Abstract:
A ceramic consisting essentially of from 1 to 15 percent of glass and 99 to 85 percent of a mixture of particulate Al 2  O 3  and particulate ZrO 2  is disclosed. ZrO 2  is present in a sufficient amount, usually from 1/4 to 6 percent based on the weight of the ZrO 2  and Al 2  O 3 , to strengthen the ceramic significantly, by comparison with an otherwise identical ceramic where the particulate ZrO 2  is replaced either by the glass or by particulate Al 2  O 3 . The glass constitutes a vitreous phase bonding the particulates into a dense, gas impervious structure, and can be a calcium magnesium silicate glass containing from 45 to 80 percent of SiO 2 , from 8 to 55 percent of CaO and MgO, and not more than 15 percent of Al 2  O 3 .

Description:
DEFINITIONS 
     As used herein, and in the appended claims, the terms &#34;percent&#34; and &#34;parts&#34; refer to percent and parts by weight, unless otherwise indicated; g means gram or grams; cm means centimeter or centimeters; and MPa means 10 6  Pascals. 
     All temperatures herein are in degrees C., unless otherwise indicated. 
     BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     This invention relates to an alumina ceramic containing a small, strengthening addition of zirconia; the ceramic is one which can be produced by a method that lends itself to mass production. 
     2. The Prior Art 
     The subject of alumina-zirconia ceramics produced both by not pressing and by sintering techniques has received a great deal of attention during recent years. A journal article, Cer. Eng. and Sci. Proc., Vol 1, 7-8(B) 1980, is considered to be typical of the prior art relating to such ceramics made by hot pressing. The article, D. Lewis III and P. F. Becher, &#34;Thermal Shock Behavior in Al 2  O 3  -based composites&#34;, reports test data indicating that alumina-zirconia composites which were studied are highly resistant to thermal shock. The data relate to alumina ceramics and to ceramics composed of alumina and up to 30 percent by volume of ZrO 2  produced by hot pressing at 1500°-1600° and 35 MPa (about 5075 pounds per square inch). The data presented indicate the alumina-zirconia ceramics to have outstanding thermal shock properties. Another journal article, J. Am. Cer. Soc., 61, No. 12, pp. 85, 86, and U.S. Pat. No. 4,218,253, are illustrative of the prior art relating to the production of such ceramics by sintering. The patent discloses (Example 1) the production of an alumina-zirconia ceramic from aluminum oxide powder (average particle size 5 microns) and monoclinic zirconium oxide powder (average particle size 1 micron). The process involves wet mixing the two powders, drying and granulating the mixture, isostatically pressing a shape from the granules, and sintering the shape at 1600° for one hour. The journal article discloses a similar process, including sintering at 1500° and 1600°, but is silent as to particle size, disclosing only that &#34;composites with a very fine and homogeneous dispersion&#34; were achieved &#34;by a wet-chemical method, starting from a zirconium sulfate-aluminum sulfate solution.&#34; It will be appreciated that hot pressing alumina-zirconia ceramics at 1500°-1600° and 35 MPa is a costly procedure, that even sintering at 1600° is costly, and that alumina produced by a wet chemical method from a zirconium sulfate-aluminum sulfate solution is a costly starting material. Accordingly, as might be expected, the ceramics produced by the methods of the subject references, and all other alumina-zirconia ceramics that have been suggested by the known prior art, are costly and have found only limited commercial use, for example as tool bits. 
     The present inventor discovered a ceramic composed of a mixture of particulate Al 2  O 3 , particulate ZrO 2  and glass bonding the Al 2  O 3  and the ZrO 2  into a dense, gas impervious structure, and also found that all or any part of the particulate ZrO 2  in such ceramics can be replaced by particulate HfO 2  or by a solid solution of HfO 2  and ZrO 2 , in particulate form, as well as that Y 2  O 3  can advantageously be present to stabilize at least a part of the ZrO 2 , the HfO 2  or the ZrO 2  -HfO 2  solid solution in a cubic crystalline structure. The glass constitutes from 1 to 15 percent of such ceramics, while particulate Al 2  O 3  constitutes from 75 to 85 percent, based upon the weight of the ZrO 2 , HfO 2 , Y 2  O 3  and Al 2  O 3 . &#34;Manning&#34;, U.S. Pat. No. 4,552,852, is directed to this discovery. 
     SUMMARY OF THE INVENTION 
     The instant invention is based upon the discovery of a ceramic which consists essentially of from 1 to 15 percent of glass and from 99 to 85 percent of a mixture of particulate Al 2  O 3  and particulate ZrO 2  in which particulate ZrO 2  is present in a sufficient amount, usually from 1/4 to 6 percent based on the weight of the ZrO 2  and Al 2  O 3 , to strengthen the ceramic significantly, by comparison with an otherwise identical ceramic where the particulate ZrO 2  is replaced either by the glass or by particulate Al 2  O 3 . The particulates should have an ultimate particle size finer than 15 microns. The glass constitutes a vitreous phase bonding the particulates into a dense, gas impervious structure and, preferably, is a calcium magnesium silicate glass containing from 45 to 80 percent of SiO 2 , from 8 to 55 percent of CaO and MgO, and not more than 15 percent of Al 2  O 3 . Preferably, the glass constitutes from 3 to 12 percent of the ceramic, most desirably from 5 to 12 percent. Available data indicate that a large increase in strength is achieved when a small addition of ZrO 2 , e.g., 1/4 percent based upon the weight of Al 2  O 3  and ZrO 2  in the ceramic, is made, and that little if any additional increase in strength is achieved when larger additions, e.g., 1/2 percent on the indicated basis, are made. Since ZrO.sub. 2 is an expensive constituent of ceramics of the type in question, it is desirable to minimize the quantity used. Accordingly, ZrO 2  preferably constitutes from 1/4 to 2 percent, most desirably from 1/2 to 11/2 percent, based upon the weight of the Al 2  O 3  and ZrO 2  therein, in a ceramic according to the instant invention. In fact, the greatest benefit from the expensive batch ingredient is achieved when ZrO 2 , on the indicated basis, ranges from 1/2 to 1 percent. 
     As is indicated above, Manning discloses that particulate HfO 2  and solid solutions of HfO 2  and ZrO 2  can be substituted for ZrO 2  in ceramics of the type in question, and that Y 2  O 3  can also be used, the purpose of the Y 2  O 3  being to stabilize the ZrO 2  or the like in a cubic crystalline structure. The same is probably true in ceramics according to the instant invention, but there is ordinarily no reason for such a ceramic to contain more than the amount of HfO 2  that is introduced thereinto by the 1 to 3 percent thereof that is present as an impurity in ZrO 2  as it occurs in nature. Accordingly, a ceramic according to the invention consists essentially of particulate Al 2  O 3 , particulate ZrO 2  and glass, but, in accordance with the recognized meaning of the recitation, may contain HfO 2 , Y 2  O 3  or other incidental ingredients so long as they do not interfere with the strengthening that is achieved because of the presence of the ZrO 2 . 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     The following examples are presented solely for the purpose of further illustrating and disclosing the invention. They are to be construed as illustrative, and not as limiting. Example 2 constitutes the best mode presently contemplated by the inventor. 
     EXAMPLE 1 
     A ceramic batch composed of 0.84 part of ZrO 2 , 82.79  parts of Al 2  O 3 , 16.07 parts of clays and other fluxes and 0.30 part sodium lignosulfonate was wet milled for 8 hours, 70 percent solids in water, in a 17-liter mill jar. The resulting batch was spray dried. The spray dried batch was then pressed isostatically at about 5500 psi. (about 38 MPa) in a cylindrical mold; the pressed shape was rotated and ground by contact with a rotating grinding wheel to a diameter of about 3.8 cm.; and the body was placed in a setter and fired in a gas fired tunnel kiln (slightly reducing atmosphere): about seventeen hours from ambient temperature of about 22° to 1545°, and about 1 1/5 hours from 1545° to 1550°, followed by cooling. The fired insulator which resulted had a diameter of about 2.5 cm. The mean Charpy Impact Strength of machined bars cut from insulators produced as described in this Example was 1.68×10 -3  foot pounds. 
     The ZrO 2  used as described above in Example 1 is commercially available from TAM Ceramics, Inc. under the trade designation &#34;Zirox 360&#34;. It consists of ZrO 2 , 1 to 3 percent of HfO 2 , assay, ZrO 2  and HfO 2  at least 98.5 percent, and incidental impurities. A sample from the shipment from which ZrO 2  was used as described herein was found to have a median particle diameter of 9.71 microns and a specific surface area of 0.97 m 2  /cm 3 . 
     The Al 2  O 3  used as described above in Example 1 is commercially available from Aluminum Company of America under the designation A-10 alumina. Substantially all of the material is minus 10 microns in ultimate particle size, the median ultimate particle size being 8 microns; the material is agglomerated, however, so that it has the following size characteristics relative to screens of the U.S. Sieve Series: 
     
         ______________________________________100 mesh         4-15 percent retained200 mesh        50-75 percent retained325 mesh        88-98 percent retained           and 2-12 percent through.______________________________________ 
    
     The material consists of Al 2  O 3 , assay 99.5 percent, and incidental impurities. 
     The sodium lignosulfonate used as described above in Example 1 is a water soluble dispersing agent which is commercially available from American Can Company under the designation &#34;MARASPERSE&#34;. 
     The clays and other fluxes used as described above in Example 1 contain SiO 2 , MgO, CaO and Al 2  O 3  in such proportions that the fired insulator contained 89.44 percent of Al 2  O 3 , 0.86 percent of ZrO 2 , 7.02 percent of SiO 2 , 1.56 percent of MgO, 0.71 percent of CaO and 0.41 percent of incidental impurities. A minor amount of the Al 2  O 3  was dissolved in a glass which also contained the SiO 2 , the MgO and the CaO. The glass constituted about 10 percent of the fired insulator. The precise amount of Al 2  O 3  dissolved in the glass was not determined but, on the basis of available phase data, it was estimated that Al 2  O 3  constituted less than 5 percent of the glass. 
     EXAMPLES 2 AND 3 
     The procedure of Example 1 was repeated to produce insulators from different ceramic batch compositions. The compositions of the ceramic batches in parts and the mean Charpy Impact Strengths are given in the following table: 
     
         ______________________________________     Control  Example 2 Example 3______________________________________ZrO.sub.2   0.00       0.42      1.26Al.sub.2 O.sub.3       83.63      83.21     82.37Clays and   16.07      16.07     16.07other fluxesSodium ligno-       0.30       0.30      0.30sulfonateCharpy Impact       1.07       1.82      1.82Strength,footpounds, × 10.sup.3______________________________________ 
    
     EXAMPLES 4-7 
     Insulators were also produced from other ceramic batch compositions using substantially the procedure of Example 1, the only differences being that the batches were milled in 7-liter mill jars, 70 percent solids in water, for 10 hours; and 0.39 part ammonium polyelectrolyte dispersant was used in place of the sodium lignosulfonate. The compositions of the ceramic batches in parts and the mean Charpy Impact Strengths are given in the following table: 
     
         ______________________________________            Exam-   Exam-   Exam- Exam-     Control            ple 4   ple 5   ple 6 ple 7______________________________________ZrO.sub.2   0.00     0.84    1.67  2.50  4.18Al.sub.2 O.sub.3       83.55    82.71   81.88 81.05 79.37Clays and   16.06    16.06   16.06 16.06 16.06other fluxesAmmonium poly-       0.39     0.39    0.39  0.39  0.39electrolytedispersantCharpy Impact       1.824    2.448   2.309 2.040 2.063Strength,footpounds, × 10.sup.3______________________________________ 
    
     EXAMPLES 8-12 
     Insulators were also produced from other ceramic batch compositions using substantially the procedure of Example 1, the only differences being that the batches were milled in 7-liter mill jars, 72 percent solids in water, for 91/2  hours. Control insulators were produced from a batch composed of 83.24 parts of Al 2  O 3 , 15.98 parts of clays and other fluxes, 0.25 part of sodium lignosulfonate and 0.53 part of ammonium polyelectrolyte dispersant, while test insulators were produced from batches composed of 82.75 parts of Al 2  O 3 , 15.98 parts of clays and other fluxes, 0.25 parts of sodium lignosulfonate, 0.53 part of ammonium polyelectrolyte dispersant and 0.49 part of various grades of zirconia. The grades of zirconia tested, the Charpy Impact Strength in footpounds ×10 3  of machined bars cut from insulators made from each of the batches, and the fired bulk density in grams per cubic centimeter of the insulators, and the cantilever breaking load in pounds of the terminal ends of spark plug insulators made from each of the batches are set forth in the following table: 
     
         ______________________________________Con-       Exam-   Exam-   Exam- Exam-  Exam-trol       ple 8   ple 9   ple 10                            ple 11 ple 12______________________________________Zirconia   --     &#34;Zirox  &#34;SC-  &#34;Zirox                              &#34;HSY-3&#34;                                     &#34;DK-1&#34;Grade          360&#34;    101&#34;  TR&#34;Charpy  1.140  1.940   1.750 2.010 1.760  1.690ImpactStrengthFired Bulk   3.524  3.569   3.571 3.571 3.575  3.571DensityCantilever   465    534     505   503   526    543BreakingLoad______________________________________ 
    
     Grade &#34;SC-101&#34; of zirconia is commercially available from Magnesium Elektron. It was found to have a median particle diameter of 4.14 microns and a specific surface area of 1.47 m 2  /cm 3 . It consists of ZrO 2 , 1-3 percent of HfO 2 , assay, ZrO 2  and HfO 2  at least 98.5 percent, and incidental impurities. 
     Grade &#34;Zirox Tr&#34; of zirconia is commercially available from TAM Ceramics, Inc. It was found to have a median particle diameter of 3.43 microns and a specific surface area of 1.49 m 2  /cm 3 . It consists of ZrO 2 , 1-3 percent of HfO 2 , assay, ZrO 2  and HfO 2  at least 98.5 percent, and incidental impurities. 
     Grade &#34;HSY-3&#34; of zirconia is commercially available from Daiichi Kigenso. It was found to have a median particle diameter of 3.37 microns and a specific surface area of 1.67 m 2  /cm 3 . It consists of ZrO 2 , 1-3 percent of HfO 2 , assay, ZrO 2  and HfO 2  at least 93.1 percent, 5.4 percent of Y 2  O 3 , and incidental impurities. P Grade &#34;DK-1&#34; of zirconia is commercially available from Daiichi Kigenso. It was found to have a median particle diameter of 3.37 microns and a specific surface area of 1.76 m 2  /cm 3 . It consists of ZrO 2 , 1-3 percent of HfO 2 , assay, ZrO 2  and HfO 2  at least 98.5 percent, and incidental impurities. 
     It will be observed from a comparison of the foregoing data concerning Examples 1-3 and the associated control with the data concerning Examples 4-7 and the associated control and that for Examples 8-12 and the associated control that the different milling procedures used caused substantial changes in the magnitudes of the Charpy Impact Strengths. The percentage increases, however, relative to the relevant controls, follow the same patterns, indicating that the strengthening caused by the added ZrO 2  is independent of the milling procedures. The percentage increases are reported in the following table: 
     
         ______________________________________     Percent of Added ZrO.sub.2     0.5 1.0      1.5   2.0    3.0 5.0______________________________________Example 2   70Example 8   70Example 9   54 Example 10 76 Example 11 54 Example 12 48Example 1         57Example 4         34Example 3                  70Example 5                      27Example 6                             12Example 7                                 13______________________________________ 
    
     EXAMPLES 13-16 
     Insulators having a nominal 92 percent Al 2  O 3  content, and containing varying amounts of ZrO 2  were also produced using substantially the procedure of Example 1, the only differences being that a different grade of Al 2  O 3  was used and that the batch was milled in 7-liter mill jars, 72 percent solids in water, for 101/2 hours. Typical batch compositions, Charpy Impact strengths and densities are given in the following table: 
     
         ______________________________________            Exam-   Exam-   Exam- Exam-    Control ple 13  ple 14  ple 15                                  ple 16______________________________________ZrO.sub.2  0.00      0.25    0.49  0.73  0.97Al.sub.2 O.sub.3      87.49     87.49   87.49 87.49 87.49Clays and  11.73     11.48   11.24 11.00 10.76other fluxesSodium ligno-      0.25      0.25    0.25  0.25  0.25sulfonateAmmonium   0.53      0.53    0.53  0.53  0.53polyelectrolytedispersantCharpy Impact      1.32      1.70    1.94  1.96  1.84Strength,footpounds × 10.sup.3Fired Bulk 3.616     3.634   3.642 3.644 3.651Density, g/cm.sup.3______________________________________ 
    
     The Al 2  O 3  used in the batches of the previous table was obtained from Aluminum Company of America under the grade designation A-121. Substantially all of the material is minus 5 microns in ultimate particle size; the material is agglomerated, however, so that it has the following size characteristics relative to screens of the U.S. Sieve Series: 
     
         ______________________________________100 mesh         4-15 percent retained200 mesh        50-75 percent retained325 mesh        88-98 percent retained           and 2-12 percent through______________________________________ 
    
     The material consists of Al 2  O 3 , assay 99.5 percent, and incidental impurities. 
     It will be noted from the data in the foregoing table that both the fired bulk densities and the strengths of the specimens produced were increased by the additions of ZrO 2  that were made in the procedures of Examples 13-16. This is generally true of ceramics according to the instant invention. Although the invention is in no way to be limited by the following theory, it is believed that the ZrO 2  additions cause a decrease of the size of the pores of the ceramic, and that both the increased density and the strengthening are consequences of this decrease. 
     It will be apparent that various changes and modifications can be made from the specific details of the invention as described above without departing from the spirit and scope thereof as defined in the appended claims.