阅读说明：本技术 一种多种元素增韧氧化锆基陶瓷材料的制备方法及其产品 (Preparation method of multi-element toughened zirconia-based ceramic material and product thereof ) 是由 邓珊 于 2020-06-19 设计创作，主要内容包括：本发明公开了一种多种元素增韧氧化锆基陶瓷材料及其制备方法。制备的材料为一种多种元素增韧氧化锆基陶瓷材料,材料的化学组成为Zr<Sub>a</Sub>Yb<Sub>b</Sub>Ce<Sub>c</Sub>Sc<Sub>d</Sub>Y<Sub>e</Sub>O<Sub>x</Sub>,其中a＝88.1～94.1,b＝4～5,c＝1～2,d＝0.5～1.5,e＝1～3,x满足其它元素化合价所需的氧原子总数。本发明提供的材料具有较高的相稳定性、高韧性、致密性的特点,该材料的最高断裂韧性可达12.34MPa·m<Sup>1/2</Sup>,最高的硬度为1120HV<Sub>10</Sub>；抗弯强度为910.4MPa；致密性为98.2％。(The invention discloses a multi-element toughened zirconia-based ceramic material and a preparation method thereof. The prepared material is a multi-element toughened zirconia-based ceramic material, and the chemical composition of the material is Zr a Yb b Ce c Sc d Y e O x Wherein a is 88.1 to 94.1, b is 4 to 5, c is 1 to 2, d is 0.5 to 1.5, e is 1 to 3, and x satisfies the total number of oxygen atoms required by the valence of other elements. The material provided by the invention has the characteristics of higher phase stability, high toughness and compactness, and the highest fracture toughness of the material can reach 12.34 MPa.m 1/2 Maximum hardness of 1120HV 10 (ii) a The bending strength is 910.4 MPa; the compactness was 98.2％。)

1. A preparation method of a multi-element toughened zirconia-based ceramic material is characterized by comprising the following steps: the preparation method comprises the following steps:

1) firstly, nanometer superfine ZrO is firstly prepared₂Sieving the powder with a 200-mesh sieve;

2) the desired ZrO₂，Yb₂O₃，CeO₂，Sc₂O₃，Y₂O₃According to Zr_aYb_bCe_cSc_dY_eO_xThe method comprises the following steps of (1) weighing, wherein a is 88.1-94.1, b is 4-5, c is 1-2, d is 0.5-1.5, e is 1-3, and x meets the stoichiometric ratio of the total number of oxygen atoms required by the valence of other elements, and then placing the weighed materials into a ball milling tank for ball milling, wherein a ball milling medium is absolute ethyl alcohol;

3) after the ball milling is finished, the obtained suspension is dried in vacuum, grinding is carried out after drying, and the ground powder is sieved by a 200-mesh sieve;

4) calcining the sieved powder in a muffle furnace at 720-830 ℃ for 0.5-3 h, granulating the obtained powder after calcining, preforming the granulated powder by a tablet press, pressing the preformed powder under 250-300 MPa to obtain a blank, sintering the blank in the muffle furnace at 1250-1600 ℃ for 1-3 h, and cooling the blank to room temperature along with the furnace to obtain the ceramic.

2. The method of claim 1, wherein: the ball milling tank in the step 2) is a polyethylene ball milling tank, and 3Y-TZP balls are used for ball milling.

3. The method of claim 1, wherein: the step 2) also comprises 2 wt% of alumina.

4. The method of claim 1, wherein: in the step 2), the ball milling speed is 300-400 r/min, and the ball milling time is 8-16 h.

5. The method of claim 1, wherein: the vacuum drying in the step 3) is drying for 12-24 hours in a vacuum oven at 60-80 ℃ to remove ethanol.

6. The method of claim 1, wherein: in the step 4), the temperature rise rate of calcining for 0.5-3 h at 720-830 ℃ is 3-5 ℃/min; the temperature rise rate of sintering at 1250-1600 ℃ for 1-3 h is 8-10 ℃/min.

7. A multi-element toughened zirconia-based ceramic material prepared according to the preparation process of any one of claims 1 to 6.

8. The multi-element toughened zirconia-based ceramic material of claim 7, wherein: the fracture toughness of the multi-element toughened zirconia-based ceramic material is 11.45-12.34 MPa-m^1/2The highest hardness is 1090-1120 HV₁₀(ii) a The bending strength is 895.5-910.4 MPa; the compactness is 97.9-98.2%.

9. The use of the multi-element toughened zirconia-based ceramic material of claim 7 or 8 in the manufacture of a fuse for charging a mobile phone.

Technical Field

The invention belongs to the technical field of zirconia-based ceramics, and particularly relates to a preparation method of a multi-element toughened zirconia-based ceramic material and a product thereof.

Background

Zirconia ceramics find wide application in modern industrial fields, for example as extrusion and wire drawing dies, Solid Oxide Fuel Cells (SOFC)_s) The catalyst or the catalyst carrier, the phase change toughening ceramic, the automobile engine part, the oxygen sensor, the thermal barrier coating for the aeroengine and the like.

Zirconia is widely used as a ceramic material, but the performance of zirconia as a ceramic material cannot meet the requirements of the existing practical production, so that the modification of zirconia is the main means for improving the performance of zirconia at present. Wherein the 3Y-TZP has the best combination of strength and toughness and is widely applied as structural ceramics. However, due to the sensitivity of stress-induced phase change toughening to temperature, the phase change toughening fails with the rise of temperature, and the medium-high temperature performance of zirconia is not ideal enough. Furthermore, hydrothermal aging makes its use in corresponding environments limited (e.g. repeated steam sterilization of medical tools, bioimplants, steam turbine components, etc.). The advantages of different rare earth stabilizers can be effectively combined by utilizing a co-doping stabilization method, wherein the Ce-Y co-stabilized zirconia has the advantages of 3Y-TZP and Ce-TZP, the mechanical property and the ageing resistance are relatively good, but compared with Y-TZP, the grain size is still larger, and the mechanical property still needs to be further improved. Because the toughness of the TZP is mainly ensured by stress-induced transformation toughening, which means that there is a certain limit to improving the toughness of the TZP in this way, and toughening the zirconia by using a proper second phase becomes an effective means. Therefore, how to further optimize the friction resistance and the high-temperature phase stability of the zirconium oxide while simultaneously realizing the strengthening and toughening of the zirconium oxide through the component design and the process optimization is a series of technical problems to be solved urgently. In addition, the distribution and content of the rare earth elements have great influence on the mechanical property of the zirconia, the influence rule and mechanism of the interaction, distribution and content of the rare earth elements doped in the multi-element rare earth co-stabilized zirconia on the microstructure and the mechanical property are not clear, and the strengthening and toughening mechanism and the synergistic relationship among the mechanisms are not clear.

Therefore, the improvement of the toughness, hardness, bending strength and compactness of the zirconia-based ceramic material still needs to be solved at present.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a preparation method of a multi-element toughened zirconia-based ceramic material and a product thereof, aiming at the defects in the prior art, wherein the ceramic material has high fracture toughness, hardness, bending strength and compactness, and the application of the ceramic material in the manufacture of a fuse for charging a mobile phone.

The invention adopts the following technical scheme:

a preparation method of a multi-element toughened zirconia-based ceramic material is characterized by comprising the following steps: the preparation method comprises the following steps:

1) firstly, nanometer superfine ZrO is firstly prepared₂Sieving the powder with a 200-mesh sieve;

2) the desired ZrO₂，Yb₂O₃，CeO₂，Sc₂O₃，Y₂O₃According to Zr_aYb_bCe_cSc_dY_eOx, wherein a is 88.1-94.1, b is 4-5, c is 1-2, d is 0.5-1.5, e is 1-3, x satisfies the stoichiometric ratio of the total number of oxygen atoms required by the valence of other elements, and then the mixture is placed in a ball milling tank for ball milling, wherein the ball milling medium is absolute ethyl alcohol;

3) after the ball milling is finished, the obtained suspension is dried in vacuum, grinding is carried out after drying, and the ground powder is sieved by a 200-mesh sieve;

4) calcining the sieved powder in a muffle furnace at 720-830 ℃ for 0.5-3 h, granulating the obtained powder after calcining, preforming the granulated powder by a tablet press, pressing the preformed powder under 250-300 MPa to obtain a blank, sintering the blank in the muffle furnace at 1250-1600 ℃ for 1-3 h, and cooling the blank to room temperature along with the furnace to obtain the ceramic.

Preferably, the ball milling tank in the step 2) is a polyethylene ball milling tank, and 3Y-TZP balls are used for ball milling.

Preferably, the step 2) further comprises 2 wt% of alumina.

Preferably, the ball milling speed in the step 2) is 300-400 r/min, and the ball milling time is 8-16 h.

Preferably, the vacuum drying in the step 3) is drying for 12-24 hours in a vacuum oven at 60-80 ℃ to remove ethanol.

Preferably, in the step 4), the temperature rise rate of 0.5-3 h of calcination at 720-830 ℃ is 3-5 ℃/min; the temperature rise rate of sintering at 1250-1600 ℃ for 1-3 h is 8-10 ℃/min.

The invention also provides a multi-element toughened zirconia-based ceramic material prepared based on the preparation method.

Preferably, the fracture toughness of the multi-element toughened zirconia-based ceramic material is 11.45-12.34 MPa-m^1/2The highest hardness is 1090-1120 HV₁₀(ii) a The bending strength is 895.5-910.4 MPa; the compactness is 97.9-98.2%.

The invention also provides a technical scheme of application of the multi-element toughened zirconia-based ceramic material in manufacturing of the protective tube for charging the mobile phone based on the application of the multi-element toughened zirconia-based ceramic material.

Compared with the prior art, the invention has at least the following beneficial effects:

1) the multi-element toughened zirconia-based ceramic material provided by the invention is prepared by mixing, wet grinding, drying, grinding, sieving, pre-sintering, compression molding and sintering raw materials, the preparation process is simple, and the formed multi-element toughened zirconia-based ceramic material has high density and excellent main mechanical index, and is suitable for industrial popularization.

2) The alumina additive is added in the ball milling process, so that the compactness of the zirconia ceramic material is improved.

3) The fracture toughness, hardness, bending strength and compactness of the zirconia-based ceramic material are improved through the synergistic effect of multiple elements, and the fracture toughness of the zirconia-based ceramic material obtained through co-doping of multiple rare earths is 11.45-12.34 MPa-m^1/2The highest hardness is 1090-1120 HV₁₀(ii) a The bending strength is 895.5-910.4 MPa; the compactness is 97.9-98.2%.

In conclusion, the multi-element toughened zirconia-based ceramic material prepared by the invention is an ideal material for practical application.

The technical solution of the present invention is further described in detail by the following examples.

Detailed Description

The invention discloses a preparation method of a multi-element toughened zirconia-based ceramic material, which comprises the following steps:

1) firstly, nanometer superfine ZrO is firstly prepared₂Powder bodySieving with 200 mesh sieve;

2) the desired ZrO₂，Yb₂O₃，CeO₂，Sc₂O₃，Y₂O₃According to Zr_aYb_bCe_cSc_dY_eOx, wherein a is 88.1-94.1, b is 4-5, c is 1-2, d is 0.5-1.5, e is 1-3, x satisfies the stoichiometric ratio of the total number of oxygen atoms required by the valence of other elements, 2 wt% of alumina is added, and then the mixture is placed in a polyethylene ball milling tank to be ball milled by 3Y-TZP balls, wherein the ball milling medium is absolute ethyl alcohol; 300-400 r/min, and the ball milling time is 8-16 h;

3) after the ball milling is finished, drying the obtained powder in a vacuum oven at 60-80 ℃ for 12-24 h to remove ethanol, grinding the dried powder, and sieving the ground powder with a 200-mesh sieve;

4) calcining the sieved powder in a muffle furnace at 720-830 ℃ for 0.5-3 h, wherein the heating rate is 3-5 ℃/min, granulating the obtained powder after calcining, preforming the granulated powder through a tablet press, pressing the preformed powder under 250-300 MPa to obtain a blank, sintering the obtained blank in the muffle furnace at 1250-1600 ℃ for 1-3 h, wherein the heating rate is 8-10 ℃/min, and cooling to room temperature along with the furnace to obtain the ceramic.

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are some embodiments of the present invention, but not all embodiments. The components of the embodiments of the present invention generally shown may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present invention is not intended to limit the scope of the invention as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.