# Patent

## Title
ZrO2-Al2O3-based ceramic sintered compact and production method thereof

## Abstract

A ZrO2—Al2O3-based ceramic sintered compact containing tetragonal ZrO2 particles having a crystallite size of from 5 to 20 nm as a main component and having an α-Al2O3 crystallite size of not greater than 75 nm and a relative density of not less than 99% can be produced by preparing a Y2O3 partially stabilized ZrO2—Al2O3-based powder having a molar ratio (mol %) of zirconia (ZrO2) and yttria (Y2O3) of from 96.5:3.5 to 97.5:2.5 and a mass ratio (mass %) of ZrO2 containing Y2O3 and alumina (Al2O3) of from 85:15 to 75:25, molding this powder by cold isostatic pressing, and then performing sintering to a high density by microwave sintering for 45 to 90 min in an inert gas atmosphere at 1200 to 1400° C. When performing microwave sintering, a heating rate is preferably from 5 to 20° C./min up to 600° C. and from 50 to 150° C./min at 600° C. or higher.

## Background
TECHNICAL FIELD
The present invention relates to a ZrO2—Al2O3-based ceramic sintered compact and a method for producing the ceramic sintered compact.
BACKGROUND ART
Ceramic materials, which have many characteristics such as chemical stability, corrosion resistance, and usability in high-temperature environments in comparison to metals, have high hardness or strength but have the drawback of low toughness, and the application thereof is limited. Further, the enhancement of reliability is viewed as important when a ceramic is used as a structural body. In order to enhance the reliability of a ceramic structure, the structure must be a dense body. To obtain a dense body, it is necessary to reduce voids—that is, the air holes in the sintered body, by sufficiently increasing the sintering temperature. However, when the sintering temperature is increased, the grains of the sintered compact become large, which causes chipping such as grain pulling out from the sintered compact surface. This becomes a source of fracture, which leads to drawback such as reduction in the structural strength of the ceramic. Further, in the case of a ceramic structure containing a plurality of metal oxides, unless the growth of sintered compact crystals of each metal oxide that is contained is controlled harmoniously, problems arise such as dominance of the characteristics of certain types of metal compounds, leading to the lack of structural functionality as a ceramic body which should be inherent to the composition.
In this way, achieving both the densification of a ceramic structure and the size reduction of sintered compact crystals has been a problem in the preparation of ceramics with guaranteed reliability.
As one method of enhancing the reliability of a ceramic structure and enhancing the toughness—that is, the fracture toughness value (KIC)—of a ceramic, it has been disclosed in Patent Document 1, for example, that a ceramic with high strength/toughness, which is a dense sintered compact having small crystals and simultaneously exhibiting a bending strength (σb) of not less than approximately 1,000 MPa (1 GPa) and a KIC of not less than 15 MPa·m1/2, is obtained by preparing a ZrO2 (0.3 to 1.7 mol % Y2O3)-25 mol % Al2O3 solid solution powder containing zirconia (ZrO2) to which yttrium oxide (Y2O3) having a function of high toughness is added, and alumina (Al2O3) having a function of high strength, by means of a sol-gel method and performing Pulsed Electric-Current Pressure Sintering (PECPS). However, in this case, there remains a problem in that the raw material preparation cost is high (the cost per 1 g of raw material is over several thousand yen).
On the other hand, in the case of a powder prepared by a solid phase reaction or the like or a powder prepared by a liquid phase method other than a sol-gel method, the composition or particle size distribution of the powder particles may not be uniform. Therefore, even when these powders are sintered, the composition in the ceramic structure may not be uniform, and although the powders are sintered at a high temperature in order to increase homogeneity, the aforementioned problems of densification and size reduction of the sintered compact crystals may not be satisfactorily resolved. Thus, the availability of a ceramic with high strength/toughness is still a problem.
Therefore, in order to resolve the problems described above, the applicants of the present invention and others proposed, in Patent Document 2 below, the production of an oxide-based ceramic (ZrO2—Al2O3-based ceramic) which simultaneously exhibits high strength and toughness by preparing a zirconia-alumina-based microparticulate powder containing a small amount of yttrium oxide (1.5 mol % Y2O3) by a coprecipitation process and then molding the powder at a high density and sintering the sintered compact crystals so as to be dense and minute by Pulsed Electric-Current Pressure Sintering (PECPS) at a high heating rate.
However, PECPS has restrictions with regard to the shape of the compact due to uniaxial pressure sintering, and the productivity is also low. From the perspective of cost reduction as well, there are many problems regarding developing ceramics to a wide range of applications.
PRIOR ART DOCUMENTS
Patent Documents


    Patent Document 1: WO/2012/153645
    Patent Document 2: JP-A-2014-189474


SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
An object of the present invention is to solve the aforementioned problems of conventional technology and to provide a method which makes it possible to obtain a highly reliable sintered compact at low cost (the cost per 1 g of raw material is less than approximately 1/100 the cost of a sintered product produced by a sol-gel method), the sintered compact simultaneously satisfying high strength and toughness and having high density and a small crystallite size, and which makes it possible to produce a high-strength/toughness ZrO2—Al2O3-based ceramic without any restriction on the shape of the compact—that is, processing the ceramic to the final shape for the use, which is more difficult to process than metals or plastic materials, is unnecessary.
Means for Solving the Problems
As a result of conducting various research, the present inventors and others discovered that a zirconia-alumina-based ceramic sintered at a high density, which has a fine nanostructure with a zirconia crystallite size of from 5 to 20 nm and an alumina crystallite size of not greater than 75 nm, and exhibits high strength and toughness, can be produced. This ceramic can be produced by first producing a dense compact with a free shape from a powder prepared with a coprecipitation process (at a lower cost, less than approximately 1/100 the cost, than a high-cost sol-gel method), or a zirconia-alumina based microparticulate powders of commercially available such as a mixed powder of zirconia which containing a small amount of yttria and alumina, and then performing microwave sintering without pressurization, while heating the interior of the sintered compact so that the same degree of rapid heating as in the case of PECPS can be achieved, thereby completing the present invention.
The ZrO2—Al2O3-based ceramic sintered compact according to an embodiment of the present invention which is capable of resolving the problems described above comprises a Y2O3 partially stabilized ZrO2—Al2O3 composite sintered compact having a molar ratio (mol %) of zirconia (ZrO2) and yttria (Y2O3) of from 96.5:3.5 to 97.5:2.5 and a mass ratio (mass %) of zirconia containing yttria and alumina (Al2O3) of from 85:15 to 75:25. And the ZrO2—Al2O3 composite sintered compact contains tetragonal ZrO2 particles having a crystallite size of from 5 to 20 nm as a main component, a crystallite size of α-Al2O3 is not greater than 75 nm, and the sintered compact has a relative density of not less than 99%. Here, “containing as a main component” means that the content ratio of the component is not less than 70 mass %.
In addition, according to an embodiment of the present invention, for the ZrO2—Al2O3-based ceramic sintered compact having the characteristics described above, a three-point bending strength is not less than 1.0 GPa; a fracture toughness is not less than 6.0 MPa·m1/2; and a Vickers hardness is not less than 12.0 GPa.
Further, the method according to an embodiment of the present invention for producing the ZrO2—Al2O3-based ceramic sintered compact described above comprises the following steps (A) and (B):
(A): preparing a Y2O3 partially stabilized ZrO2—Al2O3-based powder having a molar ratio (mol %) of zirconia (ZrO2) and yttria (Y2O3) of from 96.5:3.5 to 97.5:2.5 and a mass ratio (mass %) of zirconia containing yttria and alumina (Al2O3) of from 85:15 to 75:25; and
(B): producing a high-density compact by molding the Y2O3 partially stabilized ZrO2—Al2O3-based powder by cold isostatic pressing and then performing microwave sintering on the compact in an inert gas atmosphere at 1200 to 1400° C. for 45 to 90 min.
In the following explanations, the notation “ZrO2(3Y)-20 mass % Al2O3” refers to 80 mass % (97 mol % ZrO2-3 mol % Y2O3)-20 mass % Al2O3.
In addition, according to an embodiment of the present invention, in the production method having the characteristics described above, a heating rate during microwave sintering in (B) is from 5 to 20° C./min up to 600° C. and from 50 to 150° C./min at 600° C. or higher.
Further, according to an embodiment of the present invention, in the production method having the characteristics described above, a mixture of a Y2O3 partially stabilized ZrO2 and an Al2O3 powder or a solid solution powder produced by a coprecipitation process is used as the Y2O3 partially stabilized ZrO2—Al2O3-based powder.
Effect of the Invention
By using the production method according to an embodiment of the present invention, it is possible to produce a high-strength/toughness ZrO2—Al2O3-based ceramic having a bending strength σb of ≧1 GPa, a fracture toughness value KIC of ≧6 MPa·m1/2, and a Vickers hardness HV of ≧12 GPa from: a powder prepared with a coprecipitation process, which involves a lower cost than a high-cost sol-gel method; a powder prepared by preparing only a ZrO2 powder in which Y2O3 is solidified by a coprecipitation process and then further mixing a commercially available microparticulate Al2O3 with said powder; or a mixed powder of commercially available microparticulate partially stabilized ZrO2 and Al2O3.
In addition, in the production method according to an embodiment of the present invention using microwave sintering, the crystallite particle sizes of both the ZrO2 and Al2O3 constituting the ceramic are both far smaller than those of a ceramic produced by PECPS. Therefore, even at the same relative density and grain size of sintered body, the strength and toughness of a microwave-sintered ceramic are higher than those of a PECPS ceramic. Moreover, the production method according to an embodiment of the present invention also has the advantage that a dense sintered compact (relative density: 99.0%) can be produced at a temperature (approximately 1200° C.) approximately 150° C. lower than the sintering temperature of a sintering method using a typical electric sintering furnace with a controlled atmosphere or a PECPS method. Further, because microwave sintering is a method involving heating the interior of a sample in a pressureless manner, the restrictions on the shape of the compact are eliminated to a greater degree than a PECPS sintering method involving uniaxial pressurization and external heating. Processing the ceramic to the final shape for the use, which is more difficult than processing metals or plastic materials, becomes practically unnecessary, which yields a high possibility of leading to low cost and enhanced mass productivity.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a flowchart illustrating the steps of the ZrO2—Al2O3-based ceramic production method according to an embodiment of the present invention. In addition to the conditions of microwave sintering used in the examples, the sintering conditions of sintering with an electric sintering furnace having a controlled atmosphere and Pulsed Electric-Current Pressure Sintering (PECPS) used in the comparative examples are also listed.
FIG. 2 shows XRD patterns of various composites, in which the pattern with reference to “Starting substance” is an XRD pattern of a ZrO2(3Y)-20 mass % Al2O3 mixed powder serving as a starting material; the pattern with reference to “Atmospheric sintering with a conventional electric furnace (1350° C./120 min/Ar)” is an XRD pattern of a ceramic produced by sintering with an ordinary electric sintering furnace with a controlled atmosphere; the pattern with reference to “PECPS (1350° C./10 min/50 MPa/Ar)” is an XRD pattern of a ceramic produced by PECPS; and the pattern with reference to Microwave sintering (1350° C./60 min/N2)” is an XRD pattern of a ceramic produced by microwave sintering.
FIG. 3A to FIG. 3F illustrate scanning electron microscope (SEM) photographs of fracture surfaces for ZrO2(3Y)-20 mass % Al2O3 ceramics produced using various sintering methods (sintering temperature of 1250° C. for FIG. 3A, FIG. 3B, and FIG. 3C, and sintering temperature of 1350° C. for FIG. 3D, FIG. 3E, and FIG. 3F).
FIG. 4A to FIG. 4C illustrate SEM photographs of polished surfaces for ZrO2(3Y)-20 mass % Al2O3 ceramics produced at 1350° C. using various sintering methods.
FIG. 5 is a graph illustrating the relationships between the relative density of ZrO2(3Y)-20 mass % Al2O3 ceramics produced using various sintering methods and grain size of sintered body and sintering temperature.
FIG. 6 is a graph illustrating the relationships between the bending strength σb, Vickers hardness Hv, and fracture toughness value KIC of ZrO2(3Y)-20 mass % Al2O3 ceramics produced using various sintering methods and the sintering temperature; (a) ∘ represents sintering using an ordinary electric sintering furnace with a controlled atmosphere; (b) ● represents sintering with PECPS; and (c) the circle with the left-half filled black represents microwave sintering.
FIG. 7 illustrates transmission electron microscope (TEM) photographs of fracture surfaces of ZrO2(3Y)-20 mass % Al2O3 ceramics sintered at 1350° C. for 120 minutes in the case of sintering using an ordinary electric sintering furnace with a controlled atmosphere, 10 minutes in the case of PECPS, and for 60 minutes in the case of microwave sintering.
FIG. 8A to FIG. 8C illustrate energy-dispersive X-ray spectroscopic (EDS) electron microscope photographs of the microstructures of ZrO2(3Y)-20 mass % Al2O3 ceramics sintered at 1350° C. using various sintering methods; the photographs are, in order from left to right, an ordinary transmission electron microscope photograph, an image indicating the positions where Al is present, an image indicating the positions where oxygen O is present, and an image indicating the positions where Zr is present for sintering using an ordinary electric sintering furnace with a controlled atmosphere (FIG. 8A), PECPS (FIG. 8B), and microwave sintering (FIG. 8C).
FIG. 9 is a graph illustrating the relationships between the “grain size” and “crystallite size” of a t-ZrO2 phase and an α-Al2O3 phase in a ZrO2(3Y)-20 mass % Al2O3 ceramic produced at 1200 to 1350° C. using each sintering method. Here, a square represents a ceramic produced by atmospheric sintering; a diamond represents a ceramic produced by PECPS; and a circle represents a ceramic produced by microwave sintering.



MODE FOR CARRYING OUT THE INVENTION
Steps (A) and (B) in the method according to an embodiment of the present invention which enables the production of a high-strength/toughness ZrO2—Al2O3-based ceramic sintered compact will be described hereinafter.
In the ZrO2—Al2O3-based ceramic sintered compact according to an embodiment of the present invention, the molar ratio (mol %) of zirconia (ZrO2) and yttria (Y2O3) is from 96.5:3.5 to 97.5:2.5, and the mass ratio (mass %) of zirconia (ZrO2) containing yttria (Y2O3) and alumina (Al2O3) is from 85:15 to 75:25. The reason that the content of Y2O3 with respect to ZrO2 is limited to 2.5 to 3.5 mol % is that if the content is less than 2.5 mol % or, conversely, the content is more than 3.5%, tetragonal ZrO2 particles cannot be present as a main component. If the content of Y2O3 is less than 2.5 mol %, the number of monoclinic ZrO2 particles increases, which causes cracks and may cause the bending strength σb to be smaller than 1 GPa at room temperature or under hydrothermal conditions. If the content of Y2O3 exceeds 3.5 mol %, the number of cubic ZrO2 particles increases, which causes the fracture toughness value KIC to be smaller than 6 MPa·m1/2.
In addition, a preferable content of Y2O3 in the present invention is from 2.6 to 3.4 mol %, and a particularly preferable added amount of Y2O3 is from 2.8 to 3.2 mol %. Further, in the present invention, the reason that the content of Al2O3 is limited to 15 to 25 mass % is that if the content is less than 15 mass %, the properties of the ZrO2 ceramic become dominant and the bending strength σb becomes less than 1 GPa, whereas if the content exceeds 25 mass %, the properties of the Al2O3 ceramic become dominant and the fracture toughness value KIC becomes smaller than 6 MPa·m1/2.
Note that the bending strength σb of the ZrO2—Al2O3-based ceramic sintered compact according to an embodiment of the present invention is not less than 1.0 GPa (preferably not less than 1.2 GPa, and even more preferably not less than 1.4 GPa), the fracture toughness value KIC is not less than 6 MPa·m1/2 (preferably not less than 6.4 MPa·m1/2), and the Vickers hardness HV is not less than 12.0 GPa (preferably not less than 12.9 GPa, and even more preferably not less than 15.0 GPa).
In step (A) in an embodiment of the present invention, a commercially available Y2O3 partially stabilized ZrO2 (ZrO2 powder containing 3 mol % Y2O3 or the like) for typical zirconia ceramic production and a commercially available Al2O3 powder may be mixed and used as a starting material so as to achieve the composition described above, but it is preferable to use a solid solution powder prepared by simultaneously mixing Y2O3 and Al2O3 with ZrO2 with a coprecipitation method from the perspective of enhancing the dispersion of the composition. The solid solution powder is produced using a zirconium salt, an yttrium salt, and an aluminum salt.
When producing the Y2O3 partially stabilized ZrO2—Al2O3 solid solution powder described above, the components are first mixed so that the molar ratio (mol %) of ZrO2 and Y2O3 is from 96.5:3.5 to 97.5:2.5, and the mass ratio (mass %) of ZrO2 containing Y2O3 and Al2O3 is from 85:15 to 75:25. For this procedure, the zirconium salt is not particularly limited, but a chloride aqueous solution, a nitrate aqueous solution, a sulfate aqueous solution, or the like such as zirconium oxychloride (ZrOCl2), zirconium oxynitrate (ZrO(NO3)2), or zirconium sulfate (ZrOSO4) is typically used. The yttrium salt is also not particularly limited, but a chloride aqueous solution, a nitrate aqueous solution, a sulfate aqueous solution, or the like such as yttrium chloride (YCl3), yttrium nitrate (Y(NO3)3), or yttrium sulfate (Y2(SO4)3) is typically used. In addition, a chloride aqueous solution, a nitrate aqueous solution, or the like such as aluminum chloride (AlCl3) or aluminum nitrate (Al(NO3)3) is typically used as an aluminum salt.
Next, an alkali is added to the mixed solution containing the salts described above so as to neutralize the solution and to coprecipitate zirconium, yttrium, and aluminum as a precipitate. The resulting precipitate is filtered, washed with water, and dried, then a solid solution powder of 85 to 75 mass % ZrO2 containing from 2.5 to 3.5 mol % of Y2O3 with respect to ZrO2 (96.5 to 97.5 mol % ZrO2-3.5 to 2.5 mol % Y2O3) and 15 to 25 mass % Al2O3 (the powder is amorphous immediately after being prepared) is prepared. For this procedure, the type of alkali used for neutralization is not particularly limited, and a typical basic substance such as sodium hydroxide, potassium hydroxide, or ammonia may be used.
The obtained powder is then heat-treated for 7 to 12 hours at 650 to 750° C., which is lower than or equal to the crystallization temperature, and further preliminarily calcined in the atmosphere for 0.5 to 3 hours at 850 to 950° C., which is higher than or equal to the crystallization temperature, so as to prepare a cubic Y2O3 partially stabilized ZrO2—Al2O3 solid solution powder. Such an amorphous solid solution powder comprising 75 to 85 mass % {ZrO2 containing Y2O3(96.5 to 97.5 mol % ZrO2-3.5 to 2.5 mol % Y2O3)} and 25 to 15 mass % Al2O3 obtained by the coprecipitation process has the advantage of a lower cost (less than approximately 1/100) than that of a powder produced by a sol-gel method. Moreover, by heat-treating the prepared nanoparticles in an amorphous state (7 to 12 hours at 650 to 750° C.), the diffusion of zirconium, yttrium, and aluminum atoms/ions inside the particles is accelerated, which makes it possible to homogenize the composition within and among particles. Further, by heat-treating the nanoparticles at a temperature higher than or equal to the crystallization temperature (0.5 to 3 hours at 850 to 950° C.), it is possible to crystallize and stabilize the particles and to promote grain growth so that the crystallite size is constant within the small range.
In addition, in step (B) according to an embodiment of the present invention, a high-strength/toughness ZrO2—Al2O3-based ceramic is produced by producing a high-density compact by molding the Y2O3 partially stabilized ZrO2—Al2O3-based powder prepared in step (A) above by cold isostatic pressing, enclosing the compact with fibers made of zirconia, and then sintering the compact with microwaves having a frequency of 2.45 GHz in an inert gas atmosphere (for example, in a nitrogen gas atmosphere) for 45 to 90 minutes at 1200 to 1400° C. and preferably from 1200 to 1350° C. During this procedure, when the sintering temperature is lower than 1200° C., high bending strength (≧1 GPa) is not achieved, whereas when the sintering temperature exceeds 1400° C., a high fracture toughness value (≧6 MPa·m1/2) is not achieved, which is not preferable. A retention time of from 45 to 90 minutes is suitable to achieve sufficient densification. Note that argon, which is an inert gas, cannot be used because argon causes discharge.
In the microwave sintering used in an embodiment in the present invention, the dielectric itself is internally (centrally) heated by an electric (magnetic) field, which makes it possible to achieve energy conservation. Moreover, because the temperature distribution does not depend on the thermal conduction of the sample itself, the temperature distribution is good, and rapid heating is possible, so a dense sintered compact (relative density: not less than approximately 95%) can be produced.
In the present invention, when performing microwave sintering, it is preferable to place the compact in a boron nitride BN crucible, in which zirconia fibers (for example, ZYBF-4 manufactured by Zircar Co., Ltd.) are placed around the compact and a zirconia felt (for example, ZYF-100 manufactured by Zircar Co., Ltd.) is further placed therearound, and to irradiate the resulting configuration with microwaves. In this case, cracking can be effectively prevented from occurring in the sintered compact.
Note that in this step (B), it is typical to perform cold isostatic pressing after adding a binder to the Y2O3 partially stabilized ZrO2—Al2O3 mixed powder or a solid solution powder prepared by simultaneously mixing Y2O3 and Al2O3 prepared in step (A) and grade the particles. Polyvinyl alcohol (PVA) is preferable as a binder added in this procedure, and the heating temperature when performing microwave sintering in step (B) is preferably from 5 to 20° C./min up to 600° C. and from 50 to 150° C./min at 600° C. or higher. The reason for choosing the low heating rate of from 5 to 20° C. up to 600° C. is to prevent cracking from occurring by suppressing inhomogeneity in the temperature distribution inside the sintered compact since the temperature dependence of the dielectric constant in this temperature range differs significantly between ZrO2 and Al2O3. The reason for choosing the heating rate at 600° C. or above to the aforementioned range is that if the heating rate is less than 50° C./min, heat treatment is performed for a long time, which leads to a high production cost, whereas if the heating rate conversely exceeds 150° C./min, irregularities arise in the microstructure inside the sintered compact, which makes it difficult to produce a uniform, large sample.
The ZrO2—Al2O3-based ceramic sintered compact obtained by the method of the present invention comprising steps (A) and (B) described above is a Y2O3 partially stabilized ZrO2—Al2O3 having a molar ratio (mol %) of ZrO2 and Y2O3 of from 96.5:3.5 to 97.5:2.5 and a mass ratio (mass %) of ZrO2 containing Y2O3 and Al2O3 of from 85:15 to 75:25; the ZrO2—Al2O3 composite sintered compact containing tetragonal ZrO2 particles having a crystallite size of from 5 to 20 nm (preferably from 5.5 to 18 nm) as a main component; and a crystallite size of α-Al2O3 being not greater than 75 nm (preferably from 10 to 60 nm, and even more preferably from 15 to 50 nm). In addition, the relative density of this ZrO2—Al2O3-based ceramic sintered compact is not less than 99° %. With the method according to an embodiment of the present invention, it is possible to produce a ZrO2—Al2O3-based ceramic sintered compact having the physical properties described above, wherein the three-point bending strength is not less than 1.0 GPa; the fracture toughness value is not less than 6.0 MPa·m1/2; and the Vickers hardness HV is not less than 12.0 GPa.
With the production method according to an embodiment of the present invention comprising steps (A) and (B) described above, a dense ceramic having a tetragonal ZrO2 content of not less than approximately 90 vol % with respect to the zirconia phase is obtained from a Y2O3 partially stabilized ZrO2—Al2O3-based mixed powder or a solid solution powder prepared by simultaneously mixing Y2O3 and Al2O3, by uniformly dispersing fine Al2O3 microparticles into a ZrO2 matrix and further adding a stabilizer Y2O3 in a small amount of from 2.5 to 3.5 mol % with respect to ZrO2. As a result, the “transformation toughening mechanism” of ZrO2 easily manifests, and high toughness can be achieved. Therefore, this production method is suited for the low-cost production of a high-strength/toughness ceramic (ceramic having a bending strength σb≧1 GPa, a fracture toughness value KIC≧6 MPa·m1/2, and a Vickers hardness HV≧12 GPa).
EXAMPLES
The present invention will be described specifically hereinafter using examples, but the present invention is in no way limited to these examples. The ZrO2—Al2O3-based ceramics obtained in Examples and Comparative Examples contain from 1.3 to 2.5 wt. % of hafnium oxide with respect to zirconium oxide as an inevitable impurity.
Note that for each sintered compact produced in the following examples and the like, the bulk density (Dobs), XRD pattern, Vickers hardness (HV), fracture toughness value (KIC), the bending strength (σb), and SEM/TEM images were measured/photographed, and the characteristics of each compact were evaluated.
The bending strength σb is a value of the three-point bending strength measured under conditions with a span length of 8 mm and a cross-head feed rate of 0.5 mm/min. The fracture toughness value KIC is a value measured in accordance with the indentation (IF) method (K. Niihara et al., J. Master. Sci. Lett., 1, 13-16 (1982)), in which a square-based pyramid diamond indenter was forced into the ceramic surface at a load of 20 kg (196 N) for 15 s and the lengths of cracks generated at the four corners of the resulting indentation were evaluated.
Example 1
Production Example of the High-Strength/Toughness ZrO2—Al2O3-Based Ceramic with the Production Method According to an Embodiment of the Present Invention
a) Preparation of Raw Material Powder
First, a commercially available Y2O3 partially stabilized ZrO2-based powder (product containing 3 mol % Y2O3, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) produced by a coprecipitation process was prepared, and this Y2O3-containing ZrO2 and a commercially available Al2O powder (TM-D grade, manufactured by Taimei Chemicals Co., Ltd.) were weighed so that the mass ratio (mass %) was 80:20 and uniformly mixed using a ball mill to prepare a raw material powder.
b) Preparation of Y2O3-Containing ZrO2—Al2O3-Based Ceramic
After the raw material powder described above was subjected to preliminary sintering for 9 hours in air at 700° C. and was then subjected to preliminary sintering for 1 hour at 900° C. the raw material powder was granulated with an aqueous solution containing 3 mass % of polyvinyl alcohol (PVA). Next, the powder was graded (using a mesh with an opening size of 200 μm), and this was subjected to die molding (uniaxial pressure: 70 MPa). Next, cold isostatic press treatment was performed (245 MPa/3 min) to increase the density. The obtained compact was then dried (110° C./2 h) to remove water content in the PVA, and microwave sintering was performed in a nitrogen atmosphere at a sintering temperature of 1200° C., a sintering time of 60 min, and a heating rate of 10° C./min up to 600° C. and 100° C./min above 600° C. using a microwave sintering apparatus equipped with a 2.45 GHz microwave oscillator (3000 W output/completely water cooled) to produce a sintered compact.
The obtained sintered compact was a dense body having a sintering density of 5.44 g/cm3 and a relative density Dobj/Dx of 99.0%. The crystallite size calculated from an XRD pattern was 12.4 nm, 3.84 nm, and 47.3 nm for t-ZrO2, m-ZrO2, and α-Al2O3, respectively. As a result of measuring the mechanical characteristics of this sintered compact, the bending strength σb was 1.03 GPa, the Vickers hardness HV was 12.9 GPa, and the fracture toughness value KIC was 6.02 MPa·m1/2.
Example 2
The preparation of a raw material powder was the same as in a) of Example 1. A Y2O3-containing ZrO2—Al2O3-based ceramic was prepared in the same manner as in b) of Example 1 with the exception that the sintering temperature was set to 1250° C. The obtained sintered compact was a dense body having a sintering density of 5.44 g/cm3 and a relative density Dobs/Dx of 99.0%. The crystallite size calculated from an XRD pattern was 5.9 nm, 6.9 nm, and 15.8 nm for t-ZrO2, m-ZrO2, and α-Al2O3, respectively. As a result of measuring the mechanical characteristics of this sintered compact, the bending strength Ob was 1.26 GPa, the Vickers hardness HV was 13.1 GPa, and the fracture toughness value KIC was 6.03 MPa·m1/2.
Example 3
The preparation of a raw material powder was the same as in a) of Example 1. A Y2O3-containing ZrO2—Al2O3-based ceramic was prepared in the same manner as in b) of Example 1 with the exception that the sintering temperature was set to 1300° C. The obtained sintered compact was a dense body having a sintering density of 5.46 g/cm3 and a relative density Dobs/Dx of 99.3%. The crystallite size calculated from an XRD pattern was 17.7 nm, 9.25 nm, and 23.0 nm for t-ZrO2, m-ZrO2, and α-Al2O3, respectively. As a result of measuring the mechanical characteristics of this sintered compact, the bending strength σb was 1.41 GPa, the Vickers hardness HV was 15.7 GPa, and the fracture toughness value KIC was 6.90 MPa·m1/2.
Example 4
The preparation of a raw material powder was the same as in a) of Example 1. A Y2O3-containing ZrO2—Al2O3-based ceramic was prepared in the same manner as in b) of Example 1 with the exception that the sintering temperature was set to 1350° C. The obtained sintered compact was a dense body having a sintering density of 5.46 g/cm3 and a relative density Dobs/Dx of 99.3%. The crystallite size calculated from an XRD pattern was 13.0 nm, 4.29 nm, and 49.5 nm for t-ZrO2, m-ZrO2, and α-Al2O3, respectively. As a result of measuring the mechanical characteristics of this sintered compact, the bending strength σb was 1.54 GPa, the Vickers hardness HV was 15.7 GPa, and the fracture toughness value KIC was 6.41 MPa·m1/2.
Comparative Example 1
The preparation of a raw material powder was the same as in a) of Example 1. A Y2O3-containing ZrO2—Al2O3-based ceramic was prepared with an electric sintering furnace for the purpose of comparison with Examples 1 to 4. Sintering was performed using a commercially available electric sintering furnace in an argon atmosphere at a sintering temperature of 1200° C., a sintering time of 120 min, and a heating rate of 5° C./min. The obtained sintered compact had a sintering density of 4.15 g/cm3 and a relative density Dobs/Dx of 75.5%, and was not a dense body. The crystallite size calculated from an XRD pattern was 5.6 nm, 8.36 nm, and 48.7 nm for t-ZrO2, m-ZrO2, and α-Al2O3, respectively. As a result of measuring the mechanical characteristics of this sintered compact, the bending strength σb was 0.269 GPa, the Vickers hardness HV was 5.26 GPa, and the fracture toughness value KIC was 3.73 MPa·m1/2.
Comparative Example 2
The preparation of a raw material powder was the same as in a) of Example 1. A Y2O3-containing ZrO2—Al2O3-based ceramic was prepared in the same manner as in Comparative Example 1 with the exception that the sintering temperature of the electric sintering furnace was set to 1250° C. The obtained sintered compact had a sintering density of 4.76 g/cm3 and a relative density Dobs/Dx of 86.7% and was not a dense body. The crystallite size calculated from an XRD pattern was 32.9 n, 6.33 nm, and 9.9 nm for t-ZrO2, m-ZrO2, and α-Al2O3, respectively. As a result of measuring the mechanical characteristics of this sintered compact, the bending strength σb was 0.532 GPa, the Vickers hardness HV was 9.44 GPa, and the fracture toughness value KIC was 4.72 MPa·m1/2.
Comparative Example 3
The preparation of a raw material powder was the same as in a) of Example 1. A Y2O3-containing ZrO2—Al2O3-based ceramic was prepared in the same manner as in Comparative Example 1 with the exception that the sintering temperature of the electric sintering furnace was set to 1300° C. The obtained sintered compact had a sintering density of 5.27 g/cm3 and a relative density Dobs/Dx of 96.0%, indicating that the sintered body was dense but had a slightly low relative density. The crystallite size calculated from an XRD pattern was 34.5 nm, 41.3 nm, and 46.9 nm for t-ZrO2, m-ZrO2, and α-Al2O3, respectively. As a result of measuring the mechanical characteristics of this sintered compact, the bending strength σb was 0.557 GPa, the Vickers hardness HV was 13.8 GPa, and the fracture toughness value KIC was 5.29 MPa·m1/2.
Comparative Example 4
The preparation of a raw material powder was the same as in a) of Example 1. A Y2O3-containing ZrO2—Al2O3-based ceramic was prepared in the same manner as in Comparative Example 1 with the exception that the sintering temperature of the electric sintering furnace was set to 1350° C. The obtained sintered compact had a sintering density of 5.46 g/cm3 and a relative density Dobs/Dx of 99.3%, indicating that the sintered body was dense but had a slightly low relative density. The crystallite size calculated from an XRD pattern was 27.0 nm, 6.17 nm, and 41.7 nm for t-ZrO2, m-ZrO2, and α-Al2O3, respectively. As a result of measuring the mechanical characteristics of this sintered compact, the bending strength σb was 0.651 GPa, the Vickers hardness HV was 15.7 GPa, and the fracture toughness value KIC was 5.81 MPa·m1/2.
Comparative Example 5
The preparation of a raw material powder was the same as in a) of Example 1. A Y2O3-containing ZrO2—Al2O3-based ceramic was prepared by Pulsed Electric-Current Pressure Sintering (PECPS) for the purpose of comparison with Examples 1 to 4. Sintering was performed using a commercially available pulsed electric-current sintering apparatus (using SPS-510A manufactured by SPS Syntex (Ltd.)) in an argon gas atmosphere at a pressurization pressure of 50 MPa, a sintering temperature of 1200° C., a retention time of 10 min, and a heating rate of 70 to 80° C./min. The obtained sintered compact had a sintering density of 5.13 g/cm3 and a relative density Dobs/Dx of 93.4% and was not a dense body. The crystallite size calculated from an XRD pattern was 41.7 nm, 6.58 nm, and 53.7 nm for t-ZrO2, m-ZrO2, and α-Al2O3, respectively. As a result of measuring the mechanical characteristics of this sintered compact, the bending strength Ob was 0.276 GPa, the Vickers hardness HV was 14.0 GPa, and the fracture toughness value KIC was 4.86 MPa·m1/2.
Comparative Example 6
The preparation of a raw material powder was the same as in a) of Example 1. A Y2O3-containing ZrO2—Al2O3-based ceramic was prepared in the same manner as in Comparative Example 5 with the exception that the sintering temperature of Pulsed Electric-Current Pressure Sintering (PECPS) was set to 1250° C. for the purpose of comparison with Examples 1 to 4. The obtained sintered compact had a sintering density of 5.26 g/cm3 and a relative density Dobs/Dx of 95.7% and was not a dense body. The crystallite size calculated from an XRD pattern was 26.4 nm, 3.12 nm, and 37.1 nm for t-ZrO2, m-ZrO2, and α-Al2O3, respectively. As a result of measuring the mechanical characteristics of this sintered compact, the bending strength σb was 0.459 GPa, the Vickers hardness HV was 14.9 GPa, and the fracture toughness value KIC was 4.96 MPa·m1/2.
Comparative Example 7
The preparation of a raw material powder was the same as in a) of Example 1. A Y2O3-containing ZrO2—Al2O3-based ceramic was prepared in the same manner as in Comparative Example 5 with the exception that the sintering temperature of Pulsed Electric-Current Pressure Sintering (PECPS) was set to 1300° C. for the purpose of comparison with Examples 1 to 4. The obtained sintered compact was a dense body having a sintering density of 5.49 g/cm3 and a relative density Dobs/Dx of 99.9%. The crystallite size calculated from an XRD pattern was 34.2 nm, 14.70 nm, and 40.3 nm for t-ZrO2, m-ZrO2, and α-Al2O3, respectively. As a result of measuring the mechanical characteristics of this sintered compact, the bending strength σb was 0.973 GPa, the Vickers hardness HV was 15.1 GPa, and the fracture toughness value KIC was 5.88 MPa·m1/2.
Comparative Example 8
The preparation of a raw material powder was the same as in a) of Example 1. A Y2O3-containing ZrO2—Al2O3-based ceramic was prepared in the same manner as in Comparative Example 5 with the exception that the sintering temperature of Pulsed Electric-Current Pressure Sintering (PECPS) was set to 1350° C. for the purpose of comparison with Examples 1 to 4. The obtained sintered compact was a dense body having a sintering density of 5.44 g/cm3 and a relative density Dobs/Dx of 99.1%. The crystallite size calculated from an XRD pattern was 13.0 nm, 6.50 nm, and 97.0 nm for t-ZrO2, m-ZrO2, and α-Al2O3, respectively. As a result of measuring the mechanical characteristics of this sintered compact, the bending strength σb was 0.768 GPa, the Vickers hardness HV was 15.5 GPa, and the fracture toughness value KIC was 7.25 MPa·m1/2.
The characteristics of the present invention will be described in detail hereinafter using the drawings and tables.
Table 1 below summarizes the physical property values of the sintered compacts of Examples 1 to 4 and Comparative Examples 1 to 8.














TABLE 1










Crystallite
Crystallite
Crystallite




Sintering


size
size
size



Sintering
temperature
Dobs
Dobs/Dx
t-ZrO2
m-ZrO2
α-Al2O3



method
(° C.)
(g/cm3)
(g/cm3)
(nm)
(nm)
(nm)






















Example 1
Microwave
1200
5.44
99.0
12.4
3.84
47.3


Example 2
Microwave
1250
5.44
99.0
5.9
6.9
15.8


Example 3
Microwave
1300
5.46
99.3
17.7
9.25
23.0


Example 4
Microwave
1350
5.46
99.3
13.0
4.29
49.5


Comparative
Conventional
1200
4.15
75.5
5.6
8.36
48.7


Example 1









Comparative
Conventional
1250
4.76
86.7
32.9
6.33
9.9


Example 2









Comparative
Conventional
1300
5.27
96.0
34.5
41.3
46.9


Example 3









Comparative
Conventional
1350
5.46
99.3
27.0
6.17
41.7


Example 4









Comparative
PECPS
1200
5.13
93.4
41.7
6.58
53.7


Example 5









Comparative
PECPS
1250
5.26
95.7
26.4
3.12
37.1


Example 6









Comparative
PECPS
1300
5.49
99.9
34.2
14.70
40.3


Example 7









Comparative
PECPS
1350
5.44
99.1
13.0
6.50
97.0


Example 8












Related
FIG. 5
FIG. 9
FIG. 9
FIG. 9





to FIG. 5









From Table 1 above, only the ceramics of Examples 1 to 4 produced by microwave sintering simultaneously satisfied the sintering density condition of having a relative density Dobs/Dx of not less than 99.0% and having crystallite sizes of both t-ZrO and α-Al2O3 at this time of not greater than 25 nm and not greater than 75 nm, respectively at all of the sintering temperature ranges, and an increase in sintering density and the suppression of crystallite size growth were confirmed. In the ceramics of Comparative Examples 1 to 4 produced by the conventional method (with an atmosphere-controlled electric sintering furnace) and by PECPS, it was presumed that the results indicated different relationships between the sintering density and crystallite size due to the fact that the growth of crystallite size was accelerated by the heating method or the thermal history derived therefrom.
Table 2 below summarizes the structural characteristic values of the sintered compacts of Examples 1 to 4 and Comparative Examples 1 to 8.












TABLE 2







Sintering


KIC



Sintering
temperature 
σb
Hv
(MPa · 



method
(° C.)
(GPa)
(GPa)
m1/2)




















Example 1
Microwave
1200
1.01
12.9
6.02


Example 2
Microwave
1250
1.26
13.1
6.03


Example 3
Microwave
1300
1.41
15.7
6.90


Example 4
Microwave
1350
1.54
15.7
6.41


Comparative
Conventional
1200
0.269
5.26
3.73


Example 1







Comparative
Conventional
1250
0.532
9.44
4.72


Example 2







Comparative 
Conventional
1300
0.557
13.8
5.29


Example 3







Comparative 
Conventional
1350
0.651
15.7
5.81


Example 4







Comparative
PECPS
1200
0.276
14.0
4.86


Example 5







Comparative
PECPS
1250
0.459
14.9
4.96


Example 6







Comparative
PECPS
1300
0.973
15.1
5.88


Example 7







Comparative
PECPS
1350
0.768
15.5
7.25


Example 8










FIG. 6
FIG. 6
FIG. 6









From Table 2 above, only the ceramics of Examples 1 to 4 produced by microwave sintering yielded excellent structural characteristic values simultaneously satisfying a three-point bending strength σb of not less than 1.0 GPa and a fracture toughness value of 6.0 MPa·m1/2 at all of the sintering temperature ranges. The Vickers hardness HV for these samples was from 12.9 to 15.6 GPa. Although the reason for exhibiting excellent structural characteristics is not certain, it is conceivable that the results indicate that the increase in sintering density and the suppression of crystallite size growth that were apparent in Table 1 yielded harmonious functionality of ZrO2 and Al2O3 in contrast with the ceramics of Comparative Examples 1 to 4 produced by the conventional method (with an atmosphere-controlled electric sintering furnace) and by PECPS.
• Example of a Production Step for the High-Strength/Toughness ZrO2—Al2O3-Based Ceramic Sintered Compact Production Method According to an Embodiment of the Present Invention
FIG. 1 is a flowchart illustrating an example of each step in the high-strength/toughness ZrO2—Al2O3-based ceramic sintered compact production method according to an embodiment of the present invention using microwave sintering. The production conditions of each step used in the examples are listed, but the present invention is not limited to these conditions. Note that the sintering conditions for electric sintering and Pulsed Electric-Current Pressure Sintering (PECPS) used in the comparative examples are also listed in this flowchart.
• XRD Pattern Measurement Results
In FIG. 2, which the pattern with reference to “Starting substance” is an XRD pattern of a ZrO2(3Y)-20 mass % Al2O3 composite powder serving as a starting material prior to sintering; the pattern with reference to “Atmospheric sintering with a conventional electric furnace (1350° C./120 min/Ar)” is an XRD pattern of a ceramic produced by the conventional method, sintering with an ordinary electric sintering furnace with a controlled atmosphere; the pattern with reference to “PECPS (1350° C./10 min/50 MPa/Ar)” is an XRD pattern of a ceramic produced by PECPS; and the pattern with reference to Microwave sintering (1350° C./60 min/N2)” is an XRD pattern of a ceramic produced by microwave sintering.
It was confirmed from these XRD patterns that m-ZrO2 (monoclinic zirconia) in the starting material disappeared due to sintering, and that each of the sintered compacts comprised t-ZrO2 (tetragonal zirconia) and an α-Al2O3 phase.
• Comparison of SEM Images of Fractured Surface and Polished Surface. FIG. 3A to FIG. 3F illustrate scanning electron microscope (SEM) photographs of fracture surfaces for ZrO2(3Y)-20 mass % Al2O3 composite ceramics produced using each sintering method (sintering temperature of 1250° C. for FIG. 3A, FIG. 3B, and FIG. 3C, and sintering temperature of 1350° C. for FIG. 3D, FIG. 3E, and FIG. 3F). FIG. 4A to FIG. 4C illustrate SEM photographs of polished surfaces for ZrO2(3Y)-20 mass % Al2O3 ceramics produced at 1350° C. using each sintering method.
In the photographs of FIG. 4A to FIG. 4C, the black regions are areas where alumina particles are present. It can be seen from a comparison of these SEM photographs that the surface conditions of ceramics produced by microwave sintering differ from the surface conditions of ceramics produced by other sintering methods.
• Relative Density Measurement Results
FIG. 5 is a graph illustrating the relationship between the relative density of ZrO2(3Y)-20 mass % Al2O3 ceramics produced using each methods and sintering temperature and the relationship between relative density and crystal particle size and sintering temperature. It was confirmed from this graph that ceramics with a larger crystal particle size are obtained in the case of microwave sintering than in the case of other sintering methods, and that a dense sintered compact having a relative density of 99.0% can be produced even when the sintering temperature is 1200° C., which is approximately 150° C. lower than the temperature in a conventional sintering method.
• Measurement Results of Various Characteristics
FIG. 6 illustrates the relationships between the bending strength σb, Vickers hardness Hv, and fracture toughness value KIC of ZrO2(3Y)-20 mass % Al2O3 ceramics produced using each sintering method and the sintering temperature. In the case of microwave sintering, it was confirmed that the bending strength σb was greater (from 1.0 to 1.5 GPa) than in the case of other sintering methods, the Vickers hardness HV (12 GPa or higher) was equivalent to that of ceramics produced by Pulsed Electric-Current Pressure Sintering, and the fracture toughness value KIC is a large value (approximately 6 MPa·m1/2) even when the sintering temperature is from 1200 to 1250° C.
• Comparison of TEM Images of Fractured Surface
FIG. 7 illustrates transmission electron microscope (TEM) photographs of fracture surfaces of ZrO2(3Y)-20 mass % Al2O3 ceramics sintered at a sintering temperature of 1350° C. for 120 minutes in the case of sintering using the conventional electric sintering furnace with a controlled atmosphere, 10 minutes in the case of PECPS, and for 60 minutes in the case of microwave sintering. The photograph on the left is a photograph taken at a magnification of 20 k; the photograph in the center is a photograph taken at a magnification of 100 k; and the photograph on the right is a photograph taken at a magnification of 600 k (here, “k” refers to 1,000 times).
In these TEM images, the regions that appear white are Al2O3, and the regions that appear black are ZrO2. From a comparison of the TEM images at a magnification of 600 k, striped structures in the vertical direction are observed at the interfaces of the ZrO2 and Al2O3 particles of the ceramics produced by microwave sintering, and it is considered that thin layers that cannot be detected by X-ray diffraction are present at the interfaces.
• Comparison of EDS Images of Microstructures
FIG. 8A to FIG. 8C illustrate SEM photographs of microstructures of ZrO2(3Y)-20 mass % Al2O3 ceramics sintered at 1350° C. using each sintering method. The photographs are, in order from left to right, an ordinary transmission electron microscope photograph, an image indicating the positions where Al is present, an image indicating the positions where oxygen O is present, and an image indicating the positions where Zr is present.
From these EDS images, the aggregation of Al2O3 particles is particularly observed in the case of ceramics produced by sintering with the conventional electric sintering furnace with a controlled atmosphere (FIG. 8A), and the aggregation and particle growth of Al2O3 particles are observed in the case of ceramics produced by PECPS (FIG. 8B). In contrast, an image in which the Al2O3 particles are well dispersed is observed in the case of ceramics produced by microwave sintering (FIG. 8C).
Table 3 below summarizes the lattice constants and crystallite sizes of the tetragonal t-ZrO2 phase, the monoclinic m-ZrO2 phase, and the α-Al2O3 phase determined by X-ray diffraction measurements for the ceramics produced using each sintering method at 1350° C.







TABLE 3







Lattice constants and crystallite size of t- and m-ZrO2,


and α-Al2O3 phases in the composites sintered


at 1350° C. using each sintering method



















Crystallite


Sintering





size


conditions

a (nm)
b (nm)
c (nm)
β (°)
(nm)
















Conventional
t-ZrO2
0.361
0.361
0.518
90.0
27.0



m-ZrO2
0.521
0.596
0.485
89.0
6.17



α-Al2O3
0.476
0.476
1.30
90.0
41.7


PECPS
t-ZrO2
0.361
0.361
0.518
90.0
13.0



m-ZrO2
0.512
0.523
0.517
104
6.50



α-Al2O3
0.476
0.476
1.30
90.0
97.0


Microwave
t-ZrO2
0.361
0.361
0.517
90.0
13.0



m-ZrO2
0.577
0.538
0.513
96.4
4.29



α-Al2O3
0.475
0.475
1.30
90.0
49.5









From Table 3 above, the interaxial angles β were constant for t-ZrO2 and α-Al2O3 because t-ZrOz and α-Al2O3 are tetragonal and hexagonal, respectively. But differences in interaxial angles β were observed for the monoclinic m-ZrO2. In addition, it was observed that ceramics produced by microwave sintering exhibit a smaller ZrO2 crystallite size than ceramics produced by sintering with the conventional electric sintering furnace with a controlled atmosphere and by PECPS and exhibit a smaller Al2O3 crystallite size than ceramics produced by PECPS.
• Changes in the Crystallite Size and Crystal Particle Size of the t-ZrO2 Phase and the α-Al2O3 Phase when the Sintering Temperature is Varied
FIG. 9 is a graph illustrating the relationships between the “crystallite size” of a t-ZrO2 phase and an α-Al2O3 phase and “grain size” in a ZrO2(3Y)-20 mass % Al2O3 ceramic produced at 1200 to 1350° C. using each sintering method.
From FIG. 9, it was confirmed that a tendency is observed in which the “crystallite size” of the t-ZrO2 phase and the α-Al2O3 phase tends to decrease in the sintering temperature range of from 1200 to 1350° C. for ceramics produced by microwave sintering in comparison to ceramics produced by sintering with an ordinary electric sintering furnace with a controlled atmosphere and by PECPS, while the “grain size” increases. In particular, a characteristic feature is that in microwave sintered compacts, the crystallite size of the t-ZrO2 phase, which influences the strength σb and the fracture toughness value KIC of zirconia-based ceramics, is as small as 5 to 20 nm. It has been reported that the mechanical characteristics of polycrystals is inversely proportional to the grain size Gs if the relative density is the same. However, in zirconia-based ceramics related to the present invention, it was discovered for the first time that the strength and toughness are dependent not on the grain size but on the size of the crystallites constituting the crystal particles—that is, the “crystallite size”—are enhanced as the crystallite size decreases.
Table 4 below summarizes the values of the volume ratio of the t/m-ZrO2 phases, the relative density Dobs/Dx, the fracture toughness value KIC, the Vickers hardness HV, and the bending strength σb of the ceramics sintered at 1350° C. using each sintering method.










TABLE 4






Atmospheric
PECPS, 
Microwave



furnace sintering
Sintered at 
Sintered at



Sintered at
1350° C./10
at 1350° C./



1350° C./120 min
min/50 MPa
60 min







t/m volume ratio
93.3/6.7 (%)
99.5/0.5 (%)
96.6/3.4 (%)


Dobs, Dobs/Dx
5.46 Mg/m3
5.44 Mg/m3
5.46 Mg/m3 


Fracture toughness
(99.3%)
(99.1%)
(99.3%)


value KIC
5.81 MPa · m1/2
7.25 MPa · m1/2
6.41 MPa · m1/2


Vickers hardness Hv
15.7 GPa
15.5 GPa
15.7 GPa


Bending strength σb
0.651 GPa
0.768 GPa
1.54 GPa









The results of Table 4 above indicate that sintering yielded good results in the relative density (99.1 to 99.3%), the Vickers hardness HV (15.5 to 15.7 GPa), the fracture toughness value KIC (5.81 to 7.25 MPa·m1/2) in each sintering method. In particular, the production method according to an embodiment of the present invention using microwave sintering is excellent in that a ZrO2—Al2O3-based ceramic having a bending strength Ob greater than approximately twice that of a ceramic produced by sintering using a conventional electric sintering furnace with a controlled atmosphere or PECPS is obtained.
In addition, with regard to the point of raw material cost, whereas the cost per 1 g of raw material is more than several thousand yen for a commercially available yttria partially stabilized zirconia-alumina powder produced with a sol-gel method, a mixed powder of a typical microparticulate ZrO2(3Y) and Al2O3 or a powder prepared using a coprecipitation process used in the production method of the present invention can be produced at a low cost of less than approximately 1/100 the cost described above, so the production method according to an embodiment of the present invention using microwave sintering is a method with outstanding economic efficiency. Further, microwave sintering, which is pressureless sintering, yields high shape-imparting properties, and a ceramic produced by an embodiment according to the present invention also has the merit that it can be easily developed to other applications together with the high mechanical characteristics thereof.
INDUSTRIAL APPLICABILITY
By using the production method according to an embodiment of the present invention, a high-strength/toughness ZrO2—Al2O3-based ceramic having a bending strength σb≧1 GPa, a fracture toughness value KIC≧6 MPa·m1/2, and a Vickers hardness HV≧12 GPa can be produced. Such a high-strength/toughness ZrO2—Al2O3-based ceramic can be used in various applications in which these characteristics are required, such as ceramic machine parts, ceramics for living organisms (dental implants, artificial joints, and artificial bones), and the like, for example.

## Claims

1. A ZrO2—Al2O3-based ceramic sintered compact comprising a Y2O3 partially stabilized ZrO2—Al2O3 composite sintered compact having a molar ratio (mol %) of zirconia (ZrO2) and yttria (Y2O3) of from 96.5:3.5 to 97.5:2.5 and a mass ratio (mass %) of zirconia containing yttria and alumina (Al2O3) of from 85:15 to 75:25; wherein the ZrO2—Al2O3 composite sintered compact contains tetragonal ZrO2 particles having a crystallite size of from 5 to 20 nm as a main component, a crystallite size of α-Al2O3 is not greater than 75 nm; and the sintered compact has a relative density of not less than 99%.

2. The ZrO2—Al2O3-based ceramic sintered compact according to claim 1, wherein a three-point bending strength is not less than 1.0 GPa; a fracture toughness is not less than 6.0 MPa·m1/2; and a Vickers hardness HV is not less than 12.0 GPa.

3. A production method for a ZrO2—Al2O3-based ceramic sintered compact described in claim 1, comprising the following steps:
(A): preparing a Y2O3 partially stabilized ZrO2—Al2O3-based powder having a molar ratio (mol %) of zirconia (ZrO2) and yttria (Y2O3) of from 96.5:3.5 to 97.5:2.5 and a mass ratio (mass %) of zirconia containing yttria and alumina (Al2O3) of from 85:15 to 75:25; and
(B): producing a high-density compact by molding the Y2O3 partially stabilized ZrO2—Al2O3-based powder by cold isostatic pressing and then performing microwave sintering on the compact in an inert gas atmosphere at 1200 to 1400° C. for 45 to 90 min.

4. The method according to claim 3, wherein a heating rate during performing microwave sintering in (B) is from 5 to 20° C./min up to 600° C. and from 50 to 150° C./min at 600° C. or higher.

5. The method according to claim 3, wherein a mixture of a Y2O3 partially stabilized ZrO2 and an Al2O3 powder or a solid solution powder produced by a coprecipitation process is used as the Y2O3 partially stabilized ZrO2—Al2O3-based powder.

6. A production method for a ZrO2—Al2O3-based ceramic sintered compact described in claim 2, comprising the following steps:
(A): preparing a Y2O3 partially stabilized ZrO2—Al2O3-based powder having a molar ratio (mol %) of zirconia (ZrO2) and yttria (Y2O3) of from 96.5:3.5 to 97.5:2.5 and a mass ratio (mass %) of zirconia containing yttria and alumina (Al2O3) of from 85:15 to 75:25; and
(B): producing a high-density compact by molding the Y2O3 partially stabilized ZrO2—Al2O3-based powder by cold isostatic pressing and then performing microwave sintering on the compact in an inert gas atmosphere at 1200 to 1400° C. for 45 to 90 min.

7. The method according to claim 4, wherein a mixture of a Y2O3 partially stabilized ZrO2 and an Al2O3 powder or a solid solution powder produced by a coprecipitation process is used as the Y2O3 partially stabilized ZrO2—Al2O3-based powder.