CN110104681B - High-toughness yttria-stabilized tetragonal zirconia material not affected by sintering and preparation method thereof - Google Patents
High-toughness yttria-stabilized tetragonal zirconia material not affected by sintering and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-toughness yttria-stabilized tetragonal zirconia material not affected by sintering and a preparation method thereof, belonging to the field of zirconia ceramics. A high toughness yttria stabilized tetragonal zirconia (3Y-TZP) material unaffected by sintering, having a particle size of between 100nm and 900nm, no monoclinic phase, a sintered density of 5.63g/cm3‑6.05g/cm3And the relative density is 92.6-99.5%. Compared with the similar technology, the invention enables the raw materials to react uniformly from the atomic scale, avoids the hydrolysis of zirconium ions, so that the starting raw materials have no monoclinic phase; the sintering temperature is 1350-; the toughness is higher, and the toughness is not obviously reduced along with the sintering time and the sintering temperature.
Description
Technical Field
The invention relates to a high-toughness yttria-stabilized tetragonal zirconia material not affected by sintering and a preparation method thereof, belonging to the field of zirconia ceramics.
Background
The yttria partially stabilized tetragonal zirconia (3Y-TZP) material with the mole fraction of 3 percent has the characteristics of high melting point, low thermal conductivity, high strength, high toughness, corrosion resistance, excellent chemical stability and the like, and particularly has good mechanical properties such as bendingThe bending strength reaches 1000MPa, and the fracture toughness reaches 3.0-6.5MPam1/2The method has wide application value in the industries of machinery, electronics, petroleum, chemical engineering, aviation, aerospace, textile, precision instruments, medical treatment and the like.
The 3Y-TZP ceramic which is nearly completely compact and prepared by the traditional high-temperature sintering process is vulnerable to ZrO2The limitations of the thermodynamic phase transformation problems inherent to the substrate. According to ZrO2-Y2O3Phase diagram, 3Y-TZP has a metastable tetragonal (t') phase structure at room temperature. the t' phase is thermodynamically unstable and undergoes diffusion-controlled tetragonal (t) and cubic (c) phase transformations at temperatures above 1200 c, with the t phase further transforming to the monoclinic (m) phase (-1170 c) upon cooling. Well-known ZrO2The martensitic transformation from the t-phase to the m-phase is accompanied by a volume expansion of-4 Vol%. The stresses created by such volume changes can lead to the formation of cracks in the ceramic, which in turn can lead to cracking or even fracture of the component. Therefore, scholars at home and abroad generally adopt rapid sintering processes such as spark plasma sintering and the like to prepare compact t' -YSZ blocks so as to avoid the fragmentation of ceramics in the sintering process.
At present, the 3Y-TZP powder reported in the literature and commercialized is generally prepared by a hydrothermal synthesis method and a coprecipitation method. Because zirconium salt is easy to hydrolyze, the uniformity of metal ion distribution in the solution is reduced, and the 3Y-TZP powder prepared by the method contains a small amount of monoclinic phase. The appearance of monoclinic phase in the starting powder material not only can reduce the fracture toughness of the 3Y-TZP material, but also increases the risk of the 3Y-TZP ceramic cracking in the sintering process, so that the sintering process parameter range is narrow. Therefore, the 3Y-TZP material with high phase purity, no monoclinic phase and strong adaptability of the sintering process and the preparation method thereof can greatly improve the quality and reliability of the zirconia ceramic part and play an important role in promoting the application of the zirconia ceramic part in the field of high-performance structural ceramics.
Disclosure of Invention
The invention aims to solve the problems of monoclinic phase and narrow sintering temperature range of the zirconia (3Y-TZP), and provides a high-toughness yttria-stabilized tetragonal zirconia (3Y-TZP) material which is not influenced by sintering and a preparation method thereof. The material is of a single tetragonal zirconia structure, the grain size is between 10nm and 40nm, and the material is prepared by a Sol-spray pyrolysis method.
The technical scheme adopted by the invention for solving the problems is as follows: a high toughness yttria stabilized tetragonal zirconia (3Y-TZP) material unaffected by sintering, having a particle size of between 100nm and 900nm and a sintered density of 5.63g/cm3-6.05g/cm3And the relative density is 92.6-99.5%.
According to the present invention, there is provided a process for the preparation of a high toughness yttria stabilised tetragonal zirconia (3Y-TZP) material which is unaffected by sintering, comprising the steps of:
(1) sol preparation:
preparing transparent aqueous solution by mixing materials according to the mol ratio of Zr (NO3) 4.3H 2O to Y (NO3) 3.6H 2O to 0.94: 0.06; adding additives of citric acid and polyethylene glycol, and magnetically stirring until clear and transparent sol is obtained;
(2) preparing raw materials:
the prepared sol is atomized to a corundum crucible by taking pure air with certain pressure as an atomizing medium; after atomization, heating to a certain temperature, carrying out heat treatment to obtain the required raw material, carrying out heat preservation sintering for 1 hour, and cooling to room temperature to obtain 3Y-TZP nano powder;
(3) preparing a block material:
grinding the 3Y-TZP nano powder, pressing into a wafer by using a die, and sintering in a program-controlled high-temperature furnace to prepare the wafer.
The preparation method of the high-toughness yttria-stabilized tetragonal zirconia (3Y-TZP) material which is not affected by sintering is characterized in that (1) sol preparation:
the raw materials are prepared according to the molar ratio: zr (NO3) 4.3H 2O: Y (NO3) 3.6H 2O ═ 0.94: 0.06; deionized water is used as a solvent to prepare an aqueous solution with the total concentration of metal ions being 0.2 mol/L; sequentially adding citric acid and polyethylene glycol as additives, wherein the addition amount of citric acid is 160g/L, the molecular weight of polyethylene glycol is 20000, and the addition amount is 20 g/L; stirring by magnetic force until the mixture is clear and transparent.
The preparation of the raw materials in the step (2): air with the purity of 99.99 percent is used as an atomizing medium, and the pressure is 0.3 MPa; the corundum crucible temperature is 500-900 ℃.
The block material preparation: the 3Y-TZP material takes 3Y-TZP nano powder which is subjected to heat treatment at 900 ℃ for 1 hour as a starting material, the powder is put into an agate mortar for grinding, a proper amount of the powder is put into a stainless steel mold with the diameter of 18mm, the powder is pressed and formed under the pressure of 500MPa, the formed wafer is put into a program-controlled high-temperature furnace to be sintered for 1.5 to 2.5 hours at the temperature of 1350 to 1600 ℃, the temperature rising and falling speed is 2 ℃/min, and the wafer with the thickness of 2mm is prepared after being cooled to the room temperature.
According to the invention, after the 3Y-TZP nano powder is sintered for 2 hours at 1350-1600 ℃, no monoclinic zirconia diffraction peak appears in the XRD spectrum of the 3Y-TZP material.
Compared with the similar technology, the invention has the prominent substantive characteristics:
1. because the monoclinic phase exists in the general commercial starting powder, the occurrence of the monoclinic phase not only can reduce the fracture toughness of the 3Y-TZP material, but also increases the risk of the 3Y-TZP ceramic cracking in the sintering process, so that the sintering process parameter range becomes narrow. We provide a process that allows the feedstock to react uniformly on an atomic scale, avoiding hydrolysis of zirconium ions, so that the starting feedstock has no monoclinic phase.
2. The sintering temperature range is wider, and 1350-;
3. the toughness is higher, and the toughness is not obviously reduced along with the sintering time and the sintering temperature.
Drawings
FIG. 1 is an XRD pattern of nano 3Y-TZP powder prepared according to an example of the present invention after heat treatment at 500 deg.C-900 deg.C for 1 h; also shown is a standard PDF card map of tetragonal zirconia (accession number: PDF # 881007); the crystal grain size D in the figure is based on the peak position theta, the full width at half maximum beta and the X-ray wavelength lambda of the diffraction peak of the (111) crystal face, which are 0.15406nm, and the Sherre formula is adopted: d is calculated to be 0.89 λ/β cos θ.
Fig. 2 is an XRD spectrum of the 3Y-TZP material prepared according to an example of the present invention.
Fig. 3(a), 3(b), 3(c), 3(d), 3(e) and 3(f) are surface SEM images of the 3Y-TZP materials prepared according to the example of the present invention, respectively.
Fig. 4 is a graph of measured and theoretical densities of a 3Y-TZP material prepared according to an embodiment of the present invention as a function of sintering temperature.
Fig. 5(a), 5(b), 5(c), 5(d), and 5(e) are SEM images of vickers indentations of the polished surface of the 3Y-TZP material prepared according to the example of the present invention, respectively (load P ═ 9.8N, dwell time t ═ 10 s).
FIG. 6 is a graph of fracture toughness and Vickers hardness as a function of sintering temperature for 3Y-TZP materials prepared in accordance with examples of the present invention.
Detailed Description
According to one aspect of the present invention there is provided a high toughness yttria stabilised tetragonal zirconia material unaffected by sintering, wherein:
the 3Y-TZP nano powder is prepared by a sol-spray pyrolysis method,
the 3Y-TZP nano powder is prepared by the following steps:
zr (NO) with the purity of 99.99 percent3)4·3H2O and Y (NO)3)3·6H2O as raw material in mol ratio of Zr (NO)3)4·3H2O:Y(NO3)3·6H20.94:0.06 of O, preparing an aqueous solution with the total concentration of metal ions of 0.2mol/L by taking deionized water as a solvent, magnetically stirring for 1-3h until the solution is clear and transparent, sequentially adding citric acid hexahydrate and polyethylene glycol with the molecular weight of 20000, wherein the addition amount of the citric acid is 160g/L and the addition amount of the polyethylene glycol is 20g/L, and magnetically stirring until the solution is clear and transparent to prepare the sol.
The prepared sol is atomized into a corundum crucible by a pressure atomization method, the atomization pressure is 0.3MPa, and the temperature of the corundum crucible is 500 ℃. After the sol atomization is finished, the temperature of the corundum crucible is increased to 500-900 ℃ (the interval is 100 ℃) and is kept for 1h, and then the corundum crucible is cooled to room temperature to obtain 3Y-TZP nano powder.
According to another aspect of the invention, the 3Y-TZP nano powder is in a single tetragonal zirconia structure after being subjected to heat treatment at 500-900 ℃ for 1 hour.
According to another aspect of the invention, the grain size of the 3Y-TZP nano powder after being subjected to heat treatment at 500-900 ℃ for 1 hour is between 10nm and 40 nm.
According to a specific aspect of the invention, the 3Y-TZP material is prepared by taking 3Y-TZP nanopowder subjected to heat treatment at 900 ℃ for 1 hour as a starting material, putting the powder into an agate mortar for grinding, taking a proper amount of the powder, putting the powder into a stainless steel mold with the diameter of 18mm, performing compression molding under the pressure of 500MPa, putting the molded wafer into a program-controlled high-temperature furnace, sintering for 2 hours at 1350-1600 ℃ (interval of 50 ℃), increasing and decreasing the temperature at the rate of 2 ℃/min, and cooling to room temperature to prepare the wafer with the thickness of 2 mm.
According to another specific aspect of the invention, after sintering at 1350-1600 ℃ for 2h, no monoclinic zirconia diffraction peak appears in the XRD pattern of the 3Y-TZP material.
According to another specific aspect of the invention, the particle size of the 3Y-TZP material is between 100nm and 900nm, and the sintered density is 5.63g/cm3-6.05g/cm3And the relative density is 92.6-99.5%.
According to another specific aspect of the invention, the fracture toughness of the 3Y-TZP material is tested to be 3.94 MP.m by adopting a Vickers indentation method1/2-4.98MP·m1/2In the range of 6.61GPa-11.54GPa hardness.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1:
zr (NO) with the purity of 99.99 percent3)4·3H2O and Y (NO)3)3·6H2O as raw material in mol ratio of Zr (NO)3)4·3H2O:Y(NO3)3·6H20.94:0.06 of O, preparing an aqueous solution with the total concentration of metal ions of 0.2mol/L by taking deionized water as a solvent, magnetically stirring for 1-3h until the solution is clear and transparent, sequentially adding citric acid hexahydrate and polyethylene glycol with the molecular weight of 20000, wherein the addition amount of the citric acid is 160g/L and the addition amount of the polyethylene glycol is 20g/L, and magnetically stirring until the solution is clear and transparent to prepare the sol.
The prepared sol is atomized into a corundum crucible by a pressure atomization method, the atomization pressure is 0.3MPa, and the temperature of the corundum crucible is 500 ℃. After the sol atomization is finished, the temperature of the corundum crucible is raised to 900 ℃, the temperature is kept for 1h, and then the corundum crucible is cooled to room temperature to obtain 3Y-TZP nano powder.
Grinding the powder in an agate mortar, putting a proper amount of the powder into a stainless steel mold with the diameter of 18mm, pressing and forming under the pressure of 500MPa, putting the formed wafer into a program-controlled high-temperature furnace, sintering for 2 hours at 1350 ℃, increasing and decreasing the temperature at the speed of 2 ℃/min, cooling to room temperature, and preparing the wafer with the thickness of 2mm for testing.
The phase test was carried out using a multifunctional X-ray diffractometer, model X 'Pert PRO, manufactured by parnacho, netherlands, equipped with an X' Celerator performance detector, with the X-ray being the Cu target k α 1 and the wavelength λ being 0.15406 nm. Please refer to the XRD pattern 1# in FIG. 2. The particle size of the 3Y-TZP material was 185 + -50 nm as observed by a field emission Scanning Electron Microscope (SEM) model No. 55, manufactured by Zeiss, Germany, and the SEM image thereof is shown in FIG. 3 (a).
Calculating theoretical density rho of material according to XRD data and chemical compositiont＝6.08g/cm3The density rho of the wafer is 5.63g/cm by the Archimedes method3Calculating the relative density rho of the material according to the formula (1)rSee fig. 4 for 92.6%.
ρr＝ρ/ρt×100％(1)
Example 2:
zr (NO) with the purity of 99.99 percent3)4·3H2O and Y (NO)3)3·6H2O as raw material in mol ratio of Zr (NO)3)4·3H2O:Y(NO3)3·6H20.94:0.06 of O, preparing an aqueous solution with the total concentration of metal ions of 0.2mol/L by taking deionized water as a solvent, magnetically stirring for 1-3h until the solution is clear and transparent, sequentially adding citric acid hexahydrate and polyethylene glycol with the molecular weight of 20000, wherein the addition amount of the citric acid is 160g/L and the addition amount of the polyethylene glycol is 20g/L, and magnetically stirring until the solution is clear and transparent to prepare the sol.
The prepared sol is atomized into a corundum crucible by a pressure atomization method, the atomization pressure is 0.3MPa, and the temperature of the corundum crucible is 500 ℃. After the sol atomization is finished, the temperature of the corundum crucible is raised to 900 ℃, the temperature is kept for 1h, and then the corundum crucible is cooled to room temperature to obtain 3Y-TZP nano powder.
Grinding the powder in an agate mortar, putting a proper amount of the powder into a stainless steel mold with the diameter of 18mm, pressing and molding under the pressure of 500MPa, putting the molded wafer into a program-controlled high-temperature furnace, sintering for 2 hours at 1400 ℃, increasing and decreasing the temperature at the speed of 2 ℃/min, cooling to room temperature, and preparing the wafer with the thickness of 2mm for testing.
The phase test was carried out using a multifunctional X-ray diffractometer, model X 'Pert PRO, manufactured by parnacho, netherlands, equipped with an X' Celerator performance detector, with the X-ray being the Cu target k α 1 and the wavelength λ being 0.15406 nm. Please refer to the XRD pattern 2# in fig. 2. The particle size of the 3Y-TZP material was observed using a field emission scanning electron microscope model No. Ultra 55, manufactured by Zeiss, Germany, at 234 + -69 nm, and an SEM image thereof is shown in FIG. 3 (b).
Calculating theoretical density rho of material according to XRD data and chemical compositiont＝6.08g/cm3The density rho of the wafer is 5.88g/cm by the Archimedes method3Calculating the relative density rho of the material according to the formula (1)rSee fig. 4 for 96.7%. After the surface of the 3Y-TZP material was polished with silicon carbide sand paper, an indentation test was performed using a vickers hardness tester model HVS-30Z, manufactured by mountain technologies ltd, beijing, with an indenter load P of 9.8N and a dwell time t of 10s, and the indentation image thereof is shown in fig. 5(a), and the hardness H of the material was calculated according to the formula (2)VThe fracture toughness K of the material was calculated according to equation (3) at 6.61 ± 0.16GPaIC＝3.94±0.16MPa·m1/2Please refer to fig. 6.
HV＝P/2·a2 (2)
KIC＝0.16·HV·a1/2·(c/a)-3/2(c/a≥2.5)(3)
Example 3:
zr (NO) with the purity of 99.99 percent3)4·3H2O and Y (NO)3)3·6H2O as raw material in mol ratio of Zr (NO)3)4·3H2O:Y(NO3)3·6H20.94:0.06 of O, preparing an aqueous solution with the total concentration of metal ions of 0.2mol/L by taking deionized water as a solvent, magnetically stirring for 1-3h until the solution is clear and transparent, sequentially adding citric acid hexahydrate and polyethylene glycol with the molecular weight of 20000, wherein the addition amount of the citric acid is 160g/L and the addition amount of the polyethylene glycol is 20g/L, and magnetically stirring until the solution is clear and transparent to prepare the sol.
The prepared sol is atomized into a corundum crucible by a pressure atomization method, the atomization pressure is 0.3MPa, and the temperature of the corundum crucible is 500 ℃. After the sol atomization is finished, the temperature of the corundum crucible is raised to 900 ℃, the temperature is kept for 1h, and then the corundum crucible is cooled to room temperature to obtain 3Y-TZP nano powder.
Grinding the powder in an agate mortar, putting a proper amount of the powder into a stainless steel mold with the diameter of 18mm, pressing and forming under the pressure of 500MPa, putting the formed wafer into a program-controlled high-temperature furnace, sintering at 1450 ℃ for 2h at the temperature rising and falling rate of 2 ℃/min, cooling to room temperature, and preparing the wafer with the thickness of 2mm for testing.
The phase test was carried out using a multifunctional X-ray diffractometer, model X 'Pert PRO, manufactured by parnacho, netherlands, equipped with an X' Celerator performance detector, with the X-ray being the Cu target k α 1 and the wavelength λ being 0.15406 nm. Please refer to the XRD pattern in figure 2# 3. The particle size of the 3Y-TZP material was 269. + -.65 nm as observed by a field emission Scanning Electron Microscope (SEM) model No. 55, manufactured by Zeiss, Germany, and the SEM image thereof is shown in FIG. 3 (c).
Calculating theoretical density rho of material according to XRD data and chemical compositiont＝6.08g/cm3The density rho of the wafer is 5.95g/cm by the Archimedes method3Calculating the relative density rho of the material according to the formula (1)rSee fig. 4 for 97.9%. Performing surface polishing on the 3Y-TZP material with silicon carbide sand paper, performing indentation test with a Vickers hardness tester model HVS-30Z manufactured by mountain science and technology Limited in Beijing, with an indenter load P of 9.8N and a pressure holding time t of 10s, and calculating an indentation image according to formula (2) and FIG. 5(b)Calculating the hardness H of the materialVCalculating the fracture toughness K of the material according to the formula (3) under the condition of 10.10 +/-0.30 GPaIC＝4.26±0.26MPa·m1/2Please refer to fig. 6.
Example 4:
zr (NO) with the purity of 99.99 percent3)4·3H2O and Y (NO)3)3·6H2O as raw material in mol ratio of Zr (NO)3)4·3H2O:Y(NO3)3·6H20.94:0.06 of O, preparing an aqueous solution with the total concentration of metal ions of 0.2mol/L by taking deionized water as a solvent, magnetically stirring for 1-3h until the solution is clear and transparent, sequentially adding citric acid hexahydrate and polyethylene glycol with the molecular weight of 20000, wherein the addition amount of the citric acid is 160g/L and the addition amount of the polyethylene glycol is 20g/L, and magnetically stirring until the solution is clear and transparent to prepare the sol.
The prepared sol is atomized into a corundum crucible by a pressure atomization method, the atomization pressure is 0.3MPa, and the temperature of the corundum crucible is 500 ℃. After the sol atomization is finished, the temperature of the corundum crucible is raised to 900 ℃, the temperature is kept for 1h, and then the corundum crucible is cooled to room temperature to obtain 3Y-TZP nano powder.
Grinding the powder in an agate mortar, putting a proper amount of the powder into a stainless steel mold with the diameter of 18mm, pressing and forming under the pressure of 500MPa, putting the formed wafer into a program-controlled high-temperature furnace, sintering at 1500 ℃ for 2h at the temperature rising and falling rate of 2 ℃/min, cooling to room temperature, and preparing the wafer with the thickness of 2mm for testing.
The phase test was carried out using a multifunctional X-ray diffractometer, model X 'Pert PRO, manufactured by parnacho, netherlands, equipped with an X' Celerator performance detector, with the X-ray being the Cu target k α 1 and the wavelength λ being 0.15406 nm. Please refer to the XRD pattern 4# in fig. 2. The particle size of the 3Y-TZP material was 321. + -.91 nm as observed with a field emission scanning electron microscope model No. Ultra 55, manufactured by Zeiss, Germany, and the SEM image is shown in FIG. 3 (d).
Calculating theoretical density rho of material according to XRD data and chemical compositiont＝6.08g/cm3The density rho of the wafer is 5.98g/cm by the Archimedes method3Is calculated according to the formula (1)Relative density of material rhorSee fig. 4 for 98.4%. After the surface of the 3Y-TZP material was polished with silicon carbide sand paper, an indentation test was performed using a vickers hardness tester model HVS-30Z, manufactured by mountain technologies ltd, beijing, with an indenter load P of 9.8N and a dwell time t of 10s, and the indentation image thereof is shown in fig. 5(c), and the hardness H of the material was calculated according to the formula (2)VCalculating the fracture toughness K of the material according to the formula (3) under the condition of 10.35 +/-0.37 GPaIC＝4.13±0.22MPa·m1/2Please refer to fig. 6.
Example 5:
zr (NO) with the purity of 99.99 percent3)4·3H2O and Y (NO)3)3·6H2O as raw material in mol ratio of Zr (NO)3)4·3H2O:Y(NO3)3·6H20.94:0.06 of O, preparing an aqueous solution with the total concentration of metal ions of 0.2mol/L by taking deionized water as a solvent, magnetically stirring for 1-3h until the solution is clear and transparent, sequentially adding citric acid hexahydrate and polyethylene glycol with the molecular weight of 20000, wherein the addition amount of the citric acid is 160g/L and the addition amount of the polyethylene glycol is 20g/L, and magnetically stirring until the solution is clear and transparent to prepare the sol.
The prepared sol is atomized into a corundum crucible by a pressure atomization method, the atomization pressure is 0.3MPa, and the temperature of the corundum crucible is 500 ℃. After the sol atomization is finished, the temperature of the corundum crucible is raised to 900 ℃, the temperature is kept for 1h, and then the corundum crucible is cooled to room temperature to obtain 3Y-TZP nano powder.
Grinding the powder in an agate mortar, putting a proper amount of the powder into a stainless steel mold with the diameter of 18mm, performing compression molding under the pressure of 500MPa, putting the molded wafer into a program-controlled high-temperature furnace, sintering for 2 hours at 1550 ℃, increasing and decreasing the temperature rate to 2 ℃/min, cooling to room temperature, and preparing the wafer with the thickness of 2mm for testing.
The phase test was carried out using a multifunctional X-ray diffractometer, model X 'Pert PRO, manufactured by parnacho, netherlands, equipped with an X' Celerator performance detector, with the X-ray being the Cu target k α 1 and the wavelength λ being 0.15406 nm. Please refer to the XRD pattern 5# in fig. 2. The particle size of the 3Y-TZP material was observed to be 506 + -133 nm using a field emission scanning electron microscope model No. Ultra 55, manufactured by Zeiss, Germany, and the SEM image thereof is shown in FIG. 3 (e).
Calculating theoretical density rho of material according to XRD data and chemical compositiont＝6.08g/cm3The density rho of the wafer is 6.03g/cm by the Archimedes method3Calculating the relative density rho of the material according to the formula (1)r99.2%, please see fig. 4. After the surface of the 3Y-TZP material was polished with silicon carbide sand paper, an indentation test was performed using a vickers hardness tester model HVS-30Z, manufactured by mountain technologies ltd, beijing, with an indenter load P of 9.8N and a dwell time t of 10s, and the indentation image thereof is shown in fig. 5(d), and the hardness H of the material was calculated according to the formula (2)VThe fracture toughness K of the material was calculated according to equation (3) at 11.52 ± 0.11GPaIC＝4.30±0.21MPa·m1/2Please refer to fig. 6.
Example 6:
zr (NO) with the purity of 99.99 percent3)4·3H2O and Y (NO)3)3·6H2O as raw material in mol ratio of Zr (NO)3)4·3H2O:Y(NO3)3·6H20.94:0.06 of O, preparing an aqueous solution with the total concentration of metal ions of 0.2mol/L by taking deionized water as a solvent, magnetically stirring for 1-3h until the solution is clear and transparent, sequentially adding citric acid hexahydrate and polyethylene glycol with the molecular weight of 20000, wherein the addition amount of the citric acid is 160g/L and the addition amount of the polyethylene glycol is 20g/L, and magnetically stirring until the solution is clear and transparent to prepare the sol.
The prepared sol is atomized into a corundum crucible by a pressure atomization method, the atomization pressure is 0.3MPa, and the temperature of the corundum crucible is 500 ℃. After the sol atomization is finished, the temperature of the corundum crucible is raised to 900 ℃, the temperature is kept for 1h, and then the corundum crucible is cooled to room temperature to obtain 3Y-TZP nano powder.
Grinding the powder in an agate mortar, putting a proper amount of the powder into a stainless steel mold with the diameter of 18mm, pressing and molding under the pressure of 500MPa, putting the molded wafer into a program-controlled high-temperature furnace, sintering for 2 hours at 1600 ℃, increasing and decreasing the temperature at the rate of 2 ℃/min, cooling to room temperature, and preparing the wafer with the thickness of 2mm for testing.
The phase test was carried out using a multifunctional X-ray diffractometer, model X 'Pert PRO, manufactured by parnacho, netherlands, equipped with an X' Celerator performance detector, with the X-ray being the Cu target k α 1 and the wavelength λ being 0.15406 nm. The XRD pattern is shown in figure 2# 6. The particle size of the 3Y-TZP material was observed using a field emission scanning electron microscope model No. Ultra 55, produced by Zeiss, Germany, at 709. + -.170 nm, and an SEM image thereof is shown in FIG. 3 (f).
Calculating theoretical density rho of material according to XRD data and chemical compositiont＝6.08g/cm3The density rho of the wafer is 6.05g/cm by the Archimedes method3Calculating the relative density rho of the material according to the formula (1)r99.5%, please see fig. 4. Performing surface polishing on the 3Y-TZP material by using silicon carbide sand paper, performing indentation test by using a Vickers hardness tester with model number HVS-30Z, which is produced by mountain science and technology Limited in Beijing, wherein the indenter load P is 9.8N, the pressure maintaining time t is 10s, the indentation image is shown in figure 5(e), and calculating the hardness H of the material according to the formula (2)VCalculating the fracture toughness K of the material according to the formula (3) when the fracture toughness K is 11.54 +/-0.13 GPaIC＝4.98±0.38MPa·m1/2Please refer to fig. 6.
Claims (3)
1. A preparation method of a high-toughness yttria-stabilized tetragonal zirconia 3Y-TZP material which is not affected by sintering is characterized by comprising the following steps:
(1) sol preparation:
in molar ratio of Zr (NO)3)4•3H2O:Y(NO3)3•6H2Compounding material O0.94 to 0.06 to prepare transparent water solution; adding additives of citric acid and polyethylene glycol, and magnetically stirring until clear and transparent sol is obtained;
(2) preparing raw materials:
the prepared sol is atomized to a corundum crucible by taking pure air with certain pressure as an atomizing medium; after atomization, heating to a certain temperature, carrying out heat treatment to obtain the required raw material, carrying out heat preservation sintering for 1 hour, and cooling to room temperature to obtain 3Y-TZP nano powder;
(3) preparing a block material:
taking 3Y-TZP nano powder subjected to heat treatment at 900 ℃ for 1 hour as a starting material, putting the powder into an agate mortar for grinding, taking a proper amount of the powder into a stainless steel mold with the diameter of 18mm, performing compression molding under the pressure of 500MPa, putting the molded wafer into a program-controlled high-temperature furnace, sintering at 1350-1600 ℃ for 1.5-2.5 hours at the temperature rising and falling rate of 2 ℃/min, cooling to room temperature, and preparing a wafer with the thickness of 2mm to obtain a 3Y-TZP material; the 3Y-TZP material has the particle size of 135nm-900nm, no monoclinic phase and the sintering density of 5.63g/cm3-6.05g/cm3And the relative density is 92.6-99.5%.
2. A process for the preparation of a high toughness yttria stabilized tetragonal zirconia 3Y-TZP material unaffected by sintering as claimed in claim 1,
preparing the sol:
preparing a transparent aqueous solution with the total concentration of metal ions being 0.2mol/L by taking deionized water as a solvent; sequentially adding citric acid and polyethylene glycol as additives, wherein the addition amount of citric acid is 160g/L, the molecular weight of polyethylene glycol is 20000, and the addition amount is 20 g/L;
the preparation of the raw materials in the step (2): air with the purity of 99.99 percent is used as an atomizing medium, and the pressure is 0.3 MPa; the corundum crucible temperature is 500-900 ℃.
3. The method for preparing a high toughness yttria stabilized tetragonal zirconia 3Y-TZP material not affected by sintering as claimed in claim 1, wherein the room temperature fracture toughness of the high toughness yttria stabilized tetragonal zirconia 3Y-TZP material not affected by sintering is 3.94-4.98 MPa.m1/2In the meantime.
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