High toughness sintered bodies

Abstract

A high toughness sintered body is described, consisting essentially of from 40 to 99.5% by weight of Component A, and 0.5 to 60% by weight of Component B, wherein the mean grain size of the sintered body is 3 microns or less, and Components A and B are as follows:Component A: ZrO.sub.2 containing a stabilizer, such as Y.sub.2 O.sub.3, CaO, and MgO, in which the fraction of the tetragonal and cubic ZrO.sub.2 constitutes at least 90% by weight, and the ratio of the tetragonal ZrO.sub.2 to the cubic ZrO.sub.2 is at least 1/3; andComponent B: at least one of Al.sub.2 O.sub.3 and TiN, with impurities being 3% by weight or less of SiO.sub.2, 0.5% by weight or less of Fe.sub.2 O.sub.3, and 0.5% by weight or less of TiO.sub.2, provided that the total amount is 3% by weight or less.

Description

FIELD OF THE INVENTION

The present invention relates to high toughness sintered bodies comprising at least one of ZrO.sub.2 and HfO.sub.2, at least one of Al.sub.2 O.sub.3 and TiN, etc.

BACKGROUND OF THE INVENTION

Production of ceramic materials having improved flexural strength has been the subject of research by many investigators, because poor flexural strength is a most serious disadvantage of ceramic materials, and if ceramic materials having improved flexural strength can be developed, they can be effectively used in the fabrication of cutting tools, as synthetic bone materials, as parts for internal combustion engines, and so forth.

For example, Japanese Patent Application (OPI) No. 140762/80 (the term "OPI" as used herein refers to a "published unexamined Japanese patent application") discloses "zirconia-base cutting tool materials" comprising ZrO.sub.2 partially stabilized with oxides of Y, Ca, Mg, etc., in which the total fraction of tetragonal and cubic ZrO.sub.2 is from 60 to 95% by weight. J. S. Reed et al., Ceramic Bulletin, Vol. 55, page 717 (1976) describes that high strength ZrO.sub.2 sintered bodies can be obtained by sintering fine powdered ZrO.sub.2 which is prepared by co-precipitating a mixture of ZrOCl.sub.2 and YCl.sub.3, calcining the thus-formed powder, and stabilizing with Y.sub.2 O.sub.3.

These ceramic materials, however, are not completely satisfactory in strength, and it has, therefore, been desired to further increase the strength, because it is expected that such improved ceramic materials would have a wider variety of uses.

SUMMARY OF THE INVENTION

As a result of extensive investigations to further increase the strength of such ceramic materials, it has been found that when Al.sub.2 O.sub.3, TiN, or a combination thereof is added to form a solid solution in combination with ZrO.sub.2 ("ZrO.sub.2 " as used herein generally is intended also to refer to ZrO.sub.2 wherein HfO.sub.2 is substituted in part or in whole therefor) or is dispersed in ZrO.sub.2, the transformation temperature of ZrO.sub.2 between the tetragonal ZrO.sub.2 and the monoclinic ZrO.sub.2 is lowered and grain growth of ZrO.sub.2 is prevented, which increases the fraction of tetragonal ZrO.sub.2, the sliding resistance among ZrO.sub.2 grains in the grain boundaries, and hardness, and, furthermore, increases the high temperature (up to 1200.degree. C.) strength to as high as about 2 times the strength of ZrO.sub.2 alone.

The present invention, therefore, relates to a high toughness sintered body consisting essentially of from 40 to 99.5% by weight Component A and from 0.5 to 60% by weight Component B, wherein the mean grain size of the sintered body is 3 microns or less, wherein:

Component A is partially stabilized ZrO.sub.2 (containing, e.g., a stabilizer such as Y.sub.2 O.sub.3, CaO and MgO) in which the fraction of the tetragonal and cubic ZrO.sub.2 are at least 90% by weight, and the ratio of the tetragonal ZrO.sub.2 to the cubic ZrO.sub.2 is at least 1/3; and

Component B is at least one of Al.sub.2 O.sub.3 and TiN, with impurities being 3% by weight or less SiO.sub.2, 0.5% by weight or less Fe.sub.2 O.sub.3, and 0.5% by weight or less TiO.sub.2, provided that the total amount of impurities is 3% by weight or less (based on the total weight).

According to a preferred embodiment of the invention, it has been found that when a co-precipitation method is employed to prepare a raw material consisting essentially of the components of ZrO.sub.2 (and/or HfO.sub.2), stabilizer, and Al.sub.2 O.sub.3 (and/or TiN) the resulting raw materials are dispersed more ideally, and by using the resulting raw materials, a sintered boby can be obtained which has a uniform structure comprising fine grains, contains almost no micropores, and which has a strength as high as about 150 kg/mm.sup.2 that could not be expected from conventional ceramic materials.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the high temperature strength of sintered bodies described in Example 1 and of a comparative specimen (No. R), i.e., commercially available partially stabilized zirconia sintered body manufactured by Corning Corp.

FIG. 2 shows the high temperature strength of sintered bodies described in Example 2.

FIG. 3 shows the high temperature strength of sintered bodies described in Example 3 and of the above-described comparative specimen (No. R).

FIG. 4 shows the high temperature strength of sintered bodies described in Example 4.

FIG. 5 shows the high temperature strength of sintered bodies described in Example 5 and of the above-described comparative specimen (No. R).

DETAILED DESCRIPTION OF THE INVENTION

In the high toughness sintered body of the invention, if the Al.sub.2 O.sub.3 or TiN content is less than 0.5% by weight, the effect of the addition of Al.sub.2 O.sub.3 or TiN is poor respectively, whereas if it is more than 60% by weight, ZrO.sub.2 content is too low to give effect of strengthening and toughening due to ZrO.sub.2 phase transformation.

Furthermore, the total fraction of the tetragonal ZrO.sub.2 and the cubic ZrO.sub.2 in the ZrO.sub.2 should be at least 90% by weight thereof. When the fraction is less than 90% by weight, the toughness of the resulting sintered body is poor. It is also necessary that the ratio of the tetragonal ZrO.sub.2 to the cubic ZrO.sub.2 be at least 1/3. If the ratio is less than 1/3, the resulting sintered body has poor toughness. It is further required for the mean grain size of the sintered body to be 3 microns or less. If the mean grain size is more than 3 microns, the transformation from the tetragonal ZrO.sub.2 to the monoclinic ZrO.sub.2 will occur, resulting in a reduction in toughness.

The tolerable amounts of impurities are up to 3% by weight in the case of SiO.sub.2 and up to 0.5% by weight each in the case of Fe.sub.2 O.sub.3 and TiO.sub.2, provided that the total amount of such impurities is 3% by weight or less. If the amount of each impurity or the total amount of impurities is more than the above-specified values, sintering properties are reduced, and only a sintered body having poor toughness can be obtained.

The same characteristics as above can also be obtained when part or all of the ZrO.sub.2 is replaced by HfO.sub.2.

The following examples are given to illustrate the invention in greater detail.

EXAMPLE 1

To a monoclinic ZrO.sub.2 having the characteristics shown in Table 1 were added Y.sub.2 O.sub.3, CaO, or MgO as a stabilizer in the proportions shown in Table 2, and then fine particles of Al.sub.2 O.sub.3 having a mean particle size of 0.1 micron and a purity of 99.9% were added in proportions as shown in Table 2. The ingredients were then wet-mixed, and the resulting mixture was dried, powdered, press-molded, and sintered in an electric furnace in the air at 1,400.degree. to 1,650.degree. C. for 1 hour. After sintering, the thus-obtained sintered body was cut and ground to form a specimen of 4.times.8.times.25 mm. In this way, a series of specimens were produced. The phase composition and properties obtained from these specimens are shown in Table 2. In all the specimens, the mean grain size was less than 3 microns. When the sintering temperature was increased to higher temperatures than those shown in Table 2, the mean grain size was larger than 3 microns, and the strength was reduced.

As is shown clearly from Table 2, the addition of Al.sub.2 O.sub.3 inhibits the transformation from the tetragonal ZrO.sub.2 to the monoclinic ZrO.sub.2 and increases the fraction of the tetragonal ZrO.sub.2, improving the strength and toughness of the resulting sintered body. The hardness and high temperature flexural strength of some specimens were also measured. The results are shown in Table 3 and FIG. 1. It can be seen from the results that the hardness of the sintered body increased with increasing Al.sub.2 O.sub.3 content, for example, the hardness of specimen No. 33 with 60% Al.sub.2 O.sub.3 content was almost equal to that of Al.sub.2 O.sub.3 ceramics, and that the high temperature strength is markedly improved compared with the comparative partially stabilized zirconia sintered body which is commercially available from Corning Corp., U.S.A. (Specimen No. R).

TABLE 1______________________________________Crystal System MonoclinicSpecific Surface Area 25 m.sup.2 /gChemical Analytical ValuesZrO.sub.2 (incl. HfO.sub.2) 99% or more (containing 3 to 5% HfO.sub.2)SiO.sub.2 0.5%CaO 0.06%Fe.sub.2 O.sub.3 0.1%TiO.sub.2 0.25%______________________________________ TABLE 2__________________________________________________________________________Composition Stabilizer Crystal System of ZrO.sub.2 for ZrO.sub.2 Sintering Flexural Mono- Tetra-Specimen Al.sub.2 O.sub.3 Amount Temperature Density Strength K.sub.IC clinic gonal CubicNo. (wt %) Type (mol %) (.degree.C.) (g/cm.sup.3) (kg/mm.sup.2) (kg/mm.sup.3/2) (wt %) (wt %) (wt %) Remarks__________________________________________________________________________ 1 0.1 Y.sub.2 O.sub.3 4 1,600 5.72 35.1 9.3 24 41 35 Comparison 2 0.5 " " " 5.80 70.5 21.0 9 58 33 Present Invention 3 1.5 " " " 5.83 72.4 22.5 4 64 32 Present Invention 4 3 " 1 1,500 * -- -- 95 0 5 Comparison 5 " " 1.5 1,400 5.76 35.7 18.0 43 49 8 Comparison 6 " " 2 1,500 5.97 95.9 44.9 5 83 12 Present Invention 7 " " 2.5 " 5.95 91.7 37.8 4 77 19 Present Invention 8 " " 3 1,600 5.94 82.3 30.2 3 73 24 Present Invention 9 " " 4 " 5.88 84.1 23.8 1 67 32 Present Invention10 " " 6 " 5.75 44.6 15.0 0 28 72 Present Invention11 " " 8 " 5.67 31.2 13.0 0 0 100 Comparison12 " MgO 7 1,500 5.75 70.0 21.0 3 61 36 Present Invention13 " CaO 6 " 5.78 65.0 19.0 4 55 41 Present Invention14 10 Y.sub.2 O.sub.3 1 1,500 * -- -- 96 0 4 Comparison15 " " 2 " 5.71 99.4 38.8 4 85 11 Present Invention16 " " 3 " 5.69 87.2 32.5 2 76 22 Present Invention17 " " 4 " 5.64 85.3 30.0 1 70 29 Present Invention18 " MgO 7 " 5.53 72.5 29.1 0 68 32 Present Invention19 " CaO 6 " 5.55 67.4 27.3 0 63 37 Present Invention20 20 Y.sub.2 O.sub.3 1 " 5.45 102.2 33.6 9 87 4 Present Invention21 " " 2 " 5.43 110.8 35.0 0 90 10 Present Invention22 " " 3 " 5.41 95.1 30.9 0 81 19 Present Invention23 " " 4 " 5.37 93.0 28.2 0 74 26 Present Invention24 " MgO 7 " 5.28 79.1 27.3 0 71 29 Present Invention25 " CaO 6 " 5.30 73.5 26.2 0 67 33 Present Invention26 40 Y.sub.2 O.sub.3 1 " 4.97 107.3 27.7 0 97 3 Present Invention27 " " 2 " 4.96 121.3 26.8 0 93 7 Present Invention28 " " 3 " 4.94 106.4 25.5 0 86 14 Present Invention29 " " 4 " 4.92 104.1 24.5 0 81 19 Present Invention30 " MgO 7 " 4.87 88.5 23.9 0 78 22 Present Invention31 " CaO 6 " 4.88 82.2 23.4 0 75 25 Present Invention32 60 Y.sub.2 O.sub.3 1 1,600 4.61 82.5 22.0 0 97 3 Present Invention33 " " 2 " 4.59 75.0 21.8 0 94 6 Present Invention34 " " 3 " 4.59 65.8 21.2 0 88 12 Present Invention35 " " 4 " 4.58 64.4 20.9 0 84 16 Present Invention36 " MgO 7 " 4.55 54.7 20.7 0 82 18 Present Invention37 " CaO 6 " 4.55 50.8 20.6 0 79 21 Present Invention38 70 Y.sub.2 O.sub.3 2 " 4.43 43.3 11.5 0 94 6 Comparison__________________________________________________________________________ *disintegration TABLE 3______________________________________ Specimen No. 6 15 21 27 33______________________________________Amount of Al.sub.2 O.sub.3 (wt %) 3 10 20 40 60Hardness 83.5 84.0 85.1 86.5 87.7______________________________________Note:Measurement of Physical Properties(1) The flexural strength was measured according to JISB4104-1970, and an average value of five specimens isindicated.(2) The fracture toughness was measured according toASTM Special Technical Publication No. 410; i.e., aspecimen having a width of 4 mm, a thickness of 5 mm,and a length of 25 mm was provided with a notch havinga depth of 0.5 mm and a width of 0.15 mm, and wasmeasured by a three-point bending test with a span as20 mm. An average value of five specimens is indicated.(3) The hardness was measured by the use of a RockwellSuper Fischal hardness tester at a load of 45 kg.(4) The crystal system was analyzed by X-ray diffractionusing Geiger Flex Model RAD-.gamma.A manufactured by RigakuDenki Co., Ltd. In the first place, by X-ray diffractionof a specimen which had been mirror-polished with a 15.mu.diamond paste, the integrated strength Im of each of the(11-1) plane and the (111) plane of monoclinic ZrO.sub.2, theintegrated strength It of the (111) plane of tetragonalZrO.sub.2, and the integrated strength Ic of the (111) planeof cubic ZrO.sub.2 were measured, and the fraction of mono-clinic ZrO.sub.2 was determined by the ratio of Im/(Im + It + Ic).Then the sintered body was ground until all particlescould pass through a 325 mesh screen and the groundparticles were analyzed by X-ray diffraction under thesame conditions as above to measure the integratedstrength I'm of monoclinic ZrO.sub.2 and the integratedstrength I'c of cubic ZrO.sub.2. In this case, it isconsidered that the residual tetragonal ZrO.sub.2 in thesintered body is subjected to mechanical stress by theabove-described pulverization and undergoes a transforma-tion into monoclinic ZrO.sub.2. Therefore, the fraction ofcubic ZrO.sub.2 is determined by the ratio of I'c/(I'm + I'c)and then the fraction of tetragonal ZrO.sub.2 is determined.

EXAMPLE 2

An aqueous solution of zirconium oxychloride and an aqueous solution of yttrium chloride were mixed, co-precipitated, and calcined at 800.degree. C. to prepare a powder consisting of ZrO.sub.2 and Y.sub.2 O.sub.3. The characteristics of the powder are shown in Table 4. To the co-precipitated powder was added Al.sub.2 O.sub.3 powder having a mean particle size of 0.1 .mu.m and a purity of 99.9% in the proportions shown in Table 5. Using the powder, a sintered body was produced in the same manner as in Example 1. The results are shown in Table 5. The high temperature strength was measured in the same manner as in Example 1, and the results are shown in FIG. 2. It can be seen from the results that even when the co-precipitated ZrO.sub.2 powder is used, the addition of Al.sub.2 O.sub.3 provides a great effect, as was the case in Example 1.

TABLE 4______________________________________Amount of Y.sub.2 O.sub.3 2 mol % 3 mol %Crystal System Tetragonal TetragonalSpecific Surface 32 m.sup.2 /g 34 m.sup.2 /gAreaChemical AnalyticalValuesZrO.sub.2 (incl. HfO.sub.2) 95% (containing 93.7% (containing 3 to 5% HfO.sub.2) 3 to 5% HfO.sub.2)Y.sub.2 O.sub.3 4.04% 5.30%CaO 0.09% 0.06%Na.sub.2 O 0.05% 0.05%______________________________________ TABLE 5__________________________________________________________________________Composition Stabilizer Crystal System of ZrO.sub.2 for ZrO.sub.2 Sintering Flexural Mono- Tetra-Specimen Al.sub.2 O.sub.3 Amount Temperature Density Strength K.sub.IC clinic gonal CubicNo. (wt %) Type (mol %) (.degree.C.) (g/cm.sup.3) (kg/mm.sup.2) (kg/mm.sup.3/2) (wt %) (wt %) (wt Remarks__________________________________________________________________________101 20 Y.sub.2 O.sub.3 2 1,500 5.51 112.5 35.4 0 94 6 Present Invention102 " " 3 " 5.48 96.7 31.2 0 87 13 Present Invention103 40 " 2 " 5.03 124.0 27.3 0 97 3 Present Invention104 " " 3 " 5.01 108.1 25.9 0 90 10 Present Invention105 60 " 2 1,600 4.63 78.3 22.1 0 97 3 Present Invention106 " " 3 " 4.62 70.1 21.5 0 91 9 Present Invention__________________________________________________________________________

EXAMPLE 3

To a monoclinic ZrO.sub.2 having the characteristics shown in Table 1 above were added Y.sub.2 O.sub.3, CaO, or MgO as a stabilizer in the proportions shown in Table 6, and then fine particles of TiN having a mean particle size of 0.1 micron and a purity of 99.9% were added in proportions as shown in Table 6. The ingredients were then wet-mixed, and the resulting mixture was dried, powdered, press-molded, and sintered in an electric furnace in N.sub.2 atmosphere at 1,400.degree. to 1,650.degree. C. for 1 hour. After sintering, the thus-obtained sintered body was cut and ground to form a specimen of 4.times.8.times.25 mm. In this way, a series of specimens were produced. The phase composition and properties obtained from these specimens are shown in Table 6. In all the specimens, the mean grain size was less than 3 microns. When the sintering temperature was increased to higher temperature than those shown in Table 6, the mean grain size was larger than 3 microns, and the strength was reduced.

As is shown clearly from Table 6, the addition of TiN inhibits the transformation from the tetragonal ZrO.sub.2 to the monoclinic ZrO.sub.2 and increases the fraction of the tetragonal ZrO.sub.2, improving the strength and toughness of the resulting sintered body. The hardness and high temperature flexural strength of some specimens were also measured. The results are shown in Table 7 and FIG. 3. It can be seen from the results that the addition of TiN greatly increases the hardness and strength, and in particular, the high temperature strength is markedly improved compared with the comparative partially stabilized zirconia sintered body which is commercially available from Corning Corp., U.S.A. (Specimen No. R).

TABLE 6__________________________________________________________________________Composition Stabilizer Crystal System of ZrO.sub.2 for ZrO.sub.2 Sintering Flexural Mono- Tetra-Specimen TiN Amount Temperature Density Strength K.sub.IC clinic gonal CubicNo. (wt %) Type (mol %) (.degree.C.) (g/cm.sup.3) (kg/mm.sup.2) (kg/mm.sup.3/2) (wt %) (wt %) (wt %) Remarks__________________________________________________________________________T1 0.1 Y.sub.2 O.sub.3 4 1,600 5.74 33.4 10.8 27 38 35 ComparisonT2 0.5 " " " 5.83 67.0 29.5 10 57 33 Present InventionT3 1.5 " " " 5.86 68.8 33.8 6 63 31 Present InventionT4 3 " 1 1,400 * -- -- 96 0 4 ComparisonT5 " " 1.5 " 5.79 33.9 19.3 44 47 9 ComparisonT6 " " 2 1,500 6.01 91.1 45.3 7 82 11 Present InventionT7 " " 2.5 " 5.99 87.1 42.4 5 76 19 Present InventionT8 " " 3 1,600 5.97 79.9 41.5 4 73 23 Present InventionT9 " " 4 " 5.91 78.2 38.7 2 64 34 Present InventionT10 " " 6 " 5.79 42.4 16.1 0 25 75 Present InventionT11 " " 8 " 5.70 29.6 15.3 0 0 100 ComparisonT12 " MgO 7 1,500 5.78 66.5 37.1 4 59 37 Present InventionT13 " CaO 6 " 5.80 61.8 35.2 5 53 42 Present InventionT14 10 Y.sub.2 O.sub.3 1 " * -- -- 97 0 3 ComparisonT15 " " 2 " 5.95 94.4 43.2 6 85 9 Present InventionT16 " " 3 " 5.91 82.8 40.7 3 76 21 Present InventionT17 " " 4 " 5.86 81.0 39.1 1 70 29 Present InventionT18 " MgO 7 " 5.74 68.9 38.7 0 69 31 Present InventionT19 " CaO 6 " 5.76 64.1 37.6 0 65 35 Present InventionT20 20 Y.sub.2 O.sub.3 1 " 5.91 97.1 41.4 9 88 3 Present InventionT21 " " 2 " 5.89 105.3 41.1 5 87 8 Present InventionT22 " " 3 " 5.85 90.5 39.7 0 81 19 Present InventionT23 " " 4 " 5.81 88.4 37.7 0 73 27 Present InventionT24 " MgO 7 " 5.71 75.1 36.8 0 70 30 Present InventionT25 " CaO 6 " 5.72 69.8 35.8 0 66 34 Present InventionT26 40 Y.sub.2 O.sub.3 1 " 5.71 101.4 37.8 0 98 2 Present InventionT27 " - 2 " 5.69 115.3 36.9 0 94 6 Present InventionT28 " " 3 " 5.67 101.2 35.5 0 87 13 Present InventionT29 " " 4 " 5.64 98.9 33.9 0 80 20 Present InventionT30 " MgO 7 " 5.56 84.1 33.7 0 79 21 Present InventionT31 " CaO 6 " 5.57 78.2 32.4 0 74 26 Present InventionT32 60 Y.sub.2 O.sub.3 1 1,600 5.59 78.4 29.7 0 98 2 Present InventionT33 " " 2 " 5.58 72.3 28.3 0 93 7 Present InventionT34 " " 3 " 5.56 62.9 27.1 0 89 11 Present InventionT35 " " 4 " 5.54 62.3 25.6 0 85 15 Present InventionT36 " MgO 7 " 5.49 52.1 23.7 0 81 19 Present InventionT37 " CaO 6 " 5.50 49.5 22.9 0 80 20 Present InventionT38 70 Y.sub.2 O.sub.3 2 " 5.52 41.1 13.2 0 94 6 ComparisonT39 " MgO 7 " 5.46 39.6 12.6 0 84 16 ComparisonT40 " CaO 6 " 5.47 38.4 10.8 0 79 21 Comparison__________________________________________________________________________ *disintegration TABLE 7______________________________________ Specimen No. T6 T15 T21 T27 T33______________________________________Amount of TiN (wt %) 3 10 20 40 60Hardness 83.4 83.8 84.5 85.7 86.1______________________________________

EXAMPLE 4

An aqueous solution of zirconium oxychloride and an aqueous solution of yttrium chloride were mixed, co-precipitated, and calcined at 800.degree. C. to prepare a powder consisting of ZrO.sub.2 and Y.sub.2 O.sub.3. The characteristics of the powder are shown above in Table 4. To the co-precipitated powder was added TiN powder having a mean particle size of 0.1 .mu.m and a purity of 99.9% in the proportions shown in Table 8. Using the powder, a sintered body was produced in the same manner as in Example 3. The results are shown in Table 8. The high temperature strength was measured in the same manner as in Example 1, and the results are shown in FIG. 4. It can be seen from the results that even when the co-precipitated ZrO.sub.2 powder is used, the addition of TiN provides a great effect, as was the case with Example 3.

TABLE 8__________________________________________________________________________Composition Stabilizer Crystal System of ZrO.sub.2 for ZrO.sub.2 Sintering Flexural Mono- Tetra-Specimen TiN Amount Temperature Density Strength K.sub.IC clinic gonal CubicNo. (wt %) Type (mol %) (.degree.C.) (g/cm.sup.3) (kg/mm.sup.2) (kg/mm.sup.3/2) (wt %) (wt %) (wt Remarks__________________________________________________________________________T101 20 Y.sub.2 O.sub.3 2 1,500 5.95 106.9 41.5 6 89 5 Present InventionT102 " " 3 " 5.91 91.9 41.1 0 87 13 Present InventionT103 40 " 2 " 5.81 117.8 37.3 0 96 4 Present InventionT104 " " 3 " 5.78 102.7 35.9 0 89 11 Present InventionT105 60 " 2 1,600 5.68 74.4 29.6 0 97 3 Present InventionT106 " " 3 " 5.66 66.8 27.5 0 90 10 Present Invention__________________________________________________________________________

EXAMPLE 5

To a 1 mol% solution of zirconium oxychloride having a purity of 99.9% (wherein the ZrO.sub.2 component contains 3 to 5% of HfO.sub.2) were added yttrium chloride, magnesium chloride or calcium chloride as a stabilizer, all having a purity of 99.9%, and aluminum chloride having a purity of 99.9% so as to prepare a mixture having the composition shown in Table 9. They were uniformly mixed and then co-precipitated to obtain a hydroxide mixture. The hydroxide mixture thus prepared was dehydrated, dried, and calcined at 800.degree. C. to obtain a starting powder having a mean particle size of 200 .ANG.. The thus-obtained powder was press-molded at a pressure of 1.5 ton/cm.sup.2, and sintered in an electric furnace in the air at 1,400.degree. to 1,650.degree. C. for 1 hour. After sintering, the resulting sintered body was cut and ground to provide a specimen of 4.times.8.times.25 mm. In this way, a series of sintered bodies were produced. In all of the sintered bodies, the mean grain size was less than 3 microns. However, when the sintering temperature was increased to higher temperatures than those shown in Table 9, the mean grain sizes of resulting sintered bodies were larger than 3 microns, resulting in a reduction in strength.

As shown clearly from Table 9, the co-precipitation of Al.sub.2 O.sub.3 inhibits the transformation from the tetragonal ZrO.sub.2 to the monoclinic ZrO.sub.2 and increases the fraction of the tetragonal ZrO.sub.2, improving the strength and toughness. The hardness and high temperature flexural strength of some specimens were also measured. The results are shown in Table 10 and FIG. 5. It can be seen from the results that the hardness of the sintered body increased with increasing Al.sub.2 O.sub.3 content, for example, the hardness of the specimen No. P34 with 60% Al.sub.2 O.sub.3 content was almost equal to that of Al.sub.2 O.sub.3 ceramics, and that the high temperature strength markedly improved compared with the comparative partially stabilized zirconia sintered body commercially available from Corning Corp., U.S.A. (Specimen No. R).

TABLE 9__________________________________________________________________________Composition Stabilizer Crystal System of ZrO.sub.2 for ZrO.sub.2 Sintering Flexural Mono- Tetra-Specimen Al.sub.2 O.sub.3 Amount Temperature Density Strength K.sub.IC clinic gonal CubicNo. (wt %) Type (mol %) (.degree.C.) (g/cm.sup.3) (kg/mm.sup.2) (kg/mm.sup.3/2) (wt %) (wt %) (wt %) Remarks__________________________________________________________________________P1 0 Y.sub.2 O.sub.3 4 1,600 6.04 60.7 18.9 8 57 35 ComparisonP2 0.1 " 4 " 6.04 63.5 20.1 3 63 34 ComparisonP3 0.5 " 4 " 6.02 81.1 22.6 1 65 34 Present InventionP4 1.5 " 4 " 5.99 83.3 23.8 0 67 33 Present InventionP5 3 " 1 1,400 * -- -- 96 0 4 ComparisonP6 " " 1.5 " 5.91 41.1 18.1 41 52 7 ComparisonP7 " " 2 1,500 6.00 110.3 47.1 4 85 11 Present InventionP8 " " 2.5 " 5.99 105.5 39.7 3 79 18 Present InventionP9 " " 3 " 5.97 96.7 31.7 1 76 23 Present InventionP10 " " 4 1,600 5.95 94.6 25.0 0 68 32 Present InventionP11 " " 6 " 5.88 51.3 15.8 0 26 74 Present InventionP12 " " 8 " 5.76 35.7 13.7 0 0 100 ComparisonP13 " MgO 7 1,500 5.78 80.5 22.1 2 63 35 Present InventionP14 3 CaO 6 " 5.81 74.8 20.0 3 57 40 Present InventionP15 10 Y.sub.2 O.sub.3 1 " * -- -- 97 0 3 ComparisonP16 " " 2 " 5.79 117.3 41.5 2 89 9 Present InventionP17 " " 3 " 5.76 102.9 34.8 1 80 19 Present InventionP18 " " 4 1,600 5.74 100.7 32.1 0 73 27 Present InventionP19 " MgO 7 1,500 5.56 85.6 31.1 0 71 29 Present InventionP20 " CaO 6 " 5.58 79.5 29.2 0 67 33 Present InventionP21 20 Y.sub.2 O.sub.3 1 " 5.52 120.6 36.6 5 93 2 Present InventionP22 " " 2 " 5.51 130.7 38.2 0 95 5 Present InventionP23 " " 3 " 5.49 112.2 33.7 0 89 11 Present InventionP24 " " 4 1,600 5.48 109.7 30.7 0 78 22 Present InventionP25 " MgO 7 1,500 5.31 93.3 29.8 0 75 25 Present InventionP26 " CaO 6 " 5.33 86.7 28.6 0 71 29 Present InventionP27 40 Y.sub.2 O.sub.3 1 " 5.03 134.1 31.0 0 98 2 Present InventionP28 " " 2 " 5.03 151.6 30.1 0 96 4 Present InventionP29 " " 3 " 5.02 133.0 28.6 0 93 7 Present InventionP30 " " 4 1,600 5.01 130.1 27.4 0 86 14 Present InventionP31 " MgO 7 1,500 4.89 110.6 26.8 0 81 19 Present InventionP32 " CaO 6 " 4.90 102.8 26.2 0 79 21 Present InventionP33 60 Y.sub.2 O.sub.3 1 1,600 4.63 98.9 24.2 0 100 0 Present InventionP34 " " 2 " 4.63 90.2 23.9 0 98 2 Present InventionP35 " " 3 " 4.62 78.9 23.3 0 94 6 Present InventionP36 " " 4 " 4.62 77.3 23.1 0 89 11 Present InventionP37 " MgO 7 " 4.57 65.6 22.8 0 85 15 Present InventionP38 " CaO 6 " 4.58 61.0 22.7 0 81 19 Present InventionP39 70 Y.sub.2 O.sub.3 2 " 4.45 49.8 12.7 0 98 2 ComparisonP40 " MgO 7 " 4.39 48.0 11.5 0 86 14 ComparisonP41 " CaO 6 " 4.40 46.6 10.2 0 83 17 Comparison__________________________________________________________________________ *disintegration TABLE 10______________________________________ Specimen No. P7 P16 P22 P28 P34______________________________________Amount of Al.sub.2 O.sub.3 (wt %) 3 10 20 40 60Hardness 83.6 84.2 85.1 86.7 87.8______________________________________

While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

Claims

1. A high toughness sintered body consisting essentially of from 40 to 99.5% by weight Component A and from 0.5 to 60% by weight Component B, wherein the mean grain size of the sintered body is 3 microns or less, wherein:

Component A is partially stabilized ZrO.sub.2 which contains 1 to 6 mol% of Y.sub.2 O.sub.3, 7 mol% of MgO or 6 mol% of CaO as a stabilizer in which tetragonal and cubic ZrO.sub.2 constitute at least 90% by weight thereof and the ratio of the tetragonal ZrO.sub.2 to the cubic ZrO.sub.2 is at least 1/3; and

Component B is TiN, with impurities being 3% by weight or less of SiO.sub.2, 0.5% by weight or less of Fe.sub.2 O.sub.3, and 0.5% by weight or less of TiO.sub.2, provided that the total amount is 3% by weight or less.

2. A sintered body as in claim 1, wherein the whole or part of the ZrO.sub.2 is replaced by HfO.sub.2.

3. A sintered body as in claim 1, wherein the partially stabilized ZrO.sub.2 and the stabilizer are prepared by co-precipitation.

4. A sintered body as in claim 2, wherein the partially stabilized ZrO.sub.2 and the HfO.sub.2 which replaces part of the ZrO.sub.2 or the HfO.sub.2 which replaces the whole of the ZrO.sub.2 and the stabilizer are prepared by co-precipitation.