursor complex obtained in the step 2 to obtain precursor powder;
(4) carrying out heat treatment on the precursor powder obtained in the step 3 at 600 ℃ for 2 hours to obtain black zirconia raw material powder;
(5) and (4) performing cold static pressure forming on the black zirconia raw material powder obtained in the step (4), and sintering at 1400 ℃ for 1.5 hours to obtain the black zirconia ceramic product.
FIG. 1 is a photograph of a ceramic product obtained by sintering a black zirconia raw material powder prepared by the present invention at 900 deg.C, 1200 deg.C and 1400 deg.C, respectively, after molding. FIG. 2 is an enlarged view of the microstructure of each of the samples of FIG. 1. Fig. 3 is an XRD analysis pattern of each sample in fig. 1. As can be seen from FIG. 1, the black zirconia ceramic product can be obtained by sintering the black zirconia raw material powder prepared by the invention at different temperatures. As can be seen from fig. 2, the obtained black zirconia ceramic product has uniform color and a denser microstructure. As can be seen from fig. 3, the composition of the ceramic product after sintering at different temperatures was almost unchanged, being pure zirconia and copper oxide; the increase of the sintering temperature has certain influence on the crystallization degree and the crystal form of the zirconium oxide; in addition, the raw material powder can be completely converted into zirconium oxide and copper oxide after being sintered at 900 ℃, and the crystallization degree is higher. The results show that the prepared raw material powder has high activity and is easy to sinter.

Claims (3)

1. A process for preparing black zirconium oxide ceramic quickly and low-cost from zirconium hydroxide and copper nitrateThe preparation method comprises the following steps of providing zirconium atoms by colored ions, preparing a precursor solution by a liquid phase method, enabling the colored ions and the zirconium atoms to be uniformly mixed at an atomic level, obtaining a precursor complex by a coprecipitation method, obtaining black zirconia raw material powder by low-temperature heat treatment, carrying out compression molding on the black zirconia raw material powder, and sintering at 900 ℃ for 2 hours to obtain the black zirconia ceramic product, wherein the preparation method of the precursor complex comprises the following steps: distilled water is adopted to prepare Zr (OH)4-CuNO3Adjusting the pH value of the precursor solution to 7-10 by ammonia water, and heating in a thermostatic water bath at 60-90 ℃ for 0.5-1.5 hours to obtain a precursor complex.
2. The method for rapidly preparing the black zirconia ceramic according to claim 1, wherein the mass ratio of the zirconium hydroxide to the copper nitrate is 1:1 to 3: 1.
3. The rapid low-cost preparation method of black zirconia ceramics as claimed in claim 1, wherein the precursor complex is filtered, purified, dried and ground to obtain precursor powder, and the precursor powder is heat treated at 800 ℃ for 1-2 hours at 500 ℃ to obtain black zirconia raw material powder.
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CN108341668B (en) * 2018-04-20 2020-04-21 内蒙古科技大学 Black zirconia ceramic and preparation method thereof
CN110002867A (en) * 2019-04-22 2019-07-12 万华化学集团股份有限公司 A kind of green is zirconia ceramics and preparation method thereof
CN110467460B (en) * 2019-09-12 2022-03-11 广东东方锆业科技股份有限公司 Method for preparing composite zirconium oxide precursor by oxalate method
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