Sintered ceramic composite body and method of manufacturing same

Abstract

A sintered ceramic composite body is manufactured by preparing a powdery mixture composed of a base material composed of either one of oxide ceramic such as alumina, mullite, magnesia, or the like, and nonoxide ceramic such as silicon nitride, sialon, or the like, and a reinforcement material composed of particles or platelet particles of silicon carbide which have a size ranging from 5 to 20 .mu.m, the particles of silicon carbide being contained at a volume ratio ranging from 3 to 50%. The platelet particles have a maximum diameter ranging from 5 to 50 .mu.m and a thickness which is 1/3 or less of the maximum diameter. The powdery mixture is molded into a shaped product, which is then sintered in a temperature range from 1,400.degree. to 1,900.degree. C. for the base material which is composed of oxide ceramic or in a temperature range from 1,500.degree. to 2,000.degree. C. for the base material which is composed of nonoxide ceramic.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a sintered ceramic composite body with improved toughness and a method of manufacturing such a sintered ceramic composite body.

2. Prior Art

Ceramic materials have long been used as refractory materials and chemical materials since they are highly resistant to corrosion and heat and high in hardness. Recent advances in chemical technology allow highly pure materials to be refined and synthesized, and process control technology makes it possible to produce ceramic materials having widely varied properties, which have attracted much attention in the art. Heat-resistant alloys have heretofore been employed in applications at high temperatures or in adverse environments, such as gas turbine blades. However, there has been a demand for more excellent high-temperature structural materials in view of the recent trend in the market for higher performance. Ceramic is recognized as an important material which meets the requirements in such uses, because it is much better than other materials with respect to heat resistance, acid resistance, and corrosion resistance.

Ceramic materials such as silicon nitride, alumina, silicon carbide are generally brittle, and many of these materials have a fracture toughness of 5 MNm.sup.-3/2 or less. Various attempts have heretofore been made to improve the toughness of ceramic materials.

One effort to toughen a ceramic material involves the addition of needle-like components such as whiskers, fibers, or the like as a reinforcement material, as disclosed in Japanese Laid-Open Patent Publication No. 59-30770. It is considered that the toughness of a ceramic material with such a reinforcement material is increased by the crack deflection effect, in which cracks produced in the ceramic by whiskers or the like dispersed therein are bent, or the whisker pullout effect.

However, it is difficult to disperse needle-like reinforcing elements uniformly in a ceramic material. If fibers are used as a reinforcement material, the dispersed fibers tend to be entangled together into a fiber agglomeration in the ceramic.

Japanese Patent Publication No. 59-25748 discloses a method of toughening an alumina ceramic material with zirconia added as a reinforcement material. According to the disclosed method, zirconia is left as a metastable tetragonal system in alumina down to room temperature, and the mechanical properties of the ceramic material at room temperature are greatly improved by residual compressive stresses which are produced due to a volume expansion by 4% upon crystal system transformation that is caused from the tetragonal system into a monoclinic system owing to stresses at tip ends of produced cracks.

Even with the above ceramic toughening method, however, if the ceramic material is left for a long time in atmosphere at a temperature higher than about 900.degree. C., which is the transformation temperature, then the zirconium oxide and the base material which is a nonoxide, react with each other to the extent that the properties of the base material can no longer be maintained. As a result, the above toughening effect is not achieved.

Japanese Laid-Open Patent Publication No. 62-246865 discloses a sintered body of silicon nitride with a rare earth element, MgO, and ZrO.sub.2 added as sintering aids. Japanese Laid-Open Patent Publication No. 63-100067 shows a sintered body of silicon nitride which contains two or more of Y.sub.2 O.sub.3, Er.sub.2 O.sub.3, Tm.sub.2 O.sub.3, Yb.sub.2 O.sub.3, and Lu.sub.2 O.sub.3. However, silicon carbide is not contained as a reinforcement material.

In efforts to increase the toughness of a ceramic material with dispersed whiskers, fibers, or the like, it is difficult to disperse such materials uniformly. Even if these reinforcement elements can be dispersed relatively uniformly, it is impossible to produce sintered ceramic composite bodies of good properties unless specially handled in the manufacturing process. Use of whiskers, fibers, or other reinforcement materials is highly expensive. In the case where particles of zirconium oxide are dispersed for increased toughness, no toughening effect is achieved at high temperatures where no crystal system transformation progresses. If the ceramic material is left at a high temperature for a long period of time, then zirconium oxide and the base material which is a nonoxide react with each other, and the properties of the base material are no longer maintained.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide a sintered ceramic composite body which is toughened by adding silicon carbide particles of predetermined shape as a reinforcement material to a base material which is an oxide or a nonoxide, and a method of manufacturing such a sintered ceramic composite body.

Another object of the present invention is to provide a sintered ceramic composite body comprising a base material composed of either one of oxide ceramic such as alumina, mullite, magnesia, or the like, and nonoxide ceramic such as silicon nitride, sialon, or the like, and a reinforcement material composed of particles of silicon carbide which have a size ranging from 5 to 20 .mu.m.

Still another object of the present invention is to provide the sintered ceramic composite body wherein the particles of silicon carbide are contained at a volume ratio ranging from 3 to 50%.

Yet another object of the present invention is to provide a method of manufacturing a sintered ceramic composite body, comprising preparing a powdery mixture composed of a base material composed of either one of oxide ceramic such as alumina, mullite, magnesia, or the like, and nonoxide ceramic such as silicon nitride, sialon, or the like, and a reinforcement material composed of particles of silicon carbide which have a size ranging from 5 to 20 .mu.m, the particles of silicon carbide being contained at a volume ratio ranging from 3 to 50%, molding the powdery mixture into a shaped product, and sintering the shaped product in a temperature range from 1,400.degree. to 1,900.degree. C. for the base material which is composed of oxide ceramic or in a temperature range from 1,500.degree. to 2,000.degree. C. for the base material which is composed of nonoxide ceramic.

It is also an object of the present invention to provide a sintered ceramic composite body comprising a base material composed of either one of oxide ceramic such as alumina, mullite, magnesia, or the like, and nonoxide ceramic such as silicon nitride, sialon, or the like, and a reinforcement material composed of platelet particles of silicon carbide which have a maximum diameter ranging from 5 to 50 .mu.m and a thickness which is 1/3 or less of the maximum diameter.

A further object of the present invention is to provide the sintered ceramic composite body wherein the platelet particles of silicon carbide are contained at a volume ratio ranging from 3 to 50%.

A yet further object of the present invention is to provide a method of manufacturing a sintered ceramic composite body, comprising preparing a powdery mixture composed of a base material composed of either one of oxide ceramic such as alumina, mullite, magnesia, or the like, and nonoxide ceramic such as silicon nitride, sialon, or the like, and a reinforcement material composed of platelet particles of silicon carbide which have a maximum diameter ranging from 5 to 50 .mu.m and a thickness which is 1/3 or less of the maximum diameter, the platelet particles of silicon carbide being contained at a volume ratio ranging from 3 to 50%, molding the powdery mixture into a shaped product, and sintering the shaped product in a temperature range from 1,400.degree. to 1,900.degree. C. for the base material which is composed of oxide ceramic or in a temperature range from 1,500.degree. to 2,000.degree. C. for the base material which is composed of nonoxide ceramic.

The above and other objects, features and advantages of the present invention wi become more apparent from the following description when taken in conjunction with the accompanying drawings in which a preferred embodiment of the present invention is shown by way of illustrative example.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flowchart of a method of manufacturing a sintered ceramic composite body according to the present invention; and

FIGS. 2(a) and 2(b) are views showing defined dimensions of a silicon carbide particle used as a reinforcement material.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

A sintered ceramic composite body according to the present invention comprises, as a base material, an oxide ceramic material such as alumina, magnesia, mullite, etc., or a nonoxide ceramic material such as silicon nitride, sialon, etc., the silicon nitride containing two or more of Y.sub.2 O.sub.3, Er.sub.2 O.sub.3, Tm.sub.2 O.sub.3, Yb.sub.2 O.sub.3, Lu.sub.2 O.sub.3, or a rare earth, MgO, and ZrO.sub.2, as a reinforcement material, particles of silicon carbide. Small amounts of other elements may be contained as impurities in the above materials. It is preferable that a sintering aid be added to the materials of the sintered ceramic composite as is the case with ordinary sintered bodies composed of oxide or nonoxide ceramic. The sintered ceramic composite according to the present invention may be shaped by any of ordinary shaping processes such as pressing, slip casting, injection molding, extrusion molding, etc. The materials of the ceramic composite are sintered in a vacuum or inert gas atmosphere by hot pressing (HP), but may also be sintered by normal-pressure sintering, sinter-HIP, or capsule HIP.

The particles of silicon carbide as the reinforcement material are of a size ranging from 5 to 20 .mu.m, and 3 to 50% or preferably 10 to 30% by volume of such particles of silicon carbide are added to the base material, forming a powdery mixture. Alternatively, the particles of silicon carbide as the reinforcement material are in the form of plates having a maximum diameter ranging from 5 to 50 .mu.m, preferably, from 10 to 40 .mu.m, and a thickness which is 1/3 or less of the maximum diameter, and 3 to 50% or preferably 10 to 30% of such platelet particles of silicon carbide are added to the base material, forming a powdery mixture. The powdery mixture thus obtained is molded to shape. The shaped product is then sintered in a temperature range from 1,400.degree. to 1,900.degree. C. for the base material which is an oxide ceramic, or in a temperature range from 1,500.degree. to 2,000.degree. C. for the base material which is a nonoxide ceramic. The sintered ceramic composite body thus produced has a high degree of toughness. Platelet particles of silicon carbide are more effective for toughening the sintered ceramic composite body than particles of silicon carbide.

If the base material is a nonoxide ceramic, then silicon nitride and sialon contained in the base material are decomposed at a high rate when the sintering temperature becomes higher than 1,700.degree. C. To avoid such accelerated decomposition, the pressure of a nitrogen atmosphere used is normally increased up to a range from 9 to 9.9 kg.f/cm.sup.2. If the sintering temperature were lower than the above ranges, the density of the sintered body would be low. If the sintering temperature were higher than the above ranges, the components of the base material would be decomposed. At any rate, no dense sintered body would be produced. The optimum sintering temperature varies depending on the conditions of the normal-pressure sintering, the hot pressing, sinter-HIP, and the capsule HIP, and the size and amount of silicon carbide particles as the reinforcement material.

If the added amount of silicon carbide particles were less than 3% by volume, then no increase in the fracture toughness would be achieved. If the added amount of silicon carbide particles were larger than 50%, then the density of the produced sintered ceramic composite body would be too low and hence no dense sintered ceramic composite body would be manufactured. If the size of silicon carbide particles were smaller than 5 .mu.m, then the fracture toughness would not be improved, and if larger than 20 .mu.m, then the density of the produced sintered ceramic composite body would be too low. The fracture toughness is measured by the SEPB (Single Edge Pre-cracked Beam) process. More specifically, a test specimen is prepared according to JIS R1601, indented diamond pyramid indenter of a Vickers hardness test machine, and subjected to a load for producing a pre-crack, with a pop-in detected by earphones. Then, the test specimen is colored for the measurement of the pre-crack, subjected to a bending test, and thereafter measured for a fracture load. After the length of the pre-crack in the fractured test specimen is measured, a fracture toughness value is calculated according to the fracture toughness equation.

FIG. 1 shows a sequence of a method according to the present invention. The base material and the reinforcement material were placed in a pot mill, and mixed with water or ethanol for 24 hours, thus forming a mixture. As described above, the reinforcement material was added at a volume ratio ranging from 3 to 50%, either in the form of particles of silicon carbide having a size ranging from 5 to 20 or in the form of platelet particles of silicon carbide having a maximum diameter ranging from 5 to 50 .mu.m, and a thickness which is 1/3 or less of the maximum diameter.

FIGS. 2(a) and 2(b) show dimensional definitions of silicon carbide particles. As shown in FIG. 2(a), a silicon carbide particle has a minor-axis diameter (i.e., a minimum distance across the particle between two parallel lines contacting the particle) ranging from 5 to 20 .mu.m. FIG. 2(b) illustrates a platelet silicon carbide particle having a maximum diameter ranging from 5 to 50 .mu.m and a thickness which is 1/3 or less of the maximum diameter.

The mixture produced in the pot mill was then dried at 120.degree. C. for 24 hours, and passed through a sieve having a mesh size of 149 .mu.m, thereby forming a powder. The powder was then pressed to shape under a pressure of 200 kg/cm.sup.2, or pressed to shape under a pressure of 7 tons/cm.sup.2 by a rubber press, after which the shaped product was sintered under pressure. For the base material which is an oxide ceramic, he shaped product was sintered at an HP temperature ranging from 1,400.degree. to 1,900.degree. C. in an Ar atmosphere under 1 atm. For the base material which is a nonoxide ceramic, the shaped product was sintered at an HP temperature ranging from 1,500.degree. to 2,000.degree. C. in an N.sub.2 atmosphere under 1 atm. The HP pressure was 300 kg/cm.sup.2. For the base material which is composed of silicon nitride containing two or more of Y.sub.2 O.sub.3, Er.sub.2 O.sub.3, Tm.sub.2 O.sub.3, Yb.sub.2 O.sub.3, Lu.sub.2 O.sub.3, or silicon nitride containing a rare earth, MgO, and ZrO.sub.2, and sialon, the shaped product was sintered at an HP temperature ranging from 1,500.degree. to 2,000.degree. C. in an N.sub.2 atmosphere under 1 atm. For the base material which is composed of a nonoxide ceramic material, the shaped product was sintered at a temperature of 1,700.degree. C. or higher in an N.sub.2 atmosphere under 9.5 atm, for the reasons described above.

Tables 1--1, 1--2, and 1--3 show the results of a fracture toughness test conducted on various inventive and comparative examples. The base materials of the examples included alumina, mullite, and magnesia as oxide ceramic materials, and silicon nitride containing two or more of Y.sub.2 O.sub.3, Er.sub.2 O.sub.3, Tm.sub.2 O.sub.3, Yb.sub.O.sub.3, Lu.sub.2 O.sub.3 or silicon nitride containing a rare earth, MgO, and ZrO.sub.3, and sialon as nonoxide materials, and silicon carbide was added as a reinforcement material to the base materials under the conditions given in Tables 1--1, 1--2, and 1--3.

The sintered ceramic composite body according to the present invention is high in toughness because of silicon carbide particles of suitable shape and size dispersed at a suitable volume rate to a base material which is an oxide or a nonoxide. The sintered ceramic composite body according to the present invention requires no special equipment for its manufacture, but can be manufactured by ordinary ceramic manufacturing equipment. Therefore, the sintered ceramic body composite material can be manufactured at a low cost.

Although a certain preferred embodiment has been shown and described, it should be understood that many changes and modifications may be made therein without departing from the scope of the appended claims.

TABLE 1-1__________________________________________________________________________ BASE ADDED AMOUNT H P TEM- FRACTURE MATERIAL OF SiC SIZE OF SiC PARTICLES PERATURE TOUGHNESS No. (vol %) (vol %) (.mu.m) (.degree.C.) (M N m.sup.-3/2)__________________________________________________________________________ ALMINAINVENTIVE 1 97 3 20 1400 5.0EXAMPLE 2 95 5 20 1500 5.2 3 90 10 5 1800 5.6 4 90 10 10 1600 5.3 5 90 10 20 1600 5.4 6 85 15 20 1750 5.6 7 80 20 10 1800 5.7 8 70 30 5 1900 7.6 9 70 30 10 1750 6.0 10 50 50 5 1900 5.2 11 97 3 *PLATE-LIKE 30 .times. 5 1600 6.8 12 90 10 *PLATE-LIKE 10 .times. 3 1600 7.0 13 90 10 *PLATE-LIKE 30 .times. 5 1600 7.0 14 70 30 *PLATE-LIKE 40 .times. 5 1600 7.4 15 70 30 *PLATE-LIKE 50 .times. 5 1600 7.3 16 50 50 *PLATE-LIKE 5 .times. 1 1900 6.0COMPARA- 17 100 0 -- 1400 3.8TIVE 18 99 1 20 1700 3.9EXAMPLE 19 80 20 10 2000 3.0 20 45 55 5 1300 2.1 21 80 20 1 1600 4.1 22 80 20 30 1600 4.1 MULLITEINVENTIVE 23 70 30 10 1700 4.0EXAMPLE 24 70 30 5 1700 3.9 25 70 30 *PLATE-LIKE 30 .times. 5 1600 4.2COMPARA- 26 100 0 -- 1600 2.0TIVE 27 70 30 1 1700 2.1EXAMPLE MAGNESIAINVENTIVE 28 90 10 20 1700 3.6EXAMPLE 29 70 30 20 1800 4.0 30 70 30 *PLATE-LIKE 30 .times. 5 1800 4.6COMPARA- 31 100 0 -- 1300 1.0TIVEEXAMPLE__________________________________________________________________________ *PLATELET = MAXIMUM DIAMETER .times. THICKNESS FRACTURE TOUGHNESS (M N m.sup.-3/2) (ADVANTAGE OF n = 3) TABLE 1-2__________________________________________________________________________ BASE MATERIAL ADDED FRACTURE (vol %) AMOUNT SIZE OF SiC **SINTERING H P TEM- TOUGH- SILICON OF SiC PARTICLES ASSISTANT PERATURE NESS No. NITRIDE (vol %) (.mu.m) (wt %) (.degree.C.) (M N__________________________________________________________________________ m.sup.-3/2)INVENTIVE 1 97 3 20 Y.sub.2 O.sub.3 MgO ZrO.sub.2 1500 7.0EXAMPLE 6 4 0.5 2 95 5 20 Y.sub.2 O.sub.3 MgO ZrO.sub.2 1700 8.0 6 4 0.5 3 90 10 10 Y.sub.2 O.sub.3 MgO ZrO.sub.2 1700 8.6 6 4 0.5 4 70 30 20 Y.sub.2 O.sub.3 MgO ZrO.sub.2 1900 9.5 6 4 0.5 5 70 30 5 Y.sub.2 O.sub.3 MgO ZrO.sub.2 1800 8.4 6 4 0.5 6 50 50 5 Y.sub.2 O.sub.3 MgO ZrO.sub.2 2000 8.0 6 4 0.5 7 97 3 *PLATE-LIKE 30 .times. 5 Y.sub.2 O.sub.3 MgO ZrO.sub.2 1700 9.0 6 4 0.5 8 90 10 *PLATE-LIKE 30 .times. 5 Y.sub.2 O.sub.3 MgO ZrO.sub.2 1700 9.8 6 4 0.5 9 70 30 *PLATE-LIKE 10 .times. 3 Y.sub.2 O.sub.3 MgO ZrO.sub.2 1800 9.3 6 4 0.5 10 70 30 *PLATE-LIKE 40 .times. 5 Y.sub.2 O.sub.3 MgO ZrO.sub.2 1800 10.5 6 4 0.5 11 70 30 *PLATE-LIKE 50 .times. 5 Y.sub.2 O.sub.3 MgO ZrO.sub.2 1700 9.1 6 4 0.5 12 50 50 *PLATE-LIKE Y.sub.2 O.sub.3 MgO ZrO.sub.2 2000 8.1 6 4 0.5 Y.sub.2 O.sub.3 5.7 13 70 30 20 1800 9.3 Yb.sub.2 O.sub.3 3.8 Y.sub.2 O.sub.3 5.7 14 70 30 *PLATE-LIKE 30 .times. 5 1800 10.2 Yb.sub.2 O.sub.3 3.8 Y.sub.2 O.sub.3 4.0 15 70 30 20 1800 8.7 Er.sub.2 O.sub.3 4.0 Yb.sub.2 O.sub.3 7.0 16 70 30 20 1800 8.6 Lu.sub.2 O.sub.3 5.0 Y.sub.2 O.sub.3 3.0 17 70 30 20 1800 9.0 Tm.sub.2 O.sub.3 5.0COMPARA- 18 100 0 -- Y.sub.2 O.sub.3 MgO ZrO.sub.2 1700 6.0TIVE 6 4 0.5EXAMPLE 19 80 20 10 Y.sub.2 O.sub.3 MgO ZrO.sub.2 1400 UNMEA- 6 4 0.5 SURABLE (NOT SUF- FICIENTLY DENSE) 20 99 1 20 Y.sub.2 O.sub.3 MgO ZrO.sub.2 1750 6.3 6 4 0.5 21 40 60 20 Y.sub.2 O.sub.3 MgO ZrO.sub.2 2100 4.2 6 4 0.5 (NOT SUF- FICIENTLY DENSE) 22 80 20 1 Y.sub.2 O.sub.3 MgO ZrO.sub.2 1800 5.8 6 4 0.5 Y.sub.2 O.sub.3 5.7 23 100 0 -- 1800 7.2 Yb.sub.2 O.sub.3 3.8 Y.sub.2 O.sub.3 5.7 5.1 24 40 60 *PLATE-LIKE 30 .times. 5 1800 (NOT SUFFI- Yb.sub.2 O.sub.3 3.8 CIENTLY DENSE)__________________________________________________________________________ *PLATELET MAXIMUM DIAMTER .times. THICKNESS FRACTURE TOUGHNESS (M N m.sup.-3/2) (ADVANTAGE OF n = 3) **PROPORTION ADDED TO BASE MATERIAL OF SILICON NITRIDE TABLE 1-3__________________________________________________________________________ BASE MATERIAL ADDED AMOUNT SIZE OF SiC H P TEMP- FRACTURE (vol %) OF SiC PARTICLES ERATURE TOUGHNESS No. SIALON (vol %) (.mu.m) (.degree.C.) (M N m.sup.-3/2)__________________________________________________________________________INVENTIVE 1 70 30 10 1800 5.6EXAMPLE 2 70 30 5 1800 5.0 3 70 30 *PLATE-LIKE 30 .times. 5 1800 5.6 4 90 10 *PLATE-LIKE 30 .times. 5 1750 4.6COMPARA- 5 100 0 -- 1750 3.8TIVE 6 70 30 1 1800 3.7EXAMPLE__________________________________________________________________________ *PLATELET MAXIMUM DIAMETER .times. THICKNESS FRACTURE TOUGHNESS (M N m.sup.-3/2) (ADVANTAGE OF n = 3)

Claims

1. A tough sintered ceramic composite body consisting essentially of:

a base material selected from the group consisting of alumina, mullite, magnesia, and silicon nitride; and

a reinforcement material compose of platelet particles of silicon carbide, each particle having a maximum diameter in the range of 5 to 50 .mu.m and a thickness which is 1/3 or less of the maximum diameter.

2. A sintered ceramic composite body according to claim 1, wherein said platelet particles of silicon carbide are contained at a volume ratio ranging from 3 to 50%.

3. A sintered ceramic composite body as defined in claim 1 wherein the bas material is silicon nitride containing two or more members of the group consisting of Y.sub.2 O.sub.3, Er.sub.2 O.sub.3, Tm.sub.2 O.sub.3, Yb.sub.2 O.sub.3 and Lu.sub.2 O.sub.3.

4. A sintered ceramic composite body as defined in claim 1, wherein said base material is silicon nitride containing a rare earth element, MgO and ZrO.sub.2.

5. A method of manufacturing a tough sintered ceramic composite body, comprising the steps of:

preparing a powdery mixture consisting essentially of a base material selected from the group consisting of alumina, mullite, magnesia, and silicon nitride and a reinforcement material composed of platelet particles of silicon carbide, each particle having a maximum diameter in the range of 5 to 50 .mu.m and a thickness which is 1/3 or less of the maximum diameter, said platelet particles of silicon carbide being present at a volume ratio ranging from 3 to 50 % of the base material;

molding the powdery mixture into a shaped product; and

sintering said shaped product in a temperature range of 1,400.degree. to 1,900.degree. C. when the base material is one of alumina, mullite and magnesia or in a temperature range of 1,500.degree. to 2,000.degree. C. when the base material is silicon nitride.

6. A method of manufacturing a tough sintered ceramic composite body as defined in claim 5, wherein the base material is silicon nitride containing two or more members of the group consisting of Y.sub.2 O.sub.3, Er.sub.3 O.sub.3, Tm.sub.2 O.sub.3, Yb.sub.2 O.sub.3 and Lu.sub.2 O.sub.3.

7. A method of manufacturing a tough sintered ceramic composite body as defined in claim 5, wherein said base material is silicon nitride containing a rare earth element, MgO and ZrO.sub.2.