Abstract:
Disclosed is a BaO-xTiO 2  dielectric ceramic composition (x=3.5 to 4.5) containing BaTi 4  O 9  and Ba 2  Ti 9  O 20 , wherein the content ratio of Ba 2  Ti 9  O 20  {Ba 2  Ti 9  O 20  /(BaTi 4  O 9  +Ba 2  Ti 9  O 20 )}obtained by a X-ray diffraction maximum peak height integration method described below is less than 0.19, 
     content ratio of Ba 2  Ti 9  O 20  ={a peak height ascribed to the (421) face of Ba 2  Ti 9  O 20  +a peak height ascribed to the (222) face thereof}/[{a peak height ascribed to the (200, 140) face of BaTi 4  O 9  +a peak height ascribed to the (121) face thereof+a peak height ascribed to the (230, 150) face thereof}+{a peak height ascribed to the (421) face of Ba 2  Ti 9  O 20  +a peak height ascribed to the (222) face thereof}]. 
     In the above dielectric ceramic composition, it is possible to prevent the occurrence of hexagonal pattern cracks and hence to improve the yield.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a BaO-xTiO 2  dielectric ceramic composition, and more particularly, to a BaO-xTiO 2  dielectric ceramic composition having a Ba 2  Ti 9  O 20  /(BaTi 4  O 9  +Ba 2  Ti 9  O 20 ) ratio of less than 0.19 for preventing the occurrence of hexagonal pattern cracks. 
     The present invention is applicable for impedance matching or the like in a dielectric resonator (particularly, one with a large size of 50 mmφ or more), a microwave integrated circuit board or impedance matching in various microwave circuits in a microwave region. 
     2. The Related Art of the Invention 
     There have been known various BaO-xTiO 2  dielectric ceramic compositions, for example, disclosed in Japanese Patent Publication No. hei 1-37807, Japanese Patent Laid-open No. sho 61-10806, Japanese Patent Laid-open No. sho 61-10807, Japanese Patent Laid-open No. sho 63-117957 and the like. 
     However, the conventional dielectric ceramic compositions described above have a disadvantage of causing hexagonal pattern cracks on the surface of the resonator in a baking process thereby significantly reducing the yield. In particular, the large size resonator has such a tendency to cause the above cracks. 
     SUMMARY OF THE INVENTION 
     To solve the above problem, the present invention has been made, an object of which is to provide a BaO-xTiO 2  dielectric ceramic composition capable of preventing hexagonal pattern cracks while achieving the practical characteristics. 
     The present applicants have examined the mechanism for the occurrence of the hexagonal pattern cracks in the BaO-xTiO 2  dielectric ceramic composition, and consequently have found the fact that there is a correlation between the content ratio of Ba 2  Ti 9  O 20  and the occurrence of the cracks. 
     Namely, in a preferred mode of the present invention, there is provided a BaO-xTiO 2  dielectric ceramic composition containing BaTi 4  O 9  and Ba 2  Ti 9  O 20  (X=3.5 to 4.5), wherein the content ratio of Ba 2  Ti 9  O 20  {Ba 2  Ti 9  O 20  /(BaTi 4  O 9  +Ba 2  Ti 9  O 20 )}obtained by a X-ray diffraction maximum peak height integration method is less than 0.19. 
     The following five specified peak values are used in the above X-ray diffraction maximum peak height integration method: the first and second peak values respectively ascribed to the (421) face and (222) face of Ba 2  Ti 9  O 20  ; the third, fourth and fifth peak values respectively ascribed to the (200, 140) face, the (121) face, and the (230, 150) face of BaTi 4  O 9 . Thus, each maximum peak height is obtained, and thereby the content ratio of Ba 2  Ti 9  O 20  {Ba 2  Ti 9  O 20  /(BaTi 4  O 9  +Ba 2  Ti 9  O 20 )}  is calculated. 
     In addition, the value of [0.19] appearing in the wording [the content ratio of Ba 2  Ti 9  O 20  is less than 0.19] means the value obtained by the X-ray diffraction maximum peak height integration method. Accordingly, even using the same sample, in the case of obtaining the content ratio of Ba 2  Ti 9  O 20  by another method of, for example, integrating the area of the specified peak, the value of [0.19], that is, the boundary value is changeable to a different value depending on the method. 
     When the variable &#34;x&#34; is less than 3.5, the temperature coefficient of the resonance frequency (hereinafter, referred to as τ f ) is 50 ppm/°C. or more. When the variable &#34;x&#34; is more than 4.5, τ f  tends to approach the value of 0 but the unloaded Q (hereinafter, referred to as Qu) is reduced. Accordingly, either case is unfavorable in practical use. Also, when the content ratio of Ba 2  Ti 9  O 20  is not less than 0.19, unfavorably, there occur the hexagonal pattern cracks. 
     Also, the composition of the present invention may contain at least one of 5 to 20 pts. wt. of ZnO and 0.5 to 1 pts. wt. of Ta 2  O 5  relative to 100 pts. wt. of BaO and TiO 2 . It is well known that the addition of ZnO shifts the value of τ f  to the negative side while reducing the relative dielectric constant (hereinafter, referred to as ε r ). However, when the content of ZnO is less than 5 pts. wt., the above function is small and thus the value of τ f  is made larger. Meanwhile, when the content of ZnO is more than 20 pts. wt., conversely, the value of τ f  is made excessively small in the negative side. Also, the addition of Ta 2  O 5  is effective to improve the Qu value. When the content of Ta 2  O 5  is less than 0.5 pts. wt., the Qu value is almost similar to the case of no addition, whereas when being more than 0.5 pts. wt., the Qu value is preferably increased 1.3 to 1.4 times as much as the case of no-addition. Also, in excess of 1 pts. wt., the additional effect is saturated. In addition, by the suitable addition of both the components, it is possible to balance the values of ε r , Qu, and τ f . 
     The ceramic composition of the present invention may be manufactured by the steps of mixing specified starting materials at respective specified amounts and sintering the mixture. For example, a powder to be transformed into BaO after sintering and a TiO 2  powder in respective amounts corresponding to the desired composition are mixed, calcined and pulverized. The pulverized powder thus obtained is further mixed with a ZnO powder, a Ta 2  O 5  powder and the like in respective amounts corresponding to the desired composition, as required, and then calcined and pulverized. The resultant calcined powder is formed in a specified shape, and then baked. 
     In the dielectric ceramic composition of the present invention, it is possible to prevent the occurrence of hexagonal pattern cracks and hence to improve the yield. 
     Also, the composition of the present invention which may contain at least one kind of 5 to 20 pts. wt. of ZnO and 0.5 to 1 pts. wt. of Ta 2  O 5  relative to 100 pts. wt. of BaO and TiO 2 , is excellent in the performances of ε r , Qu, and τ f , and has practical and balanced performance. 
     Further, even in a large size dielectric ceramic body having an outside diameter of 50 mmφ or more, there occur no cracks. Therefore, the dielectric ceramic body may be utilized as large size dielectric resonator and may be practical and excellent in quality and strength. 
    
    
     BRIEF DESCRIPTION OF THE DRAWINGS 
     FIG. 1 is a graph showing the result of X-ray diffraction on the surface of a sample No. 1 in Example; 
     FIG. 2 is a graph showing the result of X-ray diffraction on the surface of a sample No. 2 in Example; 
     FIG. 3 is a graph showing the result of X-ray diffraction on the surface of a sample No. 5 in Example; 
     FIG. 4 is a graph showing the result of X-ray diffraction on the surface of a sample No. 8 in Example; 
     FIG. 5 is a graph showing the result of X-ray diffraction on the surface of a sample No. 10 in Example; 
     FIG. 6 is a graph showing the result of X-ray diffraction on the surface of a sample No. 22 in Example; and 
     FIG. 7 is a graph showing the result of X-ray diffraction on the surface of a sample No. 23 in Example; 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying drawings. The present invention will be more clearly understood with reference to the following example: 
     EXAMPLE 
     (1) Preparation of Sample 
     Powders of BaCO 3  and TiO 2  of 99.9% purity were weighed and mixed in specified amounts corresponding to each composition of [(BaO-xTiO 2 ), X; 3.8, 3.5, 4.1, 4.4]. After that, the mixture was primarily pulverized and mixed in dry by a mixer, and then calcined at 1100° C. in air for 2 hrs. and pulverized, to thus manufacture the first calcined powder. Further, in the case of further addition of powders of ZnO, Ta 2  O 5 , MnO 2  and WO 3 , as required, the ZnO powder and the like were added to the first calcined powder, and then mixed and calcined in the same manner as described above, to thus manufacture the second calcined powder. In addition, each added amount of ZnO, Ta 2  O 5 , MnO 2  and WO 3  is represented as weight (pts. wt.) to the whole BaO-xTiO 2  (100 pts. wt.). The addition compositions are shown in Tables 1 to 3. Table 1 shows such compositions that &#34;x&#34; is 3.8  and ZnO and Ta 2  O 5  are not contained. Table 2 shows such compositions that &#34;x&#34; is 3.5, 4.2 and 4.4, and ZnO and Ta 2  O 5  are not contained. Table 3 shows such compositions that &#34;x&#34; is 3.8 and ZnO and/or Ta 2  O 5 , and further MnO 2  or WO 3  are contained. 
     
                                           TABLE 1__________________________________________________________________________BaO--3.8TiO.sub.2 dielectric ceramic composition   sample (resonator) observed                      crack occurrence                               content ratio ofNo shape     baking condition                 portion                      state    Ba.sub.2 Ti.sub.9 O.sub.20__________________________________________________________________________1  200 mmφ        1230° C. × 15 hr                 surface                       hexagonal                               0.30   100 mmH   temperature rise                       pattern crack        15° C./hr2   50 mmφ        *1) 1 hr/charge                 surface                       OK      0.153   20 mmH   1230° C. × 15 hr                 surface                       hexagonal                               0.24        15° C./hr4  100 mmφ        1230° C. × 15 hr                 surface                       hexagonal                               0.31                       pattern crack5   40 mmH   temperature rise                       OK      0.16        15° C./hr6  200 mmφ        1170° C. × 8 hr                 surface                       hexagonal                               0.19                       pattern crack7  100 mmH   temperature rise                 surface                       hexagonal                               0.22        15° C./hr                       pattern crack8  200 mmφ        *2) 2 hrs/charge                 surface                       OK      0.14   100 mmH9  200 mmφ        *2) 4 hrs/charge                 surface                       hexagonal                               0.20   100 mmH                  pattern crack10 200 mmφ        1230° C. × 7 hr                 surface                       OK      0.18   100 mmH   temperature rise        26.4° C.__________________________________________________________________________ *1) maximum temperature of heat treatment in tunnel furnace is 1200° C. *2) maximum temperature of heat treatment in tunnel furnace is 1230° C. 
    
     
                                           TABLE 2__________________________________________________________________________BaO-- xTiO.sub.2 dielectric ceramic composition                observed                     crack occurrence                              content ratio ofNo x sample shape       baking condition                portion                     state    Ba.sub.2 Ti.sub.9 O.sub.20__________________________________________________________________________11 3.5200 mmφ       1330° C. × 15 hr                surface                     hexagonal                              0.28100 mmH       temperature rise                     pattern crack       15° C./hr12   200 mmφ       1330° C. × 15 hr                surface                     absence  0.14100 mmH       temperature rise       17.5° C./hr13 4.2200 mmφ       1240° C. × 8 hr                surface                     hexagonal                              0.38100 mmH       temperature rise                     pattern crack       15° C./hr14   200 mmφ       1240° C. × 8 hr                surface                     absence  0.10100 mmH       temperature rise       17.5° C./hr15 4.4200 mmφ       1220° C. × 10 hr                surface                     hexagonal                              0.42100 mmH       temperature rise                     pattern crack       20° C./hr16   200 mmφ       1220° C. × 10 hr                surface                     absence  0.12100 mmH       temperature rise       25° C./hr__________________________________________________________________________ 
    
     
                                           TABLE 3__________________________________________________________________________BaO-- 3.8TiO.sub.2 dielectric ceramic composition                        observed                             crack occurrence                                      content ratio ofNo assistant    sample shape           baking condition                        portion                             state    Ba.sub.2 Ti.sub.9 O.sub.20__________________________________________________________________________17 ZnO   200 mmφ           1250° C. × 4 hr                        surface                             absence  0.14   6 wt. pts    100 mmH           temperature rise 20° C./hr18 ZnO   200 mmφ           1250° C. × 4 hr                        surface                             absence  0.18   15 wt. pts.    100 mmH           temperature rise 20° C./hr19 Ta.sub.2 O.sub.5    200 mmφ           1270° C. × 4 hr                        surface                             absence  0.16   0.5 wt. pts.    100 mmH           temperature rise 20° C./hr20 Ta.sub.2 O.sub.5    200 mmφ           1270° C. × 4 hr                        surface                             absence  0.17   1 wt. pts.    100 mmH           temperature rise 20° C./hr21 ZnO   200 mmφ           1250° C. × 4 hr                        surface                             absence  0.15   6 wt. pts.    100 mmH           temperature rise 20° C./hr   Ta.sub.2 O.sub.5    200 mmφ           1230° C. ×  6 hr                        surface                             absence  0.14   0.5 wt. pts.    100 mmH           temperature rise 25° C./hr22 MnO.sub.2    200 mmφ           1230° C. × 7 hr                        surface                             absence  0.15   0.2 wt. pts.    100 mmH           temperature rise           26.4 ° C./hr23 WO.sub.3    200 mmφ           1230° C. × 6 hr                        surface                             absence  0.15   0.5 wt. pts.    100 mmH           temperature rise 25° C./hr24 MnO.sub.2    200 mmφ           1230° C. × 7 hr                        surface                             absence  0.15   0.2 wt. pts.    100 mmH           temperature rise   WO.sub.3     26.4° C./hr   0.2 wt. pts.25 ZnO   200 mmφ           1250° C. × 4 hr                        surface                             absence  0.18   20 wt. pts.    100 mmH           temperature rise 20° C./hr__________________________________________________________________________ 
    
     The above first or second calcined powder was combined with an organic binder in a suitable amount and an ion exchange water (260 to 500 g), being secondarily pulverized using alumina balls of 20 mm φ, and then pelletized by spraying and drying. Subsequently, the pelletized powder was formed at a pressure of 1000 kg/cm 2  into a cylindrical shape having the size corresponding to the diameter (outside diameter) and the height shown in each Table after baking (incidentally, the inside diameter is changeable within the range of 10 to 60 mm φ). 
     Next, the compact thus obtained was baked in air under the condition shown in each of Tables 1 to 3, and finally ground in the size shown in each Table, to thus form each of sample Nos. 1 to 25. In addition, Tables 1, 2 and 3 show the results in the case that &#34;x&#34; of (BaO-xTiO 2 ) are [3.8], [3.5, 4.2 and 4.4] and [3.8], respectively. Further, in Table 3, ZnO, Ta 2  O 5 , MnO 2  or WO 3  is added. 
     (2) Performance Estimation 
     In each sample, the state of causing cracks on the surface was observed by an optical microscope and a scanning electron microscope. Further, the surfaces (upper surface and barrel surface) were subjected to X-ray diffractometry, and thus the content ratio of Ba 2  Ti 9  O 20  {Ba 2  Ti 9  O 20  /(BaTi 4  O 9  +Ba 2  Ti 9  O 20 )} was obtained by a maximum peak height integration method. Each intensity of the X-ray diffraction was measured at room temperature under the condition that a time constant was 0.5 sec. and the rotational speed of a goniometer was 2θ=1°/mim using a CuKα ray which was generated at a tube voltage of 50 KV and a tube current of 80 mA and was made to pass through a slit of 1°, 1° and 0.15 mm and a Ni foil filter. In this case, as described above, with respect to Ba 2  Ti 9  O 20 , the peak intensities respectively ascribed to the (421) face and the (222) face were represented by the maximum peak heights from the background. Also, with respect to BaTi 4  O 9 , the peak intensities respectively ascribed to the (200, 140) face, (121) face and the (230, 150) face were represented by the maximum peak heights from the background. 
     Thus, the content ratio of Ba 2  Ti 9  O 20  was obtained by the following equation: 
     
         Content of Ba.sub.2 Ti.sub.9 O.sub.20 =(I.sub.(421) +I.sub.(222))/(I.sub.(421) +I.sub.(222) +I.sub.(200,140) +I.sub.(121) +I.sub.(230,150)) 
    
     The calculation of the above content ratio on the basis of, for example, the result shown in FIG. 4 is as follows: content ratio of Ba 2  Ti 9  O 20  =(A1 peak height+A2 peak height)/(A1 peak height+A2 peak height+B1 peak height+B2 peak height+B3 peak height). These calculated results are shown in Tables 1 to 3. Also, the graphs showing the results of X-ray diffraction on the sample Nos. 1, 2, 5, 8, 10, 22 and 23 are shown in FIGS. 1, 2, 3, 4, 5, 6 and 7, respectively. 
     
                       TABLE 4______________________________________Characteristics of BaO--xTiO.sub.2 dielectric ceramic composition                              temperature           relative           coefficient of sintered  dielectric                     Q.sub.u  resonance density   constant  value    frequencyNo    (g/cm.sup.3)           ε r                     (4.5 GHz)                              τ f (ppm/°C.)______________________________________ 2    4.692     34.5      4100     012    4.609     39.2      3060     +16.217    4.682     36.0      3100     +6.018    4.694     33.8      3200     020    4.690     38.5      4000     +18.021    4.658     35.8      3250     +6.822    4.698     34.6      4100     023    4.690     34.5      4300     024    4.608     34.5      4300     025    4.703     33.0      3000     -8.4______________________________________ 
    
     Further, in each sample shown in Table 4, the sintered density was measured by an Archimedes&#39; method, and also the values of ε r , Qu, and τ f  are measured by a parallel conductive plate type dielectric cylinder resonator method (TE 011  mode). The results are shown in Table 4. In addition, the resonance frequency lies near 4.5 GHz. 
     As a result, there occur hexagonal pattern cracks for the content ratio of Ba 2  Ti 9  O 20  not less than 0.19; but there occurs no hexagonal pattern crack for that less than 0.19. Even in a cylindrical sample having an outside diameter of 50 mm φor more, particularly, of 200 mm φ, there occur no cracks. In the terms of this point, the ceramic composition of the present invention is highly excellent in quality as compared with the conventional one. Also, even in the larger size ceramic composition having an outside diameter of 280 mm φ and a height of 130 to 140 mm, there occurs no crack. 
     In addition, as shown in Table 1, Ba 2  Ti 9  O 20  is a high temperature stable phase as compared with BaTi 4  O 9 , and thus tends to be excessively baked. Consequently Ba 2  Ti 9  O 20  is increased which promotes the tendency of causing the hexagonal pattern cracks. Also, it is considered that the occurrence ratio of Ba 2  Ti 9  O 20  is related to the heat quantity in high temperatures including not only the baking temperature (maximum value) and holding time but also the temperature rising speed. 
     Further, as shown in Table 4, each sample is excellent in the balance of the performances. Particularly, the following samples are preferable: ZnO (Nos. 17, 18 and 25); Ta 2  O 5  (No. 20); ZnO and Ta 2  O 5  in suitable amounts respectively (No. 21); MnO 2  (No. 22), WO 3  (No. 23); and MnO 2  and WO 3  (No. 24) in a suitable amount. Also, each of the sample Nos. 22, 23 and 24 has the large sintered density, and is excellent in degree of sintering. Further, by addition of ZnO, it is possible to freely adjust the τ f , particularly, to be a small value near 0. 
     The above samples are practical because they do not crack and they are excellent in the practical performances. 
     In addition, the present invention is not limited to the above example; but may be variously modified according to the objects and applications within the scope of the present invention. Namely, the baking temperature, baking time, temperature rising speed and the like may be variously modified. Also, the starting material for producing BaO may include peroxide, hydroxide and nitrate and the like other than the above BaCO 3 . 
     Further, by use of a sintering assistant (for example, at least one kind of MnO 2 , WO 3 , ZrO 2 , SnO 2  and the like), it is possible to improve the degree of sintering while keeping the above dielectric ceramic characteristics and preventing the occurrence of cracks.