Dielectric ceramics composite material

Abstract: A dielectric ceramic composite material comprising a dielectric ceramics and a glass having a softening temperature lower than the sintering temperature of the dielectric ceramics, wherein said particles of the dielectric ceramics are randomly dispersed in a matrix of the glass. This composite material can he formed by molding a mixture of the dielectric ceramics powder and glass powder at first, and by firing this mold (including a film thereof) at the softening temperature of the glass or higher. The obtained dielectric ceramics composite material can be extensively utilized as various ceramic functional elements or electronic components incorporated in various piezoelectric, pyroelectric, ferroelectric memory, actuator elements and many others.

Description: The present invention relates to a ceramics composite material having dielectric properties. More particularly, this relates to a ferroelectric ceramics composite material to constitute piezoelectric elements applied to electric filters, oscillators, actuators and others, pyroelectric elements applied to infrared sensors and others, and ferroelectric memory elements applied to non-volatile RAMs and others. This invention relates also to an electrostrictive ceramics composite material to constitute electronics components incorporated in positioning devices of precision instruments, actuators incorporated in video tape-recorders for auto-tracking, and others. The ferroelectric ceramics such as piezoelectric ceramics belong to the family of dielectric ceramics, and it has been known that it can be made of either a binary system ceramics such as Pb(Ti, Zr)O₃, ternary system ceramics such as Pb(Mg 1/3 Nb 2/3 ) X Ti Y Zr Z O₃, or a quadruple system ceramics such as Pb(Zn 1/3 Nb 2/3 ) A (Sn 1/3 Nb 2/3 ) B Ti C Zr D O₃. Almost all constituting elements of these ceramics have ceramics compositions, and these can be obtained by molding the raw ceramics materials or calcined powders of these into a desired form, and firing the mold at a high temperature. On the other hand, ferroelectric ceramics composites can be derived by mixing the powder of above cited ceramics into organic material such as rubber or epoxy resin, and can be produced through a relatively low temperature manufacturing process. Since the conventional ferroelectric ceramics have to be fired at a relatively high temperature ranging from 1100 to 1300°C, only refractory metal such as platinum can be employed as the internal electrodes of the ceramics elements such as a piezoelectric element and a pyroelectric element. Moreover, since these ceramics can hardly be formed into films, only refractory metal such as platinum or heat-resistive ceramics can be used as the forming substrate thereof. On the other hand, since the ferroelectric ceramics composites comprised of ferroelectric ceramics and organic material are definitely disadvantageous in terms of their low heat-resistance and low mechanical Q factors, these can hardly be used as the ceramics elements of oscillators or filters. Meanwhile, as for the electrostrictive ceramics which is a family of dielectric ceramics, the binary system ceramics such as Pb(Mg 1/3 Nb 2/3 ) X Ti Y O₃, and ternary system ceramics such as Pb(Ni 1/3 Nb 2/3 )O₃ -PbTiO₃-Ba(Zn 1/3 Nb 2/3 )O₃ had been known by the Japanese Patent Publication No. 61-31926. Almost all the constituting elements of these ceramics are of ceramic compositions also, and these ceramics can be obtained by molding the raw ceramics materials or calcined powders of these into a desired form, and firing the mold at a high temperature. Meanwhile, electrostrictive ceramics composites can be derived by mixing the powder of above cited ceramics into an organic material such as rubber or epoxy resin, and can be produced through a relatively low temperature manufacturing process. Since actuator elements utilizing the electrostrictive ceramics require no polarizing process afterward, and show no hysteresis in elecric field vs strain, less deterioration of characteristics by aging, and higher heat resistance over the one utilizing the conventional piezoelectric ceramics, the actuator elements made of these ceramics are now extensively employed in various actuators. Since the firing temperature of conventional electrostrictive ceramics is relatively high, and it is within a range from 1100 to 1300°C, only refractory platinum can be employed as the internal electrodes of these actuator elements. In addition to the above, since these electrostrictive ceramics can hardly be formed into films, and the forming substrate can be constituted of only refractory platinum or highly heat resistive ceramics. On the other hand, since the electrostrictive ceramics composites comprised of electrostrictive ceramics and organic material are definitely disadvantageous because of their low heat resistance and low elastic constants, so that these can hardly withstand against high amplitude mechanical stresses. GB-A-2161647 discloses a piezo-electric device comprising a thin layer of piezo-electric ceramic material mounted on the substrate. In this device the piezo-electric ceramic material is a composition of a piezo-electric ceramic in powder form within a glass like binding agent. The present invention provides a ceramic composite material comprising: 10 to 90% by volume of a ferro-electric ceramic material or an electrostricture ceramic material; 5 to 15% by volume of an inorganic whisker; and the remaining volume of a glass having a softening temperature lower than the sintering temperature of said ceramic material. The new ceramic composite material according to this invention has a high heat resistance and excellent dielectric properties, and further can advantageously be produced using a relatively low temperature manufacturing process. The ferroelectric ceramics employed here can be a binary system ceramics such as Pb(Ti, Zr)0₃, ternary system ceramics such as Pb(Mg 1/3 Nb 2/3 ) X Ti Y Zr Z O₃ (where X+Y+Z=1), a quadruple system ceramics such as Pb(Zn 1/3 Nb 2/3 ) A (Sn 1/3 Nb 2/3 ) B Ti C Zr D O₃ (Where A+B+C+D=1), or a ferroelectric ceramic composition such as BaTiO₃, PbTiO₃, PbNb₂O₆, (Na, K)NbO₃, etc. The electrostrictive ceramics employed here can be a binary system ceramics such as Pb(Mg 1/3 Nb 2/3 ) X Ti Y O₃ (where X+Y =1), ternary system ceramics such as Pb(Ni 1/3 Nb 2/3 )O₃-PbTiO₃-Ba(Zn 1/3 Nb 2/3 )O₃, or other electrostrictive ceramics composition. Furthermore, the glass employed here can be a glass of either PbO·B₂O₃, PbO·B₂O₃·SiO₂, PbO·ZnO·B₂O₃, ZnO·B₂O₃·SiO₂, or other system. The ceramics composite material of the present invention can be prepared by mixing the powder of dielectric ceramics, the inorganic whisker and the powder of glass having a softening temperature lower than the sintering temperature of the dielectric ceramics, and by firing the mixture, Since it can be fired at a temperature close to the softening temperature of the glass powder (e.g., in a range from 300 to 800°C), the ceramics composite material can be prepared at a temprerature considerably lower than the sintering temperature of conventional ceramics comprised of purely dielectric ceramics, and this fact is advantageous from the aspect of manufacturing various ceramic elements. For an instance, stainless steel or such which is less heat resistive can be used as a substrate forming the ceramics composite materials of the invention. Comparing with the conventional ceramics composite materials prepared by mixing the powder of dielectric ceramics into organic resin, the ceramics composite material of the invention is superior than the former in respect of the heat resistance because no organic material which are subject to thermal deterioration is included therein. Therefore, the ceramics composite material of the invention can be extensively utilized to construct various piezoelectric, pyroelectric, ferroelectric memory, and actuator elements. Since its relatively low firing temperature is particularly advantageous to construct ceramics elements by coating the ceramics composite on a substrate and by firing this afterward. Moreover, since the ceramics composite material of the invention can be produced by using very fine dielectric ceramics powder and glass powder having very small average particle sizes, the elements can be made into a form of very thinfilm. Fig. 1 is a schematic sectional view of the invented ceramics composite material comprising a dielectric ceramics and a glass, and this shows its structure. Fig. 2 is a schematic sectional view of the piezoelectric, pyroelectric, or ferroelectric element made of the invented ceramics composite material comprising a ferroelectric ceramics and a glass. This shows its fundamental structure. Fig. 3 is a schematic sectional view of the actuator element made of the invented ceramics composite material comprising a electrostrictive ceramics and a glass. This shows its fundamental structure. Now a ferroelectric ceramics composite material consisted of a ferroelectric ceramics and a glass, is explained in the following for its detail. As shown in Fig. 1, the ferro-electric ceramics composite material 1 consists of particles of ferroelectric ceramics 2 which are randomly dispersed into a matrix of glass 3. The ceramics composite material 1 having the above shown structure can be prepared by mixing powders of ferroelectric ceramics and glass having a softening temperature lower than the sintering temperature of said ceramics, and by firing the mixture at a temperature lower then the sintering temperature of the ceramics and equal or higher than the softening temperature of the glass. Since only the glass powder melts and no change of the ceramics particles is produced at that temperature range, the particles of ferroelectric ceramics 2 are evenly dispersed and fixed in the matrix of glass 3. The average particle size of the ferroelectric ceramics 2 in this case is desirable to 2 microns(micron meters) or smaller in order to attain a high packing density of the ceramics composite material 1. When the ceramics powder having an average particle size of 0.6 microns or smaller is employed, the ceramics composite material 1 having an extremely high packing density of 98% or more to the theoretically attainable density can be obtained. In contrast to the above, when ceramics powder having an average particle size more than 2 microns is employed, ceramics composite material 1 having a lower packing density, or porous composite material, is produced. Satisfactory results will be obtained when ferroelectric ceramics powder having an average particle size exceeding the critical particle size of the ferroelectricity is employed. The volume proportion between the ferroelectric ceramics and the glass is arbitrary determined according to the desired ferroelectric characteristics. Howoever, an excessively high volume of the ferroelectric ceramics may result in inadequate sintering because of the lower firing temperature. On the other hand, an excessively small volume of it may result in an inadequate electrical characteristics. Therefore, the volume proportion of the ferroelectric ceramics in the ceramics composite material is desirable to set within a range from 10 to 90%. As for the ferroelectric ceramics mentioned above any of the ferroelectric ceramics can be employed. More concretely, any of the binary system ceramics having a composition such as Pb(Ti, Zr)O₃, ternary system ceramics composition such as Pb(Mg 1/3 Nb 2/3 ) X Ti Y Zr Z O₃ (where X+Y+Z=1), the quadruple system ceramics composition such as Pb(Zn 1/3 Nb 2/3 ) A (Sn 1/3 Nb 2/3 ) B Ti C Zr D O₃ (where A+B+C+D=1), or the ferroelectric ceramics composites containing BaTiO₃, PbTiO₃, PbNb₂O₆, (Na, K)NbO₃, etc., can be employed. As for the glass 3 mentioned above any of the glass materials having a softening temperature lower than the sintering temperature of the ferroelectric ceramics can be employed. lore concretely, the employment of any of the glasses such as PbO·B₂O₃, PbO·B₂O₃·SiO₂, PbO·ZnO· B₂O₃, ZnO·B₂O₃·SiO₂, or other system, is desirable. Furthermore, the employment of a crystallized glass derived from the above-mentioned glass is highly desirable because of its possible higher heat resistance of the obtained ceramics composite material. The employment of a glass having a high chemical stability and a thermal expansion coefficient close to that of the ferroelectric ceramics is also highly desirable. An electrostrictive ceramics composite material can be derived by employing an electrostrictive ceramics instead of the above-described ferro-electric ceramics. The electrostrictive ceramics mentioned here can be a binary system ceramics sush as Pb(Mg 1/3 Nb 2/3 ) X Ti, Y O₃ (where X+Y=1), ternary system ceramics sush as Pb(Ni 1/3 Nb 2/3 )O₃-PbTiO₃-Ba(Zn 1/3 Nb 2/3 )O₃, or other electrostrictive ceramics compositions. The desirable average particle size and the volume proportion of the electrostrictive ceramics in this case are identical with those of the case of ferroelectric ceramics composites. That is, the average particle size of the electrostrictive ceramics is desirable to 2 microns or smaller and preferably 0.6 microns or smaller for attaining a dense packing density thereof. In contrast to the above, the lower limit of average particle size is determined by critical particle size of electrostriction. The desirable volume proportion in this case is within a range from 10 to 90% also. Although the above explanation has been made for the ceramics composite material consisted of ferroelectric cermics (or electrostrictive ceramics) and glass, the ceramics composite material can be obtaind by employing these constituting ceramics and glass as the main materials, and other ceramics materials such as alumina, zirconia, titania, or others can be added thereto so far as these materials do not obstruct the purpose of the invention. A ceramics composite material of the invention comprised of the above described dielectric ceramics (ferroelectric ceramics or electrostrictive ceramics), glass and inorganic whiskers is then explained below. The objective of the addition of inorganic whiskers is to improve the mechanical strength such as the flexural strength, and a proper amount of the whiskers of magnesia, zirconia, SiC, Si₃N₄, ZnO, potassium titanate, barium titanate, strontium titanate, or other ceramics can be employed. Besides, the fiber of glass such as heat-resistive silica glass can be employed as the wiskers. The size of the employed whiskers is preferably within a range from 2 to 50 microns. The whiskers having a fiber length more than 50 microns may tend to lower the packing density, and ferroelectric or electrostrictive properties, the whiskers having a length less than 2 microns may contribute very little to improve the flexural strength of the composite. Beside the above, the employment of whiskers having a length proportionally shorter to the average particle size of dielectric ceramics is recommendable. The amount of whisker addition is desirable to 15 volume% or less for the dielectric ceramics composite, otherwise, the ferroelectric or electrostrictive properties will be sacrificed. Several examples of the invention and other exemplary materials are now shown in the followings. Example 1(not part of the invention) In preparing the first examples a ferro-electric calcined powder material of Pb(zn 1/3 Nb 2/3 ) 0.09 (Sn 1/3 Nb 2/3 ) 0.09 Ti 0.42 Zr₀. ₄₀O₃ ceramics added by 0.5 wt% of MnO₂, which was prepared by mixing its raw powder materials, calcining the mixture at 1250°C for two hours and pulverizing down into particles having an average size of about 4 microns by means of a ball-mill, was mixed with the powder of PbO·B₂O₃ system CF-8 glass having an average particle size of 3.8 microns and incluing a small amount of ceramics, manufactured by Nippon Electric Glass Co., Ltd., at a volume ratio shown in Table 1. After ethanol as a dispersive medium was added to the mixture of these powders, the mixture was pulverized down to a powder having an average particle size of about 0.2 microns by using a media agitating mill (Motor Mill M50, manufactured by Eiger Engineering, Ltd., wherein zirconia balls having an average diameter of 0.4 mm were used and the mill was driven at a rim speed of 10 m/s), and the mixture was dried afterward. The product was then granulated by using pure water, and the granules were sized by using a 500 micron filter. Then, thus obtaind granules were pressed into a die to from a disk having a diameter of 13 mm and thickness of about 1 mm. The ferroelectric ceramics composite samples specified by Nos. 2 to 7 were obtained by firing the disk in an electric furnace at the firing temperature shown in Table 1 for two hours. Both the temperature increment and decrement rates employed thereat were 400°C per hour. Then, Cr-Au double layered electrodes were deposited on both sides of the fired disk, and the piezoelectric elements having a structure shown in Fig. 2 were prepared by applying a DC electric field of 3 kV/mm thereon in a silicon oil bath kept at 100°C for 30 minutes for polarization. In Fig. 2, 1 is a ferroelectric ceramics composite, and 4 is a pair of electrodes. The dielectric constants, electromechanical coupling coefficients, dielectric loss-tangents of these sample disks were determined, and the results of these are tabulated in Table 1. However, No. 1 and No. 8 sample refer to the ceramics samples prepared for the purpose of contrast only. As seen in Table 1, although the coupling coefficients and dielectric constants of the ferroelectric ceramics composite samples specified by Nos. 2 to 7 are slightly lower than those of No. 8 contrast sample, these can be prepared at firing temperatures considerably lower than that for the contrast. Moreover, if the No. 8 contrast sample is fired at a temperature lower than 1000°C, it will not be sintered and show zero coupling coefficient, i.e., no piezoelectricity. The average particle size of the ferroelectric ceramics particles in samples Nos. 2 to 7 determined by microscopic observation is about 0.2 microns, and this is identical with that of the unfired samples. An experiment same as the above was conducted for the cases where the average particle sizes of the ferroelectric ceramics powder pulverized by using the media agitating mill were different from those of afore-mentioned samples, and the ferroelectric ceramics powder and the glass powder were mixed at a ratio same as the one employed to prepare No. 5 sample. The densities of the fired samples made of the pulverized and mixed powder having average particle sizes of 1.9, 0.92, 0.58, 0.22 and 0.052 microns were 92, 94, 98, 98, and 98% of the respective theoretical densities. Thus, densities of more than 90% of the theoretical densities were obtained when powders having average particle sizes of 2 microns or smaller were employed. Particularly when a powder having an average particle size of 0.6 microns or smaller was employed, a ceramics composite having an extremely high density of 98% was obtained. In the above-explained examples, a method to prepare the ceramics composites from the mixed powder of ferro-electric ceramics and glass which was pulverized together, were shown. However, the identical results are obtained by mixing the powder of ferroelectric ceramics and the powder of glass which are independently pulverized. When this manufacturing method was employed, the respective densities of the fired ceramics composites obtained by using powders having average particle sizes of 4.2, 1. and 0.45 microns were 69, 88, and 94% respectively to the theoretical densities. In this case, high density ceramics composites are obtained also when powder having an average particle size of 2 microns or smaller is employed. The critical particle size showing the ferroelectricity was found to be approximately 0.02 microns in the cases of ferroelectric ceramics composites of the present example, so that the ferroelectric ceramics composites can be obtained when a ferroelectric ceramics powder having an average particle size of about 0.02 microns or more is employed. The displacement of the piezoelectric elements in the thickness direction was determined by using a differential transformer type displacement meter when a DC electric field of 2 kV/mm was applied between the electrodes of the polarized No. 5 specimen. A displacement of 0.38 microns in the thickness direction was observed so that a function as a mechanical actuator was confirmed. Furthermore, the terminal voltage generated between the electrodes when a temperature change was given to the No. 5 sample, was measured. Since this experiment confirmed a generation of voltage proportional to the magnitude of the temperature change, a function as a pyroelectric element of this element was confirmed. The D-E hysteresis loop of the No. 5 ceramics composite was also measured, and the results showed an coercive force E c of 2.3 kV/mm and a residual polarization P r of 14.6 µC/cm² so that a function of the ceramics composite as a ferroelectric memory element was confirmed. Example 2 In preparing Example 2 according to the invention, a ferroelectric calcined powder material of Pb(Zn 1/3 Nb 2/3 ) 0.09 (Sn 1/3 Nb 2/3 ) 0.09 Ti₀. ₄₂Zr₀. ₄₀O₃ ceramics added by 0.5 wt% of MnO₂, which was prepared by mixing its raw powder materials, calcining the mixture at 1250°C for two hours and pulverizing down into particles having an average size of about 4 microns by means of a ball-mill, was mixed with the glass powder employed to prepare Example 1 at the ratios shown in Table 2. After ethanol as a dispersive medium was added to the mixture of these powders, the mixture was pulverized down to a powder having an average particle size of about 0.2 microns by using a media agitating mill same as the one used in Example 1, and the mixture was dried afterward. Then, magnesia whiskers having an average diameter of about 2 microns and an average length of 24 microns were shown in Table 2, and the mixture was made into granules by using pure water, and the granules were sized by passing through a 500 micron mesh filter. The granules were pressed into a die to form a disk having a diameter of 13 mm and a thickness of about 1 mm. The ferroelectric ceramics composite samples specified by Nos. 9 to 11 were obtained by firing the disks in an electric furnace at the firing temperature shown in Table 2 for two hours. Both the temperature increment and decrement rates employed thereat were 400°C per hour. Then, Cr-Au electrodes were deposited on both sides of the fired disk, and the ferroelectric ceramic disks were prepared by applying a DC electric field of 3 kV/mm thereon in a silicon oil bath kept at 100°C for 30 minutes for polarization. The dielectric constants, electromechanical coupling coefficients, dielectric loss-tangents and flextural strengths of these sample disks were meassured, and the results of these are tabulated in Table 2. However, sample No. 9 refers to a ceramics sample containing no whiskers, and this is used as a contrast only. As showm in Table 2, the flexural strengths of the ferroelectric ceramics composite samples containing whiskers specified by Nos. 10 and 11 are higher than the one without containing the whiskers. Example 3 Two sample Nos. 12 and 13 were prepared by using the materials employed to prepare the sample No. 3 in Example 1 and the sample No. 10 in Example 2, except that a crystallized glass (PbO·ZnO·B₂O₃ system glass LS-7105, having an average particle size of 7.5 microns and a softening temperature of 400°C, manufactured by Nippon Electric Glass Co.,Ltd) was employed in this case. The ferroelectric ceramics composite samples were manufactured by the method employed in Examples 1 and 2. The electrical characteristics such as the dielectric constants and the deformation temperature of these samples were measured, and the results of these are tabulated in Table 3 together with the ones of sample Nos. 3 and 10. However, the deformation temperature is defined as the temperature at which the edge of disk sample is rounded off after it is kept for a period of 5 hours. No. Type of glass Firing temp. (°C) Coupl. coef. Kp Dielectric constant at 1 kHz Dielectric loss-tang at 1 kHz Deformation temp. (°C) 3 Amorphous glass 450 0.15 176 0.0049 560 12 Crystallized glass 450 0.16 201 0.0067 700or higher 10 Amorphous glass 450 0.30 305 0.0039 560 13 Crystallized glass 450 0.32 330 0.0051 700or higher As shown in Table 3, the deformation temperature of ferroelectric ceramics composites can be substantially higher by using a crystallized glass over the case where amorphous glass is employed. This means a substantially higher heat resistance of the ferroelectric ceramics composite which can withstand against mechanical machining conducted at a high temperature or high-temperature heattreatment. Example 4 (not part of the invention) In preparing Example 4, a calcined powder of 0.5Pb(Ni 1/3 Nb 2/3 )O₃-0.4PbTiO₃-0.1Ba(Zn 1/3 Nb 2/3 )O₃ electrostrictive ceramics was prepared by calcining a mixture of its raw materials at 1200°C for two hours, and it was pulverized into particles having an average size of about 3.2 microns by means of a ball-mill. Then, it was mixed with the glass powder employed to prepare samples of Example 1 at the ratios shown in Table 4. After ethanol as a dispersive medium was added to tne mixture of these powders, the mixture was pulverized down to a powder having an average particle size of about 0.2 microns by using a media agitating mill same as the one used in Example 1, and the mixture was dried afterward. Then, the mixture was made into granules by using pure water, and the granules were sized by using a 500 micron mesh filter. The granules were then pressed into a die to form a rectangular plate having a length of 10 mm, a width of 5 mm and a thickness of about 1 mm. The samples of electrostrictive ceramics composite specified by Nos. 15 to 20 shown below were obtained by firing the plates in an electric furnace at the firing temperature shown in Table 4 for two hours. Both the temperature increment and decrement rates employed thereat were 400°C per hour. Then, Cr-Au double-layered electrodes were deposited on both sides of the fired disk, and the electrostrictive ceramic disks were prepared by applying a DC electric field of 2 kV/mm thereon for polarization. The displacements along the lengthwise direction were measured by using a differential transformer type displacement meter, and the results are tabulated in Table 4 wherein the displacement in % is expressed by a displacement ratio against the sample length before the electric field is applied, and the samples Nos. 14 and 21 are contrasts. No. Mixing Ratio (in Vol.%) Powder of ferro-electric ceramics Powder of glass Firing temp. (°C) Displacement (%) 14 0 100 430 0.0 15 10 90 400 0.002 16 20 80 450 0.009 17 40 60 450 0.011 18 60 40 500 0.017 19 80 20 500 0.020 20 90 10 550 0.018 21 100 0 1120 0.035 As seen from Table 4, the displacements of the electrostrictive ceramics composite samples Nos. 15 to 20 are slightly lower than that of the contrast sample No. 21, but these can be fired at temperatures substantially lower than that of the contrast. Moreover, if the contrast sample No. 21 is fired at a temperature less than 1000°C, it is not sintered. The average particle size of the electrostrictive ceramics particles in samples Nos. 15 to 20 determined by microscopic observation is about 0.2 microns, and this is identical with that of the unfired samples. An experiment same as the above was conducted for the cases where the average particle sizes of the electrostrictive ceramics powder pulverized by using the media agitating mill were different from those of the afore-mentioned samples, and the electrostrictive ceramics powder and the glass powder were mixed at a ratio same as the one employed to prepare No. 18 sample. The densities of the fired samples made of the pulverized and mixed powder having average particle sizes of 2.4, 1.12, 0.56, 0.19 and 0.063 microns were 93, 94, 98, 99 and 98% of the respective theoretical densities, Thus, densities of more than 90% of the theoretical densities are obtained when powders having average particle sizes of 2.4 microns or smaller were employed. Particularly when a powder having an average particle size of 0.6 microns or smaller was employed, a ceramics composite having an extremely high density of 98% or more was obtained. In the above-explained Example 4, a method to prepare the ceramics composites from the mixed powder of electrostrictive ceramics and glass which was pulverized together, were shown. However, the identical results are obtained by mixing the powder of electrostrictive ceramics and the powder of glass which are independintly pulverized. When this manufacturing method was employed, the respective densities of the fired ceramics composites obtained by using powders having average particle sizes of 3.2, 1.9 and 0.51 microns were 70, 89 and 93% respectively to the theoretical densities. In this case, high density ceramics composites are obtained also when powder having an average particle size of 2 microns or smaller is employed. In the above-explained Example 4, the critical particle size showing electrostricity in the electrostrictive ceramics composites was found to be about 0.02 microns, so that an electrostrictive ceramics composite can be obtained when electrostrictive ceramics particles having an average particle size of 0.02 microns or more is employed. Example 5 In preparing Example 5 according to the invention, a calcined powder of 0.5Pb(Ni 1/3 Nb 2/3 )O₃-0.4PbTiO₃-0.1Ba(Zn 1/3 Nb 2/3 )O₃ electrostrictive ceramics which was prepared by mixing its raw materials, calcining the mixture at 1200°C for two hours and pulverizing into particles having an average size of about 3.2 microns by means of a ball-mill, was mixed with the glass powder employed to perpare samples of Example 1 at the ratios shown in Table 5. After ethanol as a dispersive medium was added to the mixture of these powders, the mixture was pulverized down to a powder having an average particle size of about 0.2 microns by using a media agitating mill same as the one used in Example 1, and the mixture was dried afterward. Then, magnesia whiskers having an average diameter of about 2 microns and an average length of about 24 microns were added to the dried mixture, and the mixture was made into granules by using pure water, and the granules were sized by using a 500 micron mesh filter. The glanules were then pressed into a die to from a rectangular plate having a length of 10 mm, a width of 5 mm and a thickness of about 1 mm. The samples of electrostrictive ceramics composite specified by Nos. 23 and 24 shown below were obtained by firing the plates in an electric furnace at the firing temperature shown in Table 5 for two hours. Both the employed temperature increment and decrement rates were 400°C per hour. Then, Cr-Au double-layered electrodes were deposited on both sides of the fired disk, and the electrostrictive ceramic disks were prepared by applying a DC electric field of 2 kV/mm thereon for polarization. The displacements along the lengthwise direction were measured by using the previously mentioned differential transformer type displacement meter and the flexural strengths were measured. The results of these are tabulated in Table 5 wherein the sample No. 22 is a contrast in which no whiskers are included. No. Mixing Ratio (in Vol.%) Powder of electrostrictive ceramics Powder of glass Magnesia whiskers Firing temp. (°C) Flexural Strength (MPa) Displacement (%) 22 50 50 0 450 63 0.018 23 50 45 5 450 88 0.017 24 50 40 10 450 101 0.016 Table 5 shows that the fluxural strengths of Nos. 23 and 24 electrostrictive ceramics composite samples containing whiskers are considerably higher than that of the contrast sample No. 22 containing no whiskers. Example 6 Two samples Nos. 25 and 26 were prepared by using the materials employed to prepare No. 16 sample in Example 4 and No. 23 sample in Example 5, except that a crystallized glass (PbO·ZnO·B₂O₃ system glass LS-7105, having an average particle size of 7.5 microns and a softening temperature of 400°C, manufactured by Nippon Electric Glass Co., Ltd.) was employed in this case. The electrostrictive ceramics composite samples were manufactured by the method substantially identical with the one employed in Example 4 and 5. The displacements and the deformation temperatures of these samples were measured, and the results of these are shown in Table 6 together with the ones of Nos. 16 and 23. However, the deformation temperature is defined as the temperature at which the edge of disk sample is rounded off after it is kept for a period of 5 hours. No. Type of glass Firing temp. (°C) Displacement (%) Deformation temperature(°C) 16 Amorphous glass 450 0.009 560 25 Crystallized glass 450 0.010 700 or higher 23 Amorphous glass 450 0.017 560 26 Crystallized glass 450 0.020 700 or higher As shown in Table 6, the deformation temperatures of electrostrictive ceramics composites comprised of crystallized glass are substantially higher than the samples comprised of amorphous glass. This means a substantially higher heat resistance of the electrostrictive ceramics composite which can withstand against mechanical machining conducted at a high temperature or high-temperature heattreatment. Example 7 (not part of the invention) In preparing Example 7 a calcined powder of 0.5Pb(Ni 1/3 Nb 2/3 )O₃-0.4PbTiO₃-0.1Ba(Zn 1/3 Nb 2/3 ) 03 electrostrictive ceramics which was prepared by mixing its raw materials, calcining the mixture at 1200°C for to hours and pulverizing into particles having an average size of about 3.2 microns by means of a ball-mill, was mixed with the glass powder employed to prepare samples of Example 1 at a ratio employed to prepare No. 17 sample in Table 4. After ethanol as a dispersive medium was added to the mixture of these powders, the mixture was pulverized down to a powder having an average particle size of about 0.2 microns by using a media agitating mill same as the one used in Example 1, and this slurry was dip-coated on the both sides of a stainless-steel plate having a length of 20 mm, a with of 5 mm, and a thickness of 0.05 mm leaving a 5 mm-long space on the end of plate. The coated electrostrictive ceramics composite layer was dried and fired at a temperature of 450°C for two hours. Cr-Au double layered electrodes were deposited on both sides of the thus obtained electrostrictive ceramic thin film having an average thickness of 0.045 mm, saving 1 mm wide strip regions on the peripheral regions on both sides. And then, thus-obtained electrostritive element was mounted into an actuator element. A schematic sectional view of the actuator element is shown in Fig. 3 wherein the numeral 10 is an electrostrictive ceramics composite film formed on the stainless steel plate 12, 11a and 11b are the Cr-Au electrodes formed on the electrostrictive ceramics composite film 10, and 13 is a mounting block on which an end 14 of the electrostrictive element is mounted. The electrostrictive element is mounted on the mounting block 13 by means of an epoxyresin adhesive. An application of DC potential between the electrode 11a or 11b and the stainless steel plate 12 will cause a displacement of the free-end 15 of the element in right or left direction while the mounted end 14 is fixed. The flexure displacement of the free-end 15 of the element produced by an application of 2 kV/mm electric field between the electrode 11a and the stainless steel plate, was measured by means of an optical microscope, and a leftward displacement of the free-end of 122 microns was confirmed. Likewise, a rightward displacement of 105 mm was observed when the same electric field was applied between the electrode 11b and the stainless steel plate 12.

Claims: A ceramic composite material comprising: 10 to 90% by volume of a ferro-electric ceramic material or an electrostrictive ceramic material; 5 to 15% by volume of inorganic whiskers; and the remaining volume of a glass having a softening temperature lower than the sintering temperature of said ceramic material. A ceramic composite material according to Claim 1, in which the average length of said inorganic whisker is in the range 2 to 50µm.

Inventors: KUGIMIYA KOICHI, NISHIDA MASAMITSU, KUGIMIYA, KOICHI, NISHIDA, MASAMITSU, KUGIMIYA, KOICHI, 2-1-32, CHOKOJIMINAMI,, NISHIDA, MASAMITSU 3-13-20, KOMATSU,
Applicants: MATSUSHITA ELECTRIC IND CO LTD, MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.
Application year: 1992
Main classification: H01L41
IPC codes: H01L41