CN107840658B - Preparation method of zirconia ceramic with high fracture toughness - Google Patents
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Abstract
The invention discloses a preparation method of zirconia ceramic with high fracture toughness. The invention adopts the method that CaO-Al is mixed 2O3‑SiO2Mixed precursor sol of (a) and Y ion-stabilized ZrO 2The composite powder is uniformly mixed in a ball milling mode, and then the TZP ceramic is obtained after the processes of drying, calcining, granulating, forming, sintering and the like. The microstructure of the TZP ceramic prepared by the invention consists of zirconia with two grain sizes and fine-grain alumina, and the microstructure has three toughening mechanisms, namely phase change toughening, grain refinement toughening and large grain bridging toughening. Therefore, the TZP ceramic prepared by the invention has the advantages of high toughness, high strength, low firing temperature, simple process, low cost, easy industrial production and the like.
Description
Technical Field
The invention relates to the field of oxide ceramic preparation, in particular to a preparation method of zirconia ceramic with high fracture toughness.
Background
The yttrium oxide stabilized tetragonal polycrystalline zirconia (Y-TZP) ceramic material has the mechanisms of small grain size, phase change, toughness enhancement and the like, so that the yttrium oxide stabilized tetragonal polycrystalline zirconia (Y-TZP) ceramic material has good mechanical properties and is widely applied to the fields of chemical industry, machinery, petroleum, electronics, communication and aerospace. However, with the rapid improvement of the scientific and technological level in China, higher requirements are put forward on the mechanical properties of the zirconia ceramic material, and meanwhile, the low-energy-consumption production also puts forward a challenge for the low-temperature sintering of zirconia.
the traditional zirconia ceramic material adopts single stabilizer (Y, Ca, Mg, etc.) to stabilize zirconia, while the Ca-TZP and Mg-TZP ceramics have the defects of high sintering temperature and difficult complete densification and limited application fields, Y-TZP is the zirconia ceramic which is most widely applied at present, but the ceramic toughness is still lower eram.Int.，Vol.43，No，16319-16322，2017]The fracture toughness of the Y-TZP ceramic measured by SENB is mostly concentrated at 8-14MPa 1/2The fracture toughness of the Y-TZP ceramic obtained by the SEVNB method is mostly concentrated at 4-7MPa 1/2Thus by a single Y 2O3As a stabilizer, it is difficult to further improve the fracture toughness of the Y-TZP ceramic. The Chinese invention patent CN02111146.4 adopts a coprecipitation method to prepare Y/Mg-TZP, MgO and Y 2O3The content of (B) is 5-14 mol% and 0.2-2 mol%, respectively, and Y is 2O3-Al2O3-SiO2The glass frit is used as a sintering aid to obtain the TZP ceramic material with the grain size of 200-400nm, and the fracture toughness is only 5.2-8.3MPa 1/2. Chinese patent CN02110868.4B discloses a method for preparing CaO-Al by melting 2O3-SiO2Glass frit is added into the Y-TZP ceramic powder by a mechanical mixing method to obtain the TZP ceramic material with the fracture toughness of only 9.5-9.8MPa 1/2. Because the glass solution is added by a mechanical mixing method, the stabilizer is unevenly distributed in the zirconia, so that the fracture toughness of the TZP ceramic material is difficult to obviously improve. Chinese patent CN200710165634.2 adopts coprecipitation method to prepare MgO 2-Al2O3-SiO2Mixing the sol with commercial Y-TZP powder mechanically to obtain TZP powder with fracture toughness of 11.3-13.5MPa 1/2. Among these TZP ceramic materials, MgO 2-Al2O3-SiO2The sol can form more glass phase locally, meanwhile, Mg ions are uniformly fused into zirconia crystal lattices, the generated crystal grains are narrow in distribution, the toughening mechanism is single, and the performance is further improved although the sintering temperature is lower, so that the fracture toughness is not obviously improved compared with that of the traditional Y-TZP ceramic material. Therefore, introducing other toughening mechanisms into the Y-TZP ceramic matrix to improve the fracture toughness is an important way for improving the fracture toughness of the zirconia. For the crystal whisker or fiber toughened zirconia ceramic material, the crystal whisker or fiber is difficult to be uniformly dispersed in the Y-TZP ceramic matrix, the non-uniform dispersion can cause the reduction of the mechanical property, and the composite material is not used The method adopts normal pressure sintering densification, and needs hot pressing sintering, so that industrial production is difficult to realize. Therefore, in order to improve the fracture toughness of the Y-TZP ceramic, a preparation method which is simple and effective in process and suitable for industrial production needs to be explored.
Disclosure of Invention
The invention aims to provide a preparation method of the high-fracture-toughness Y-TZP ceramic, which obviously reduces the sintering temperature, has low energy consumption and obviously improves the mechanical property.
The method introduces Ca, Si, Al and Y ions into the TZP ceramic by a precipitation method, generates a local liquid phase by the Ca ions to reduce the sintering temperature and generate large crystal grains, and simultaneously inhibits the growth of the surrounding small crystal grains and reduces the sintering temperature. And simultaneously introducing toughening mechanisms such as phase change toughening, large-particle bridging and small-grain refining and the like into the zirconia matrix, thereby obviously improving the mechanical property of the Y-TZP ceramic material. Meanwhile, the liquid phase sintering mode can obviously reduce the sintering temperature.
The purpose of the invention is realized by the following technical scheme.
1. The preparation method of the zirconia ceramic with high fracture toughness is characterized by comprising the following steps:
(1) Mixing soluble salt of calcium ion, soluble salt of aluminum ion and Si (OC) 2H5)4Adding water to prepare a mixed solution; stirring, dropwise adding ammonia water to adjust the pH of the mixed solution to generate a precipitate, washing with water, and performing centrifugal separation to obtain a composite sol A;
(2) Adding water into zirconium oxychloride octahydrate and yttrium chloride hexahydrate for mixing, dropwise adding ammonia water to adjust the pH value to generate a precipitate, washing and centrifuging to obtain a zirconium hydroxide precursor, and drying to obtain composite powder B;
(3) Mixing the composite sol A obtained in the step (1), the composite powder B obtained in the step (2), water and a dispersing agent, drying, sieving, calcining, ball-milling, and spray-granulating to obtain composite powder C;
(4) And (4) carrying out dry pressing forming and sintering on the composite powder C obtained in the step (3) to obtain the zirconia ceramic with high fracture toughness.
Further, in the step (1), the calcium ion The soluble salt is CaCl 2.2H2O and Ca (NO) 3)2.4H2Any one or a combination of O; the soluble salt of the aluminum ion is AlCl 3.6H2O and Al (NO) 3)3.6H2Any one or a combination of O.
Further, in the step (1), the soluble salt of calcium ion, the soluble salt of aluminum ion and Si (OC) 2H5)4According to CaO, Al 2O3、SiO2In a molar ratio of (2-5): (3-10): (0.5-3) in proportion.
further, in the step (1), the concentration of the ammonia water is 0.1-0.2 ml/L, and the pH of the mixed solution is 8.7-10.
Further, in the step (2), zirconium oxychloride octahydrate and yttrium chloride hexahydrate are mixed according to ZrO 2、Y2O3In a molar ratio of (0.5-3): (99.5-97) weighing; adding water, mixing to obtain solution with pH of 8.7-10, drying at 100-300 deg.C for 0.5-1 h.
Further, in the step (3), the dispersing agent is one or more of ammonium polyacrylate, polyethylene glycol, sodium tripolyphosphate, sodium carboxymethylcellulose, trisodium phosphate and sodium hexametaphosphate in any proportion.
Further, in the step (3), the mass ratio of the composite sol A to the composite powder B in the step (2) to water to the dispersant is (10-30): (70-90): (100-120): (0.5-3).
Further, in the step (3), the drying temperature is 90-110 ℃, and the mesh number of the sieve is 100-200. The calcination temperature is 600-900 ℃; the ratio of calcined powder, grinding medium and water in the ball milling process is 1: 2: (1-1.5), the rotating speed and the ball milling time are respectively 400-500r/min and 2-4 h.
in the step (3), the spray granulation operation process parameters are that the temperature of drying air is 250-300 ℃, the air outlet temperature is 110-150 ℃, and the flow rate of slurry is 1.8-2.3L/h.
Further, in the step (4), the pressure of the dry pressing is 15-30MPa, and the sintering temperature and the heat preservation time are 1300-1400 ℃ and 1-2h respectively.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The prepared Y-TZP ceramic has good mechanical property, the highest strength reaches 1520MPa, and the highest fracture toughness measured by the SENB method reaches 18.5MP.m 1/2。
(2) The Y-TZP ceramic has low sintering temperature, can be sintered after being sintered for 1 to 2 hours at 1300 to 1400 ℃, and has the advantage of energy conservation.
(3) The process for preparing the Y-TZP ceramic is simple and is suitable for industrial production.
Compared with the prior art, the invention has the following remarkable advantages and progresses:
1) According to the invention, Ca, Si, Al and Y ions are introduced into the zirconium oxide by a coprecipitation method, so that various toughening mechanisms such as phase change toughening, particle bridging, grain refinement and the like are synergistic, and an unexpected technical effect is achieved.
2) According to the invention, the zirconium oxide exists in a tetragonal phase at room temperature by means of Ca and Y ions, so that more tetragonal zirconium oxide can be obtained to have phase change in the crack propagation process, and the effect of phase change and toughness enhancement is achieved;
3) The invention uses CaO-SiO 2-Al2O3A ternary system forms a liquid phase at a lower temperature (1200 ℃), and TZP large grains with higher Ca ion content grow in a zirconia matrix finally, so that the effect of bridging and toughening the large grains is achieved, and the sintering temperature is reduced;
4) According to the invention, the TZP grains of small grains are further refined by the existence of TZP large grains and the grains of alumina existing on the zirconia grain boundary, so that the effects of refining and toughening the grains are achieved;
5) According to the invention, according to the characteristic that Al ions are difficult to enter zirconia crystal lattices, alumina crystal grains are formed on zirconia crystal boundaries, and the second dispersion toughening effect is achieved.
6) In general, the maximum bending strength of the TZP ceramic material prepared by the invention is 1520MPa, and the fracture toughness measured by the SENB method reaches 18.5MP.m 1/2Fracture toughness measured by SEVNB method Is 10.3MP.m 1/2(ii) a Has excellent mechanical property, low sintering temperature and low energy consumption.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of a polished surface of the high toughness zirconia ceramic prepared in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) cross-section of the high toughness zirconia ceramic prepared in example 1;
FIG. 3 is a characteristic X-ray Energy Dispersion Spectrum (EDS) chart of the surface of the sintered sample in example 1;
FIG. 4 is an X-ray diffraction (XRD) pattern of the surface of the sintered sample in example 1;
FIG. 5 is an X-ray diffraction (XRD) pattern of a cross section of the high toughness zirconia ceramic prepared in example 1, measured for strength by three-point bending and fracture toughness by SENB method and SEVNB method.
Detailed Description
For a better understanding of the present invention, the present invention will be further described with reference to the following specific examples and drawings, but the present invention is not limited thereto.
meanwhile, according to the reports of documents [ W.ZHao, P.Rao, Z.L.ing, A new method for the preparation of ultra-short V-latches to measure fracture toughness in ceramics, J.Eur.Ceram.Soc., Vol.34, No, 4059-4062, 2014], the fracture toughness value measured by the SENB method is higher, so that the SENB method and the SEVNB method are adopted to test the fracture toughness, and the fracture toughness of the SEVNB method is the real fracture toughness of the material.
Example 1
(1) With CaCl 2·2H2O、AlCl3.6H2O and Si (OC) 2H5)4Is prepared from CaO and Al 2O3:SiO2the molar ratio of the components is 2: 10: 0.5, the prepared solution is stirred for 0.5h, ammonia water with the concentration of 0.1 ml/L is slowly added to adjust the PH value to 8.7 to generate a precipitate, and the precipitate is washed by water and centrifuged to obtain CaO-Al 2O3-SiO2And (3) compounding the precursor sol.
(2) According to Y 2O3And ZrO 2In a molar ratio of 0.5: 99.5 weigh adding water to mix zirconium oxychloride octahydrate and yttrium chloride hexahydrate, dropwise adding 0.15 ml/L ammonia water, adjusting the pH value to 9.2 to generate a precipitate, washing and centrifuging to obtain a zirconium hydroxide precursor, and drying at 100 ℃ for 0.5h to obtain the composite powder B.
(3) The CaO-Al is added 2O3-SiO2the composite precursor sol, the composite powder B, water and a dispersing agent (the mass ratio of ammonium polyacrylate to sodium carboxymethylcellulose is 1:1) in the step (2) are mixed according to the mass ratio of 30: 70: 100: 3, the mixture is subjected to ball milling for 2 hours in a 500r/min planetary mill to obtain mixed slurry, the mixed slurry is dried at 90 ℃ and then screened by a 100-mesh screen, the obtained powder is calcined at 600 ℃, then the water, zirconia ball stone and the calcined powder are mixed according to the ratio of 1: 2: 1.5, ball milling is carried out to obtain mixed slurry, the ball milling parameters are 500r/min and 2 hours, the mixed slurry is subjected to spray granulation to obtain granulated powder, and the operation parameters are that the temperature of drying air is 250 ℃, the air outlet temperature is 150 ℃ and the slurry flow rate is 1.8L/h.
(4) And (4) dry-pressing and molding the granulation powder in the step (3) under 15MPa, and sintering for 2 hours at 1400 ℃ to obtain the TZP ceramic.
The test piece obtained in example 1 was found to have a density of 97.3%, a three-point bending strength of 1180MPa (span 30mm, loading rate 0.5mm/s) and a fracture toughness of 16.8MP.m measured by the SENB method 1/2(span 30mm, load rate 0.05mm/s) and a fracture toughness of 9.8MP.m measured by SEVNB method 1/2(span 30mm, load rate 0.05 mm/s). SEM, EDS and XRD characterization are carried out on the TZP ceramic, and as shown in figure 1, the sintered TZP ceramic has part of large grains and small grains with uniform size. As can be seen from the cross-sectional SEM image of fig. 2, the large grains all fractured in a transgranular fracture manner, and the small grains fractured in a grain-aligned fracture manner. As shown in FIG. 3, the Ca ion content of the large grains reached 2.21 wt%, and the content of the surrounding small grains was 0.62 wt%. As shown in FIG. 4, the sintered TZP ceramic phase composition is a stable tetragonal phase, and as shown in FIG. 5, 30 vol% of zirconia is phase-transformed in the cross section after SEVNB test, and 52 vol% of zirconia is phase-transformed in the cross section after strength test.
Example 2
(1) With CaCl 2·2H2O and Ca (NO) 3)2.4H2O (molar ratio of 1:1) and Al (NO) 3)3.6H2O、Si(OC2H5)4Is prepared from CaO and Al 2O3:SiO2the molar ratio of the CaO to the Al is 5: 3: 3, the prepared solution is stirred for 0.5h, ammonia water with the concentration of 0.15 ml/L is slowly added to adjust the PH value to 9.2 to generate precipitate, and the precipitate is washed by water and centrifuged to obtain CaO-Al 2O3-SiO2And (3) compounding the precursor sol.
(2) According to Y 2O3And ZrO 2the method comprises the steps of weighing zirconium oxychloride octahydrate and yttrium chloride hexahydrate according to the molar ratio of 2: 98, adding water, mixing, dropwise adding 0.1 ml/L ammonia water, adjusting the pH to 8.7 to generate a precipitate, washing, centrifuging to obtain a zirconium hydroxide precursor, and drying at 200 ℃ for 1h to obtain the composite powder B.
(3) CaO-Al in the step (1) 2O3-SiO2the composite precursor sol, the composite powder B, water and a dispersing agent (the mass ratio of polyethylene glycol to sodium tripolyphosphate is 1:1) in the step (2) are mixed according to the mass ratio of 20: 80: 120: 3, the mixture is subjected to ball milling for 2 hours in a 500r/min planetary mill to obtain mixed slurry, the mixed slurry is dried at 110 ℃ and then screened by a 200-mesh screen, the obtained powder is calcined at 600 ℃, then, the water, zirconia ball stone and the calcined powder are mixed according to the ratio of 1: 2: 1 and subjected to ball milling to obtain mixed slurry, the ball milling parameters are 400r/min and 4 hours, the mixed slurry is subjected to spray granulation to obtain granulated powder, and the operation parameters are that the drying air temperature is 300 ℃, the air outlet temperature is 150 ℃ and the slurry flow rate is 2.3L/h.
(4) And (4) dry-pressing and molding the granulated powder in the step (3) under 15MPa, and sintering at 1300 ℃ for 1h to obtain the TZP ceramic.
The test results show that the density of the sample obtained in example 2 reaches 97.8%, the three-point bending strength reaches 1080MPa (span 30mm, loading rate 0.5mm/s), and the SENB fracture toughness is 15.8MP.m 1/2(span 30mm, load rate 0.05mm/s) and a fracture toughness of 8.8MP.m measured by SEVNB method 1/2(span 30mm, load rate 0.05 mm/s). SEM and XRD characterization is carried out on the prepared TZP ceramic, In the sintered TZP ceramic, there are some large grains, and the small grains are uniform in size (see fig. 1). As can be seen from the cross-sectional SEM pictures, the large grains all fractured in a transgranular fracture manner, and the small grains fractured in an epitaxial fracture manner (see fig. 2). The Ca ion content of the large grains reached 2.71 wt%, and the content of the surrounding small grains was 0.42 wt% (see FIG. 3). The sintered TZP ceramic phase composition became a stable tetragonal phase (see fig. 4), with 30 vol% zirconia phase transformed in the fracture surface after the SEVNB test and 53 vol% zirconia phase transformed in the fracture surface after the strength test (see fig. 5).
Example 3
(1) With Ca (NO) 3)2.4H2O、AlCl3.6H2O and Al (NO) 3)3.6H2O (molar ratio of 1:1), Si (OC) 2H5)4Is prepared from CaO and Al 2O3:SiO2the molar ratio of the components is 3: 6: 1.5, the prepared solution is stirred for 0.5h, ammonia water with the concentration of 0.2 ml/L is slowly added to adjust the PH value to 9 to generate a precipitate, and the precipitate is washed by water and centrifuged to obtain CaO-Al 2O3-SiO2And (3) compounding the precursor sol.
(2) According to Y 2O3And ZrO 2the method comprises the steps of weighing zirconium oxychloride octahydrate and yttrium chloride hexahydrate according to the molar ratio of 1.5: 98.5, adding water, mixing, dropwise adding 0.1 ml/L ammonia water, adjusting the pH to 9.5 to generate a precipitate, washing, centrifuging to obtain a zirconium hydroxide precursor, and drying at 300 ℃ for 0.5h to obtain the composite powder B.
(3) CaO-Al in the step (1) 2O3-SiO2The composite precursor sol, the composite powder B in the 2), water and a dispersing agent (ammonium polyacrylate) according to a mass ratio of 15: 85: 100: 3, mixing, and ball milling for 2 hours in a planetary mill of 500r/min to obtain mixed slurry. The mixed slurry was dried at 100 ℃ and sieved through a 150-mesh sieve, and the obtained powder was calcined at 600 ℃. And then mixing water, zirconia ball stone and calcined powder according to the proportion of 1: 2: 1.2, and obtaining mixed slurry after ball milling. The ball milling parameters are as follows: 500r/min and 2 h. And (3) carrying out spray granulation on the mixed slurry to obtain granulation powder, wherein the operation parameters are as follows: temperature of drying air the temperature of the air outlet is 250 ℃, the temperature of the air outlet is 130 ℃, and the flow rate of the slurry is 1.8L/h.
(4) And (4) dry-pressing and molding the granulated powder in the step (3) under 15MPa, and sintering at 1350 ℃ for 2h to obtain the Y-TZP ceramic.
The density of the sample obtained in example 3 is 98.1%, the three-point bending strength is 1520MPa (span 30mm, loading rate 0.5mm/s), and the fracture toughness of SENB method is 18.5MP.m 1/2(span 30mm, load rate 0.05mm/s) and a fracture toughness of 10.3MP.m measured by SEVNB method 1/2(span 30mm, load rate 0.05 mm/s). SEM and XRD characterization is carried out on the prepared TZP ceramic, and the sintered TZP ceramic has a part of large grains and small grains with uniform size (see figure 1). As can be seen from the cross-sectional SEM pictures, the large grains all fractured in a transgranular fracture manner, and the small grains fractured in an epitaxial fracture manner (see fig. 2). The Ca ion content of the large grains reached 2.41 wt%, and the content of the surrounding small grains was 0.73 wt% (see FIG. 3). The sintered TZP ceramic phase composition became a stable tetragonal phase (see fig. 4), and 35 vol% of zirconia phase transformed in the cross-section after the SEVNB test, and 63 vol% of zirconia phase transformed in the cross-section after the strength test (see fig. 5).
Example 4
(1) With CaCl 2·2H2O、AlCl3.6H2O and Si (OC) 2H5)4Is prepared from CaO and Al 2O3:SiO2the molar ratio of the components is 2: 3: 3, the prepared solution is stirred for 0.5h, ammonia water with the dilution concentration of 0.1 ml/L is slowly added to adjust the PH value to 10 to generate precipitation, and CaO-Al is obtained after washing and centrifugation 2O3-SiO2And (3) compounding the precursor sol.
(2) According to Y 2O3And ZrO 2the method comprises the steps of weighing and preparing zirconium oxychloride octahydrate and yttrium chloride hexahydrate according to the molar ratio of 2.5: 97.5, adding water for mixing, dropwise adding 0.2 ml/L ammonia water, adjusting the pH value to 9 to generate a precipitate, washing and centrifuging to obtain a zirconium hydroxide precursor, and drying at 250 ℃ for 0.5h to obtain the composite powder B.
(3) CaO-Al in the step (1) 2O3-SiO2Compounding the precursor sol, the composite powder B, water and a dispersing agent (the mass ratio of ammonium polyacrylate to trisodium phosphate is 1:1) in the step (2) are mixed according to the mass ratio of 10: 80: 110: 0.5, the mixture is subjected to ball milling in a 500r/min planetary mill for 2 hours to obtain mixed slurry, the mixed slurry is dried at 100 ℃ and then screened by a 100-mesh screen, the obtained powder is calcined at 900 ℃, then the water, zirconia ball stone and the calcined powder are mixed according to the ratio of 1: 2: 1.5, ball milling is carried out to obtain mixed slurry, the ball milling parameters are 450r/min and 3 hours, the mixed slurry is subjected to spray granulation to obtain granulated powder, and the operation parameters are that the temperature of drying air is 250 ℃, the air outlet temperature is 110 ℃ and the slurry flow rate is 2.1L/h.
(4) And (4) dry-pressing and molding the granulation powder in the step (3) under 25MPa, and sintering for 2 hours at 1400 ℃ to obtain the TZP ceramic.
The density of the sample obtained in example 4 was 97.5%, the three-point bending strength was 981MPa (span 30mm, loading rate 0.5mm/s), and the fracture toughness was 14.3MP.m as measured by the SENB method 1/2(span 30mm, load rate 0.05mm/s) and fracture toughness of 7.8MP.m measured by SEVNB method 1/2(span 30mm, load rate 0.05 mm/s). SEM and XRD characterization is carried out on the prepared TZP ceramic, and the sintered TZP ceramic has a part of large grains and small grains with uniform size (see figure 1). As can be seen from the cross-sectional SEM pictures, the large grains all fractured in a transgranular fracture manner, and the small grains fractured in an epitaxial fracture manner (see fig. 2). The large grains had a Ca ion content of 2.31 wt%, the surrounding small grains had a content of 0.52 wt% (see fig. 3), the sintered TZP ceramic phase composition became a stable tetragonal phase (see fig. 4), 26 vol% of zirconia was phase-transformed in the cross-section after the SEVNB test, and 43 vol% of zirconia was phase-transformed in the cross-section after the strength test (see fig. 5).
Example 5
(1) With CaCl 2·2H2O、Al(NO3)3.6H2O and Si (OC) 2H5)4Is prepared from CaO and Al 2O3:SiO2the molar ratio of (1) to (2) is 4: 7, the prepared solution is stirred for 0.5h, ammonia water with the concentration of 0.2 ml/L is slowly added to adjust the PH value to 9 to generate a precipitate, and the precipitate is treated by water Washing and centrifuging to obtain CaO-Al 2O3-SiO2And (3) compounding the precursor sol.
(2) According to Y 2O3And ZrO 2the method comprises the following steps of weighing zirconium oxychloride octahydrate and yttrium chloride hexahydrate according to the molar ratio of 3: 97, adding water, mixing, dropwise adding 0.15 ml/L ammonia water, adjusting the pH to 9.5 to generate a precipitate, washing, centrifuging to obtain a zirconium hydroxide precursor, and drying at 300 ℃ for 0.5h to obtain the composite powder B.
(3) CaO-Al in the step (1) 2O3-SiO2the preparation method comprises the following steps of (1) mixing the composite powder B, water and a dispersing agent (the mass ratio of polyethylene glycol to sodium hexametaphosphate is 1:1) in the composite precursor sol and 2) according to the mass ratio of 10: 90: 100: 2, carrying out ball milling in a 500r/min planetary mill for 2 hours to obtain mixed slurry, drying the mixed slurry at 100 ℃, sieving the dried mixed slurry with a 200-mesh sieve to obtain powder, calcining the obtained powder at 800 ℃, mixing the water, zirconia ball stone and the calcined powder according to the ratio of 1: 2: 1.5, carrying out ball milling to obtain mixed slurry, carrying out spray granulation on the mixed slurry for 3 hours to obtain granulated powder, wherein the operation parameters comprise that the temperature of drying air is 300 ℃, the air outlet temperature is 150 ℃ and the slurry flow rate is 2.3L/h.
(4) And (4) dry-pressing and molding the granulated powder in the step (3) under 30MPa, and sintering at 1400 ℃ for 1h to obtain the TZP ceramic.
The density of the sample obtained in example 5 was determined to be 96.0%, the three-point bending strength was 1307MPa (span 30mm, loading rate 0.5mm/s), and the fracture toughness was determined to be 14.3MP.m by the SENB method 1/2(span 30mm, load rate 0.05mm/s) and fracture toughness of 7.8MP.m measured by SEVNB method 1/2(span 30mm, load rate 0.05 mm/s). SEM and XRD characterization is carried out on the prepared TZP ceramic, and the sintered TZP ceramic has a part of large grains and small grains with uniform size (see figure 1). As can be seen from the cross-sectional SEM pictures, the large grains all fractured in a transgranular fracture manner, and the small grains fractured in an epitaxial fracture manner (see fig. 2). The Ca ion content of the large grains reached 2.41 wt%, and the content of the surrounding small grains was 0.62 wt% (see FIG. 3). The TZP ceramic phase after sintering consisted of a stable tetragonal phase (see FIG. 4), break after SEVNB test In the above, 28 vol% of zirconia was phase-transformed, and in the cross section after the strength test, 47 vol% of zirconia was phase-transformed (see FIG. 5).
Example 6
(1) With CaCl 2·2H2O、Al(NO3)3.6H2O and Si (OC) 2H5)4Is prepared from CaO and Al 2O3:SiO2the molar ratio of the CaO to the Al is 1: 10: 2, the prepared solution is stirred for 0.5h, ammonia water with the concentration of 0.1 ml/L is slowly added to adjust the PH value to 9 to generate a precipitate, and the precipitate is washed by water and centrifuged to obtain CaO-Al 2O3-SiO2And (3) compounding the precursor sol.
(2) According to Y 2O3And ZrO 2the method comprises the following steps of weighing zirconium oxychloride octahydrate and yttrium chloride hexahydrate according to the molar ratio of 3: 97, adding water, mixing, dropwise adding 0.2 ml/L ammonia water, adjusting the pH to 10 to generate a precipitate, washing, centrifuging to obtain a zirconium hydroxide precursor, and drying at 300 ℃ for 0.5h to obtain the composite powder B.
(3) CaO-Al in the step (1) 2O3-SiO2the preparation method comprises the following steps of (1) mixing the composite powder B, water and a dispersing agent (the mass ratio of polyethylene glycol to sodium hexametaphosphate is 1:1) in the composite precursor sol and 2) according to a mass ratio of 20: 80: 100: 2, carrying out ball milling in a 500r/min planetary mill for 2 hours to obtain mixed slurry, drying the mixed slurry at 100 ℃, sieving the dried mixed slurry with a 200-mesh sieve to obtain powder, calcining the obtained powder at 800 ℃, mixing the water, zirconia ball stone and the calcined powder according to a ratio of 1: 2: 2, carrying out ball milling to obtain mixed slurry, carrying out spray granulation on the mixed slurry for 3 hours to obtain granulated powder, wherein the operation parameters comprise that the temperature of drying air is 300 ℃, the air outlet temperature is 140 ℃ and the flow rate of the slurry is 2.3L/h.
(4) And (4) dry-pressing and molding the granulation powder in the step (3) under 30MPa, and sintering at 1500 ℃ for 1h to obtain the TZP ceramic.
The density of the sample obtained in example 5 was determined to be 98.0%, the three-point bending strength was determined to be 835MPa (span 30mm, loading rate 0.5mm/s), and the fracture toughness was determined to be 8.9MP.m by the SENB method 1/2(span 30mm, load rate 0.05mm/s), measured by the SEVNB method The fracture toughness obtained is 5.2MP.m 1/2(span 30mm, load rate 0.05 mm/s). The prepared TZP ceramic is characterized by SEM and XRD, and the crystal grain size in the sintered TZP ceramic is relatively uniform (see figure 1). As can be seen from the SEM image of the cross section, the grains are mainly in the epitaxial fracture. The Ca ion content of the larger grains was 0.72 wt%, and the content of the surrounding small grains was 0.56 wt% (see FIG. 3). The sintered TZP ceramic phase composition became a stable tetragonal phase (see fig. 4), with 10 vol% of zirconia undergoing phase transformation in the fracture surface after the SEVNB test and 23 vol% of zirconia undergoing phase transformation in the fracture surface after the strength test (see fig. 5).
Example 7
(1) With CaCl 2·2H2O and Ca (NO) 4)2.4H2O (molar ratio of 1:1) and Al (NO) 3)3.6H2O、Si(OC2H5)4Is prepared from CaO and Al 2O3:SiO2the molar ratio of the components is 5: 10: 0.1, the prepared solution is stirred for 0.5h, ammonia water with the concentration of 0.1 ml/L is slowly added to adjust the PH value to 9 to generate a precipitate, and the precipitate is washed by water and centrifuged to obtain CaO-Al 2O3-SiO2And (3) compounding the precursor sol.
(2) According to Y 2O3And ZrO 2the method comprises the following steps of weighing zirconium oxychloride octahydrate and yttrium chloride hexahydrate according to the molar ratio of 3: 97, adding water, mixing, dropwise adding 0.15 ml/L ammonia water, adjusting the pH to 8.7 to generate a precipitate, washing, centrifuging to obtain a zirconium hydroxide precursor, and drying at 300 ℃ for 0.5h to obtain the composite powder B.
(3) CaO-Al in the step (1) 2O3-SiO2The composite precursor sol, the composite powder B in the 2), water and a dispersant (polyethylene glycol) according to a mass ratio of 20: 80: 100: 2, mixing, and ball milling for 2 hours in a planetary mill of 500r/min to obtain mixed slurry. The mixed slurry is dried at 100 ℃ and sieved by a 200-mesh sieve, and the obtained powder is calcined at 800 ℃. And then mixing water, zirconia ball stone and calcined powder according to the proportion of 1: 2: 2, and mixing and ball-milling to obtain mixed slurry. The ball milling parameters are as follows: 400r/min and 3 h. Spray granulating the mixed slurry to obtain granulated powder the parameters are that the temperature of the drying air is 200 ℃, the air outlet temperature is 110 ℃, and the flow rate of the slurry is 1.8L/h.
(4) And (4) dry-pressing and molding the granulated powder in the step (3) under 20MPa, and sintering at 1480 ℃ for 1h to obtain the TZP ceramic.
The density of the sample obtained in example 5 was found to be 94.0%, the three-point bending strength to be 771MPa (span 30mm, loading rate 0.5mm/s), and the fracture toughness to be 10.2MP.m as measured by SENB method 1/2(span 30mm, load rate 0.05mm/s) and a fracture toughness of 6.5MP.m measured by SEVNB method 1/2(span 30mm, load rate 0.05 mm/s). The prepared TZP ceramic is characterized by SEM and XRD, and the sintered TZP ceramic has uniform grain size and larger average grain size (see figure 1). As can be seen from the SEM image of the cross section, the grains are mainly in the epitaxial fracture. The Ca ion content of the larger grains was 2.31 wt%, and the content of the surrounding small grains was 2.10 wt% (see FIG. 3). The sintered TZP ceramic phase composition became a stable tetragonal phase (see fig. 4), 29 vol% of the zirconia phase transformed in the cross-section after the SEVNB test, and 43 vol% of the zirconia phase transformed in the cross-section after the strength test (see fig. 5).
Claims (8)
1. The preparation method of the zirconia ceramic with high fracture toughness is characterized by comprising the following steps:
(1) Mixing soluble salt of calcium ion, soluble salt of aluminum ion and Si (OC) 2H5)4Adding water to prepare a mixed solution; stirring, dropwise adding ammonia water to adjust the pH of the mixed solution to generate a precipitate, washing with water, and performing centrifugal separation to obtain a composite sol A; soluble salts of calcium ions, soluble salts of aluminum ions and Si (OC) 2H5)4According to CaO, Al 2O3、SiO2In a molar ratio of (2-5): (3-10): (0.5-3) weighing;
(2) Adding water into zirconium oxychloride octahydrate and yttrium chloride hexahydrate for mixing, dropwise adding ammonia water to adjust the pH value to generate a precipitate, washing and centrifuging to obtain a zirconium hydroxide precursor, and drying to obtain composite powder B; zirconium oxychloride octahydrate and yttrium chloride hexahydrate according to ZrO 2、Y2O3In a molar ratio of (0.5-3): (99.5-97) weighing;
(3) Mixing the composite sol A obtained in the step (1), the composite powder B obtained in the step (2), water and a dispersing agent, drying, sieving, calcining, ball-milling, and spray-granulating to obtain composite powder C; the mass ratio of the composite sol A to the composite powder B to the water to the dispersant is (10-30): (70-90): (100-120): (0.5-3); the calcination temperature is 600-900 ℃;
(4) And (4) carrying out dry pressing forming and sintering on the composite powder C obtained in the step (3) to obtain the zirconia ceramic with high fracture toughness.
2. The method for preparing zirconia ceramic with high fracture toughness as claimed in claim 1, wherein in step (1), the soluble salt of calcium ion is CaCl 2 .2H2O and Ca (NO) 3)2 .4H2Any one or a combination of O; the soluble salt of the aluminum ion is AlCl 3 .6H2O and Al (NO) 3)3 .6H2Any one or a combination of O.
3. the method for preparing zirconia ceramic with high fracture toughness of claim 1, wherein in the step (1), the concentration of the ammonia water is 0.1-0.2 ml/L, and the pH of the mixed solution is 8.7-10.
4. The method for preparing zirconia ceramic with high fracture toughness according to claim 1, wherein in the step (2), the pH of the solution obtained after adding water and mixing is 8.7-10, the drying temperature is 100-300 ℃, and the drying time is 0.5-1 h.
5. The method for preparing zirconia ceramic with high fracture toughness as claimed in claim 1, wherein in step (3), the dispersant is one or more of ammonium polyacrylate, polyethylene glycol, sodium tripolyphosphate, sodium carboxymethylcellulose, trisodium phosphate and sodium hexametaphosphate in any ratio.
6. The method for preparing zirconia ceramic with high fracture toughness according to claim 1, wherein in the step (3), the drying temperature is 90-110 ℃, and the mesh number of the sieving is 100-200; the ratio of calcined powder, grinding medium and water in the ball milling process is 1: 2: (1-1.5), the rotating speed and the ball milling time are respectively 400-500r/min and 2-4 h.
7. the method for preparing zirconia ceramic with high fracture toughness according to claim 1, wherein in the step (3), the operating process parameters of spray granulation are that the temperature of drying air is 250-300 ℃, the air outlet temperature is 110-150 ℃, and the flow rate of slurry is 1.8-2.3L/h.
8. The method for preparing zirconia ceramic with high fracture toughness according to claim 1, wherein in the step (4), the pressure of the dry pressing is 15-30MPa, and the sintering temperature and the holding time are 1300-1400 ℃ and 1-2h respectively.
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