Black zirconia ceramic material

Abstract

The invention relates to the field of ceramic materials, in particular to a black zirconia ceramic material which is prepared from the following raw materials in percentage by mass: 3-7% of a coloring agent, 2-4% of Y2O3, 1-2% of a sintering aid and the balance of ZrO2, the coloring agent comprises a transition metal oxide, La1-xTbxFeO3 and a spinel type composite metal oxide, x is greater than 0 and less than or equal to 0.1, the prepared black zirconia ceramic material has the advantages of being good in coloring effect, high in coloring stability and excellent in mechanical property, and the application field of the black zirconia ceramic material is widened.

Description

Technical Field

[0001] The present invention relates to the field of ceramic materials, and specifically to a black zirconia ceramic material. Background Art

[0002] Due to its high strength, high toughness and biocompatibility, zirconia ceramic materials are widely used in the fields of precision structural components, medical implants and high-end decorative materials. With the improvement of the performance requirements of ceramic materials in the fields of consumer electronics, aerospace, etc., black zirconia ceramics with both high blackness aesthetic characteristics and excellent mechanical properties have become a research hotspot. However, traditional black colorants such as carbon black can achieve a certain blackness, but due to poor compatibility with the ceramic matrix, the performance of the ceramic material will be severely deteriorated after addition. And metal oxide colorants volatilize severely during high-temperature solid-phase sintering, not only with poor color rendering effect, but also with unstable color. After long-term use, it will turn white or gray, affecting the visual perception. Summary of the Invention

[0003] Object of the Invention: Aiming at the above technical problems, the present invention provides a black zirconia ceramic material.

[0004] The technical solution adopted is as follows:

[0005] A black zirconia ceramic material is made from the following raw materials in mass percentages:

[0006] Colorant 3 - 7%, Y2O3 2 - 4%, sintering aid 1 - 2%, and the balance is ZrO2;

[0007] The colorant includes transition metal oxides, La 1-x Tb x FeO3 and spinel-type composite metal oxides, where 0 < x ≤ 0.1.

[0008] Further, the mass ratio of the transition metal oxides, La 1-x Tb x FeO3 and the spinel-type composite metal oxides is 1 - 5:1 - 5:1 - 5.

[0009] Further, the transition metal oxides are a composition of Fe2O3 and MnO2.

[0010] Further, the mass ratio of Fe2O3 to MnO2 is 3 - 5:1.

[0011] Further, the preparation method of La 1-x Tb x FeO3 is as follows:

[0012] Dissolve lanthanum salt and terbium salt in deionized water to obtain solution A, dissolve iron salt in deionized water to obtain solution B, mix solution A and solution B evenly, slowly drop the sodium hydroxide solution into the mixed solution until the pH value of the solution ≥ 10, then stop dropping, stir the reaction solution at room temperature for 1 - 10 h, collect the precipitate, wash, dry and grind the precipitate, and then calcine it in a muffle furnace at 700 - 900 °C for 1 - 5 h.

[0013] Further, x = 0.02.

[0014] Further, the spinel - type composite metal oxide is a composition of ZnFe2O4 and CoAl2O4.

[0015] Further, the mass ratio of ZnFe2O4 to CoAl2O4 is 1 - 5:1 - 5.

[0016] Further, the sintering aid is a composition of CaO and TiO2.

[0017] Further, the mass ratio of CaO to TiO2 is 1 - 5:1 - 5.

[0018] Advantages of the present invention:

[0019] The present invention provides a black zirconia ceramic material. The colorant composed of transition metal oxides, La 1-x Tb x FeO3 and spinel - type composite metal oxide not only has the advantages of good color - rendering effect and high coloring stability, but also the prepared black zirconia ceramic material has excellent mechanical properties, which is beneficial to broadening the application fields of black zirconia ceramic materials;

[0020] Due to its unique perovskite crystal structure, LaFeO3 can finely regulate the absorption spectrum range after being added, enhance the depth and uniformity of black color - rendering, is not prone to phase change at high temperature, can reduce color shift caused by grain - boundary migration, so that the zirconia ceramic still maintains a stable black color after high - temperature sintering. Tb doping can inhibit the formation of lattice defects and oxygen vacancies, reduce color non - uniformity caused by defect scattering, further improve the coloring effect and mechanical strength, and enhance the thermal - aging resistance of zirconia ceramic materials;

[0021] In the spinel - type composite metal oxide, electrons of metal elements transition between d - orbitals of different energy levels, absorb light of a certain wavelength, and the corresponding light range is in the visible light region. When irradiated with light, electrons absorb light energy and transition from the ground state to the excited state. Each spinel metal oxide presents its complementary color after absorbing visible light waves in a certain visible - light band. In this application, by combining ZnFe2O4 and CoAl2O4, it cooperates with the other components to present a pure black color. Description of the drawings

[0022] Figure 1 Photograph of the black zirconia ceramic material prepared in Example 1 Detailed implementation mode

[0023] For those not specified in the examples, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. For reagents or instruments without indicating the manufacturer, they are all conventional products that can be obtained through commercial purchase. Technologies not mentioned in the present invention refer to the prior art. Unless otherwise specified, the following examples and comparative examples are parallel tests and adopt the same treatment steps and parameters.

[0024] Fe2O3: Zibo Huitie Pigment Co., Ltd.;

[0025] MnO2: Qinghe County Yaoxie Metal Materials Co., Ltd.;

[0026] La 0.98 Tb 0.02 FeO3: Self-made;

[0027] ZnFe2O4; Merck;

[0028] CoAl2O4; Hubei Xinghengye Technology Co., Ltd.;

[0029] Y2O3: Ningbo Beijiaer New Materials Co., Ltd.;

[0030] CaO: Ningbo Beijiaer New Materials Co., Ltd.;

[0031] TiO2: Ningbo Beijiaer New Materials Co., Ltd.;

[0032] ZrO2: Ningbo Beijiaer New Materials Co., Ltd.

[0033] Example 1:

[0034] A black zirconia ceramic material is made from the following raw materials in mass percentages:

[0035] Colorant 5%, Y2O3 3%, sintering aid 1%, and the balance is ZrO2;

[0036] The colorant consists of transition metal oxides, La 0.98 Tb 0.02 FeO3 and spinel-type composite metal oxides with a mass ratio of 3:1:1.

[0037] The transition metal oxides consist of Fe2O3 and MnO2 with a mass ratio of 3:1;

[0038] The spinel-type composite metal oxides consist of ZnFe2O4 and CoAl2O4 with a mass ratio of 1:1.

[0039] The sintering aid is CaO and TiO2 with a mass ratio of 1:1.

[0040] Among them, La 0.98 Tb 0.02 The preparation method of LaTbFeO3 is as follows:

[0041] First, prepare a sodium hydroxide solution with a concentration of 3 mol / L. Then, weigh 0.98 mmol of lanthanum nitrate hexahydrate and 0.02 mmol of terbium nitrate hexahydrate respectively and add them to 25 ml of deionized water, and continuously stir to obtain solution A. Then, weigh 1 mmol of iron nitrate hexahydrate and dissolve it in 25 ml of deionized water to obtain solution B. Mix solution A and solution B evenly. Slowly drip the prepared sodium hydroxide solution into the mixed solution to form a large amount of reddish-brown flocculent precipitate. Stop dripping until the pH value of the solution ≥ 10. Continuously stir the reaction solution at room temperature for 5 h, then collect the precipitate. Wash the precipitate repeatedly with deionized water and absolute ethanol, dry it in an oven at 60 °C for 12 h, then grind it in an agate mortar for about 30 min. Finally, put the obtained powder into a quartz crucible, place it in a muffle furnace, heat it to 800 °C at a rate of 5 °C / min, and calcine it at this temperature for 5 h. Take it out after cooling to room temperature.

[0042] The preparation method of the above black zirconia ceramic material is as follows:

[0043] After drying the raw materials, add them to the ball milling tank of a planetary ball mill, use absolute ethanol as the ball milling aid, ball mill for 10 h, and the ball milling speed is 65 r / min. The slurry obtained after ball milling is subjected to high-energy ball milling for 3 h by a horizontal sand mill, and the ball milling speed is 2200 r / min. Dry the slurry after high-energy ball milling at 65 °C, grind and crush it in an agate mortar to obtain a mixed powder. First, dry-press and preform the mixed powder by an electric tablet press, the pressure is 8 MPa, and the pressure holding time is 60 s. Then, perform cold isostatic pressing densification treatment at 200 MPa to obtain a green body. Place the green body in a muffle furnace, heat it to 1450 °C at a rate of 10 °C / min, keep it warm and sinter for 3 h, and then naturally cool to room temperature to obtain the black zirconia ceramic material. For details, see Figure 1 .

[0044] Example 2:

[0045] A black zirconia ceramic material is made from raw materials with the following mass percentages:

[0046] Colorant 7%, Y2O3 4%, sintering aid 2%, and the balance is ZrO2;

[0047] The colorant consists of transition metal oxides, La 0.98 Tb 0.02 LaTbFeO3 and spinel-type composite metal oxides with a mass ratio of 3:1:1.

[0048] The transition metal oxide is composed of Fe2O3 and MnO2 with a mass ratio of 3:1;

[0049] The spinel-type composite metal oxide is composed of ZnFe2O4 and CoAl2O4 with a mass ratio of 1:1.

[0050] The sintering aid is CaO and TiO2 with a mass ratio of 1:1.

[0051] Among them, La 0.98 Tb 0.02 The preparation method of LaTbFeO3 is the same as that in Example 1;

[0052] The preparation method of the above black zirconia ceramic material is as follows:

[0053] After drying the raw materials, add them into the ball mill tank of a planetary ball mill, use absolute ethanol as the ball milling aid, ball mill for 10 h, the ball milling speed is 65 r / min, subject the slurry obtained after ball milling to high-energy ball milling for 3 h by a horizontal sand mill, the ball milling speed is 2200 r / min, dry the slurry after high-energy ball milling at 65 °C, grind and crush it with an agate mortar to obtain a mixed powder, preform the mixed powder by dry pressing with an electric tablet press, the pressure is 8 MPa, the pressure holding time is 60 s, then perform cold isostatic pressing densification treatment at 200 MPa to obtain a green body, place the green body in a muffle furnace, heat it to 1450 °C at a rate of 10 °C / min, hold for sintering for 3 h, and then naturally cool to room temperature.

[0054] Example 3:

[0055] A black zirconia ceramic material is made from raw materials with the following mass percentages:

[0056] Colorant 3%, Y2O3 2%, sintering aid 1%, and the balance is ZrO2;

[0057] The colorant is composed of a transition metal oxide, La 0.98 Tb 0.02 LaTbFeO3 and a spinel-type composite metal oxide with a mass ratio of 3:1:1.

[0058] The transition metal oxide is composed of Fe2O3 and MnO2 with a mass ratio of 3:1;

[0059] The spinel-type composite metal oxide is composed of ZnFe2O4 and CoAl2O4 with a mass ratio of 1:1.

[0060] The sintering aid is CaO and TiO2 with a mass ratio of 1:1.

[0061] Among them, La 0.98 Tb 0.02The preparation method of FeO3 is the same as that in Example 1;

[0062] The preparation method of the above-mentioned black zirconia ceramic material is as follows:

[0063] After drying the raw materials, add them into the ball milling tank of a planetary ball mill, use absolute ethanol as the ball milling aid, ball mill for 10 h, and the ball milling speed is 65 r / min. The slurry obtained after ball milling is subjected to high-energy ball milling for 3 h by a horizontal sand mill, and the ball milling speed is 2200 r / min. The slurry after high-energy ball milling is dried at 65 °C, ground and crushed by an agate mortar to obtain a mixed powder. The mixed powder is preformed by dry pressing with an electric tablet press, the pressure is 8 MPa, and the pressure holding time is 60 s. Then, it is densified by cold isostatic pressing at 200 MPa to obtain a green body. The green body is placed in a muffle furnace, heated to 1450 °C at a rate of 10 °C / min, held for sintering for 3 h, and then naturally cooled to room temperature.

[0064] Comparative Example 1:

[0065] It is basically the same as Example 1, except that the colorant does not contain La 0.98 Tb 0.02 FeO3.

[0066] Comparative Example 2:

[0067] It is basically the same as Example 1, except that commercially available LaFeO3 is used instead of La in the colorant 0.98 Tb 0.02 FeO3.

[0068] Comparative Example 3:

[0069] It is basically the same as Example 1, except that the colorant does not contain spinel-type composite metal oxides.

[0070] Comparative Example 4:

[0071] It is basically the same as Example 1, except that ZnFe2O4 is not contained in the spinel-type composite metal oxide.

[0072] Comparative Example 5:

[0073] It is basically the same as Example 1, except that CoAl2O4 is not contained in the spinel-type composite metal oxide.

[0074] Performance test:

[0075] ① Use the black zirconia ceramic materials prepared in Examples 1-3 and Comparative Examples 1-5 of the present invention as specimens for performance testing;

[0076] Use a CM-3600A colorimeter to measure the chromaticity values L * , a * and b* , L * The L value is the whiteness value, ranging from 0 to 100, where 0 represents complete black and 100 represents complete white. a * > 0, the color tends to be red. a * < 0, the color tends to be green. b * > 0, the color tends to be yellow. b * < 0, the color tends to be blue.

[0077] The four-sided indentation method was used to test the fracture toughness of the specimens. After polishing the specimens, a HV-50 Vickers hardness tester was used to perform point pressing on the polished ceramic surface with a test force of 5 kgf. By measuring the crack length and the diagonal length of the square hole, the fracture toughness of the specimens was calculated according to the toughness formula.

[0078] The test results are shown in Table 1 below:

[0079] Table 1:

[0080]

[0081] From the comparison of Examples 1-3 in Table 1 above, it can be seen that the black zirconia ceramic material prepared by the present invention has a deep black color and high fracture toughness;

[0082] From the comparison of Example 1 with Comparative Examples 1-2, it can be seen that La 0.98 Tb 0.02 The addition of FeO3 plays a positive role in improving the color and mechanical properties of the black zirconia ceramic material;

[0083] From Example 1 and Comparative Examples 3-5, it can be seen that the addition of the spinel-type composite metal oxide plays a positive role in improving the color and mechanical properties of the black zirconia ceramic material.

[0084] ② Another set of specimens from Example 1 and Comparative Examples 1-2 were placed in an 80 °C oven for 1000 h of aging, and then the colorimetric values L * , a * and b * of the specimens were measured respectively using a CM-3600A colorimeter to compare the black color change of the specimens before and after aging. The colorimetric values L * , a * and b * of the specimens after aging are shown in Table 2 below:

[0085] Table 2:

[0086]

[0087] From the comparison of Example 1 with Comparative Examples 1-2 in Table 2 above, it can be seen that for the specimens of Comparative Examples 1-2 after thermal aging, L* and a * and b * both increased to varying degrees, while for the sample L of Example 1 * and a * and b * basically remained unchanged. Therefore, the addition of La 0.98 Tb 0.02 FeO3 played a positive role in the thermal aging resistance of the black zirconia ceramic material.

[0088] The above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit them. Although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the present invention in each embodiment.

Claims

1. A black zirconia ceramic material, characterized in that, Made from raw materials with the following mass percentages: Colorant 3 - 7%, Y2O3 2 - 4%, sintering aid 1 - 2%, the balance being ZrO2; The colorant includes transition metal oxides, La 1-x Tb x FeO3 and spinel type composite metal oxide, wherein 0<x≤0.

1.

2. The black zirconia ceramic material according to claim 1, wherein The transition metal oxide, La 1- x Tb x The mass ratio of the FeO3 and the spinel-type composite metal oxide is 1-5:1-5:1-5.

3. The black zirconia ceramic material according to claim 1, characterized in that, The transition metal oxide is a composition of Fe2O3 and MnO2.

4. The black zirconia ceramic material according to claim 3, wherein The mass ratio of Fe2O3 to MnO2 is 3 - 5:

1.

5. The black zirconia ceramic material according to claim 1, wherein, The La 1-x Tb x The preparation method of FeO3 is as follows: Dissolve lanthanum salt and terbium salt in deionized water to obtain solution A, dissolve iron salt in deionized water to obtain solution B, mix solution A and solution B evenly, slowly drop the sodium hydroxide solution into the mixed solution until the pH value of the solution ≥ 10, stop dropping, continuously stir and react the reaction solution at room temperature for 1 - 10 h, collect the precipitate, wash, dry and grind the precipitate, and then calcine it in a muffle furnace at 700 - 900 °C for 1 - 5 h.

6. The black zirconia ceramic material according to claim 1, characterized in that, x＝0.02。 7. The black zirconia ceramic material according to claim 1, characterized in that, The spinel - type composite metal oxide is a composition of ZnFe2O4 and CoAl2O4.

8. The black zirconia ceramic material according to claim 7, wherein The mass ratio of ZnFe2O4 to CoAl2O4 is 1 - 5:1 - 5.

9. The black zirconia ceramic material according to claim 1, wherein The sintering aid is a composition of CaO and TiO2.

10. The black zirconia ceramic material according to claim 9, wherein, The mass ratio of CaO to TiO2 is 1 - 5:1 - 5.

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