Patent Publication Number: US-4147670-A

Title: Nonohmic ZnO ceramics including Bi2 O3, CoO, MnO, Sb2 O.sub.3

Description:
BACKGROUND OF THE INVENTION 
     This invention relates to materials of nonohmic resistors, namely, resistors having nonlinear voltage-current characteristics and, more particularly, to materials of nonohmic resistors for use in electric communication apparatus. 
     Nonohmic resistors (hereafter called varistors) have widely been used in surge-absorbing devices, voltage-stabilizing devices, lightning arrestors, and others. In general, a varistor is evaluated by a voltage nonlinear exponent α and a breakdown voltage V i  used in an equation: 
     
         I/i = (V/V.sub.i).sup.α, 
    
     where V i , named the breakdown voltage hereinabove, represents a voltage applied across the varistor to cause a predetermined current i to flow therethrough and I generally represents a current flowing through the varistor when a voltage V is applied thereacross. 
     Sophisticated varistors are silicon varistors, silicon-carbide varistors, selenium rectifiers, cuprous oxide rectifiers, and the like and have various defects such that they have small voltage nonlinear exponents α, that their characteristics are hardly optionally adjustable or controllable, and/or that they are bulky. It has recently been proposed by Michio MATSUOKA in &#34;Japanese Journal of Applied Physics,&#34; Vol. 10, No. 6 (June 1971), pages 736-746, to provide a varistor as a sintered body or mass of zinc oxide ceramics with five additives of bismuth(III) oxide, cobalt(II) oxide, manganese(II) oxide, chromium(III) oxide, and antimony(III) oxide and to thereby remove the above-mentioned defects and widen the field of application of the varistors. The proposed varistor, however, is still unsatisfactory for use in those circuits of recent highly developed electric communication apparatus in which a varistor is mostly used with a load imposed thereon as a surge-absorbing element for absorbing a large current pulse inevitably appearing in the circuit upon on-off of a switch for the circuit and under like circumstances. Furthermore, the proposed varistor is defective in that continued application thereto of a certain electric power results in a decrease in the breakdown voltage V i  and a consequent increase in the leakage current. The proposed varistor likewise when supplied repeatedly with large current pulses does not tend to retain its excellent nonohmic characteristics. 
     Except for specific electric circuits, the voltage nonlinear exponent α of a varistor should be about 30 or more. The breakdown voltage V i  should be adjustable to a nominal voltage preselected for the varistor in consideration of the usage thereof. Dielectric properties are also important when a varistor is used in communication apparatus. The varistor shows a small impedance for that frequency of a signal used in communication apparatus which is rendered more and more higher with the progress of communication techniques. It is therefore desirable that a varistor has a smaller capacitance or dielectric constant ε. It is also desired that a varistor has a smaller dielectric loss (tanδ). The conventional varistor comprising zinc oxide as its principal constituent has had as large as dielectric constant ε and a dielectric loss (tanδ) as about 1000 or more and 10% or more, respectively, and has been unsatisfactory for use in communication apparatus. 
     Proposals have also been made to render the varistors more resistive against the continued load and the large current pulses. One of the proposals is to make the varistor which consists mainly of zinc oxide to include various vitreous materials by one method or another. The improvements thereby achieved, however, have been either for the load or for the large current pulse. This proves that the mechanism of variation caused in the varistor characteristics by the load is different from the mechanism for the large current pulse and that the improvement has consequently been possible for only one of the load and the large current pulse. Furthermore, addition of the vitreous material has raised the breakdown voltage V i  to about 500 volts or more. As a result, varistors for use in communication apparatus have to be rendered very thin in order to provide a compromise between the voltage of the signal used therein and the breakdown voltage so that the varistors do not further withstand a high surge voltage and that the varistors have only weak mechanical strength and unduly large capacitance. 
     SUMMARY OF THE INVENTION 
     It is therefore a general object of the present invention to provide a material for a varistor which is quite satisfactorily usable in a circuit of electric communication apparatus. 
     It is a specific object of this invention to provide a material for a varistor having excellent nonohmic, dielectric, load-resistive, and large current pulse-resistive characteristics. 
     In accordance with one embodiment of this invention, there is provided a nonohmic ceramic material consisting essentially of a main component of zinc oxide, auxiliary components of bismuth(III) oxide of 0.1-10%, cobalt(II) oxide of 0.05-10%, manganese(II) oxide of 0.25-4%, and antimony(III) oxide of 0.05-6%, the percentages being by mol, and as an additional additive borosilicate lead and zinc glass, the material including the additional components of 0.1-10% by weight. 
    
    
     BRIEF DESCRIPTION OF THE DRAWING: 
     FIGS. 1 through 12 show various characteristics of nonohmic ceramic materials according to preferred embodiments of the present invention. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENTS 
     Nonohmic ceramic materials according to a first embodiment of the present invention consist essentially of a main component of zinc oxide, auxiliary components of 0.1-10% by mol of bismuth(III) oxide, 0.05-10% by mol of cobalt(II) oxide, 0.25-4% by mol of manganese(II) oxide, 0.05-6% by mol of antimony(III) oxide, and additional components of 0.1-10% by weight of borosilicate lead-zinc glass. 
     According to a second embodiment of this invention, the percentages of the bismuth, manganese, and antimony oxides are changed to 0.1-6%, 0.25-10%, and 0.1-10% by mol, respectively, with borosilicate zinc glass substituted for the borosilicate lead-zinc glass. 
     According to a third embodiment of this invention, use is made of the percentages of the bismuth oxide and of the other auxiliary component oxides as in the second and the first embodiments, respectively, with the additional components changed to borosilicate lead glass of 0.1-3% by weight. 
     According to a fourth embodiment of this invention, the percentages of the antimony oxide is changed in the second embodiment to 0.1-6% by mol with at least one of lead(II) oxide, aluminium oxide, cerium oxide, barium oxide, titanium(IV) oxide, tin(IV) oxide, tantalum(V) oxide, phosphorus pentoxide, calcium oxide, diarsenic trioxide, and zirconium(IV) oxide (except the lead oxide only) added to the borosilicate zinc glass. 
     According to a fifth embodiment of this invention, nonohmic ceramic materials consist essentially of a main component of zinc oxide, auxiliary components of 0.10-3.00% by mol of bismuth(III) oxide, 0.10-10.00% by mol of cobalt(II) oxide, 0.10-5.00% by mol of manganese(II) oxide, and 0.10-5.00% by mol of antimony(III) oxide, and additional components of 0.01-0.50% by mol of silicon(IV) oxide, 0.01-1.00% by mol of boron oxide, and 0.01-0.50% by mol of lead(II) oxide. It is obvious that the additional components correspond to or are equivalent to borosilicate lead glass although actual formation of the glass in the ceramics has not yet been confirmed. The ceramic materials contain from 0.03% to about 3% by weight of the additional components, namely, the borosilicate lead glass equivalent. 
     In addition to the properties mentioned in the preamble of the instant specification, it is necessary for a varistor that its electrodes do not exfoliate even when the varistor is subjected to repeated temperature cycles. It has been confirmed that a varistor made of any ceramic material according to the first through fifth embodiments of this invention is strong against temperature cycles. 
     As starting materials for varistors made of ceramic materials according to the first through fourth embodiments, use was made of powdered zinc oxide of a purity equal to 99% or higher, bismuth(III) oxide, cobalt(II) oxide, manganese(II) carbonate, antimony(III) oxide, and borosilicate lead and/or zinc glass frit. The glass frit was of various compositions listed by percentages by weight in Tables 1 and 2 hereunder. According to the fifth embodiment, use was made, in addition to the above-mentioned oxides and carbonate, of powdered silicon(IV) oxide, boron oxide, and lead(II) oxide to provide the additional components corresponding or equivalent to borosilicate lead glass. Typical percentages by mol of the additional compositions are given in Table 3 below, wherein the compositions marked with asterisks are outside of the percentages used in the fifth embodiment. 
     
                       Table 1                                                     
______________________________________                                    
glass frit   SiO.sub.2                                                    
                      B.sub.2 O.sub.3                                     
                               ZnO    PbO                                 
AA           10.8     27.2     60.0   2.0                                 
AB           2.0      10.0     12.5   75.5                                
AC           9.5      27.0     63.4   0.1                                 
AD           0.1      55.4     44.4   0.1                                 
AE           12.0     23.5     56.0   8.5                                 
AF           27.0     8.0      0.1    64.9                                
AG           72.3     20.7     0.1    6.9                                 
BA           11.8     28.1     60.1                                       
BB           42.1     10.4     47.5                                       
BC           22.1     22.8     55.1                                       
BD           65.3     9.5      25.2                                       
BE           39.2     21.0     39.8                                       
CA           26       8               66                                  
CB           35       13              52                                  
CC           75       15              10                                  
CD           50       10              40                                  
CE           50       25              25                                  
CF           34       28              38                                  
______________________________________                                    
 
    
     
                       Table 2                                                     
______________________________________                                    
 glass frit                                                               
          DA      DB      DC    DD    DE    DF                            
SiO.sub.2 11.8    2.1     12.0  9.2   10.7  6.2                           
B.sub.2 O.sub.3                                                           
          28.1    9.4     23.2  27.8  28.5  18.6                          
ZnO       60.1    12.3    52.1  50.4  50.9  24.1                          
PbO               70.1    6.8               43.3                          
Al.sub.2 O.sub.3  0.6           0.4   0.2                                 
CeO.sub.2         1.1           3.8   5.1                                 
BaO                       2.6               1.8                           
TiO.sub.2         3.9           4.1                                       
SnO.sub.2                 1.8               2.2                           
Ta.sub.2 O.sub.5                      0.2   1.1                           
P.sub.2 O.sub.5           1.1   3.6                                       
CaO                       0.2                                             
As.sub.2 O.sub.3          0.4                                             
ZrO.sub.2                       0.7         3.7                           
______________________________________                                    
 
    
     
                       Table 3                                                     
______________________________________                                    
glass equivalent                                                          
                SiO.sub.2                                                 
                         B.sub.2 O.sub.3                                  
                                  PbO                                     
*EA             0.00     0.30     0.05                                    
EB              0.01     &#34;        &#34;                                       
EC              0.05     &#34;        &#34;                                       
ED              0.10     &#34;        &#34;                                       
EE              0.50     &#34;        &#34;                                       
*EF             1.00     &#34;        &#34;                                       
*EG             0.05     0.00     &#34;                                       
EH              &#34;        0.01     &#34;                                       
EI              &#34;        0.05     &#34;                                       
EJ              &#34;        0.10     &#34;                                       
EK              &#34;        1.00     &#34;                                       
*EL             &#34;        2.00     &#34;                                       
*EM             &#34;        0.30     0.00                                    
EN              &#34;        &#34;        0.01                                    
EO              &#34;        &#34;        0.10                                    
EP              &#34;        &#34;        0.50                                    
*EQ             &#34;        &#34;        1.00                                    
______________________________________                                    
 
    
     Throughout the first through fourth embodiments, the powdered oxides and carbonate were weighed out, mixed together with addition thereto of pure water in a ball mill for twenty-four hours, filtered, dried, calcined at 650° C.-850° C., and pressure-shaped into disks, 16 mm in diameter, with addition thereto of a small amount of a binder (5% aqueous solution of polyvinyl alcohol). For the fifth embodiment, weighed out powder of the oxides and carbonate of the auxiliary and additional components were mixed for two hours by the use of a grinder before the calcination. The disks were sintered at 1100° C.-1300° C. for one hour into ceramics, which were ground to a thickness of 1 mm. A pair of silver electrodes, 8 mm in diameter, were fired to each ground ceramic disk to provide a sample. 
     The voltage nonlinear exponent α and the breakdown voltage V i  were calculated from the results of measurement of the voltage-current characteristics carried out by the use of d.c. power or pulses produced by a curve tracer. The capacitance and the loss factor (tanδ) were measured by the use of a capacitance bridge at 1 kHz. The load characteristics were evaluated by a change in the breakdown voltage V i  for a current of 10 microamperes at room temperature before and after a power of 1.5 W/cm 2  was imposed for three hours on each sample kept at 80° C. in a thermostat. The large current pulse characteristics were similarly evaluated by a variation in the breakdown voltage V 10 μA before and after current pulses of 200 amperes (the current wave form being 10 × 200 microseconds) were caused to flow through each sample twenty times at an interval of 30 seconds. For use in communication apparatus, the load and the large current pulse characteristics should be about 20% and about 5%, respectively, or less. The temperature cycle test was carried out for a change in the capacitance before and after each sample was subjected fifteen times to a temperature cycle of -65° C., 25° C., 125° C., and 25° C. 
     Typical results are listed in Table 4 wherein V i , the breakdown voltage, is given in volts for the above-mentioned samples when the current density is 1 mA/cm 2 , tanδ, the loss factor, is given in percentage, and &#34;L,&#34; &#34;P,&#34; and &#34;T&#34; represent in percentages the load and the large current pulse characteristics and the results of temperature cycle tests, all mentioned above. Samples numbered with asterisks are not made of nonohmic ceramic materials according to the first through fifth embodiments. The temperature cycle tests were not carried out for samples made of nonohmic ceramic materials including the borosilicate lead glass equivalents listed in Table 3. For reference, similar data are shown in Table 4 for like samples made of zinc oxide ceramics including no borosilicate glass equivalent. 
     
                                           Table 4                                 
__________________________________________________________________________
No.                                                                       
   ZnO Bi.sub.2 O                                                         
           CoO                                                            
              MnO                                                         
                 Sb.sub.2 O.sub.3                                         
                     glass                                                
                        α                                           
                          V.sub.i                                         
                             ε                                    
                                 tanδ                               
                                    L    P    T                           
__________________________________________________________________________
glass: AA                                                                 
*1 95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.05                                                 
                        45                                                
                          260                                             
                             800 10.5                                     
                                    -79  -10  -130                        
2  &#34;   &#34;   &#34;  &#34;  &#34;   0.1                                                  
                        48                                                
                          245                                             
                             770 7.5                                      
                                    -15  -4   0                           
3  &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        61                                                
                          267                                             
                             637 3.4                                      
                                    -7   +1   &#34;                           
4  &#34;   &#34;   &#34;  &#34;  &#34;   3.0                                                  
                        53                                                
                          260                                             
                             600 2.8                                      
                                    -10  -2   &#34;                           
5  &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        46                                                
                          252                                             
                             553 3.4                                      
                                    -13  -3   &#34;                           
6  &#34;   &#34;   &#34;  &#34;  &#34;   10.0                                                 
                        42                                                
                          250                                             
                             503 4.6                                      
                                    -18  -5   &#34;                           
*7 &#34;   &#34;   &#34;  &#34;  &#34;   20.0                                                 
                        43                                                
                          250                                             
                             500 7.5                                      
                                    -25  -10  -20                         
*8 96.0                                                                   
       0.0 &#34;  &#34;  &#34;   1.0                                                  
                         7                                                
                          163                                             
                             698 30.5                                     
                                    -99  -30  0                           
9  95.9                                                                   
       0.1 &#34;  &#34;  &#34;   &#34;  40                                                
                          283                                             
                             585 8.5                                      
                                    -20  -4   &#34;                           
10 95.6                                                                   
       0.4 &#34;  &#34;  &#34;   &#34;  63                                                
                          343                                             
                             467 1.6                                      
                                    -15  0    &#34;                           
11 92.0                                                                   
       4.0 &#34;  &#34;  &#34;   &#34;  39                                                
                          161                                             
                             912 8.5                                      
                                    -12  -2   &#34;                           
12 86.0                                                                   
       10.0                                                               
           &#34;  &#34;  &#34;   &#34;  30                                                
                          100                                             
                             960 9.5                                      
                                    -19  -4   &#34;                           
*13                                                                       
   76.0                                                                   
       20.0                                                               
           &#34;  &#34;  &#34;   &#34;  15                                                
                          100                                             
                             970 20.0                                     
                                    -50  -10  -15                         
*14                                                                       
   96.0                                                                   
       1.0 0.0                                                            
              &#34;  &#34;   &#34;  60                                                
                          360                                             
                             430 5.5                                      
                                    -75  -25  0                           
15  95.95                                                                 
       &#34;    0.05                                                          
              &#34;  &#34;   &#34;  82                                                
                          350                                             
                             499 3.8                                      
                                    -18  -5   &#34;                           
16 95.6                                                                   
       &#34;   0.4                                                            
              &#34;  &#34;   &#34;  72                                                
                          291                                             
                             556 3.5                                      
                                    -15  -3   &#34;                           
17 92.0                                                                   
       &#34;   4.0                                                            
              &#34;  &#34;   &#34;  65                                                
                          256                                             
                             598 2.7                                      
                                    -13  -3   &#34;                           
18 86.0                                                                   
       &#34;   10.0                                                           
              &#34;  &#34;   &#34;  48                                                
                          304                                             
                             532 5.2                                      
                                    -19  -5   &#34;                           
*19                                                                       
   76.0                                                                   
       &#34;   20.0                                                           
              &#34;  &#34;   &#34;  40                                                
                          300                                             
                             530 5.2                                      
                                    -60  -20  -20                         
*20                                                                       
   96.0                                                                   
       &#34;   1.0                                                            
              0.0                                                         
                 &#34;   &#34;  40                                                
                          194                                             
                             1020                                         
                                 2.3                                      
                                    -99  -35  -11                         
21  95.75                                                                 
       &#34;   &#34;   0.25                                                       
                 &#34;   &#34;  46                                                
                          205                                             
                             760 2.4                                      
                                    -19  -5   0                           
22 95.6                                                                   
       &#34;   &#34;  0.4                                                         
                 &#34;   &#34;  51                                                
                          224                                             
                             634 2.6                                      
                                    -15  -4   &#34;                           
23 92.0                                                                   
       &#34;   &#34;  4.0                                                         
                 &#34;   &#34;  66                                                
                          295                                             
                             528 8.5                                      
                                    -13  -3   &#34;                           
*24                                                                       
   86.0                                                                   
       &#34;   &#34;  10.0                                                        
                 &#34;   &#34;  60                                                
                          300                                             
                             400 8.5                                      
                                    -30  -15  -20                         
*25                                                                       
   97.0                                                                   
       &#34;   &#34;  1.0                                                         
                 0.0 &#34;  51                                                
                          155                                             
                             2398                                         
                                 5.9                                      
                                    -99  -32  0                           
26  96.75                                                                 
       &#34;   &#34;  &#34;   0.05                                                    
                     &#34;  53                                                
                          150                                             
                             960 5.5                                      
                                    -20  -4   &#34;                           
27 96.6                                                                   
       &#34;   &#34;  &#34;  0.4 &#34;  53                                                
                          150                                             
                             730 5.3                                      
                                    -15  +1   &#34;                           
28 93.0                                                                   
       &#34;   &#34;  &#34;  4.0 &#34;  47                                                
                          329                                             
                             249 2.6                                      
                                    -12  -2   &#34;                           
29 91.0                                                                   
       &#34;   &#34;  &#34;  6.0 &#34;  40                                                
                          350                                             
                             198 8.5                                      
                                    -18  -5   &#34;                           
*30                                                                       
   87.0                                                                   
       &#34;   &#34;  &#34;  10.0                                                     
                     &#34;  35                                                
                          360                                             
                             200 9.0                                      
                                    -30  -15  &#34;                           
glass: AB                                                                 
*31                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.05                                                 
                        48                                                
                          220                                             
                             800 9.5                                      
                                    -30  -6   -18                         
32 &#34;   &#34;   &#34;  &#34;  &#34;   0.1                                                  
                        48                                                
                          212                                             
                             866 8.6                                      
                                    -15  -4   0                           
33 &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        48                                                
                          210                                             
                             794 6.6                                      
                                    -15  +1   &#34;                           
34 &#34;   &#34;   &#34;  &#34;  &#34;   3.0                                                  
                        40                                                
                          180                                             
                             1100                                         
                                 9.5                                      
                                    -45  +1   &#34;                           
glass: AC                                                                 
*35                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.05                                                 
                        50                                                
                          234                                             
                             850 10.9                                     
                                    -40  -10  -35                         
36 &#34;   &#34;   &#34;  &#34;  &#34;   0.1                                                  
                        53                                                
                          234                                             
                             839 7.4                                      
                                    -20  -5   0                           
37 &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        61                                                
                          256                                             
                             538 3.0                                      
                                    -8   +4   &#34;                           
38 &#34;   &#34;   &#34;  &#34;  &#34;   3.0                                                  
                        62                                                
                          277                                             
                             396 2.7                                      
                                    -12  0    &#34;                           
39 &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        61                                                
                          280                                             
                             357 4.8                                      
                                    -15  -3   &#34;                           
40 &#34;   &#34;   &#34;  &#34;  &#34;   10.0                                                 
                        51                                                
                          282                                             
                             273 6.7                                      
                                    -19  -5   &#34;                           
*41                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   20.0                                                 
                        50                                                
                          280                                             
                             270 7.0                                      
                                    -35  -5   -20                         
glass: AD                                                                 
*42                                                                       
   93.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.05                                                 
                        42                                                
                          275                                             
                             900 7.9                                      
                                    -30  -3    -40                        
43 &#34;   &#34;   &#34;  &#34;  &#34;   0.1                                                  
                        44                                                
                          280                                             
                             880 6.8                                      
                                    -18  -4   0                           
44 &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        40                                                
                          285                                             
                             850 8.5                                      
                                    -50  -10  &#34;                           
glass: AE                                                                 
*45                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.05                                                 
                        45                                                
                          250                                             
                             890 15.0                                     
                                    -5   -7   -15                         
46 &#34;   &#34;   &#34;  &#34;  &#34;   0.1                                                  
                        47                                                
                          249                                             
                             870 7.8                                      
                                    -4   -4   0                           
47 &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        46                                                
                          300                                             
                             814 3.4                                      
                                    -10  -4   &#34;                           
48 &#34;   &#34;   &#34;  &#34;  &#34;   3.0                                                  
                        42                                                
                          350                                             
                             650 2.7                                      
                                    -15  -5   &#34;                           
49 &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        40                                                
                          360                                             
                             600 1.0                                      
                                    -25  -6   &#34;                           
glass: AF                                                                 
*50                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.05                                                 
                        45                                                
                          250                                             
                             850 9.0                                      
                                    -40  - 4  -13                         
51 &#34;   &#34;   &#34;  &#34;  &#34;   0.1                                                  
                        47                                                
                          249                                             
                             830 6.7                                      
                                    -13  -4   0                           
52 &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        46                                                
                          300                                             
                             692 3.1                                      
                                    -15  -2   &#34;                           
53 &#34;   &#34;   &#34;  &#34;  &#34;   3.0                                                  
                        42                                                
                          350                                             
                             520 2.8                                      
                                    -13  -3   &#34;                           
54 &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        40                                                
                          400                                             
                             500 5.0                                      
                                    -50  -6   -15                         
glass: AG                                                                 
*55                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.05                                                 
                        45                                                
                          270                                             
                             815 11.0                                     
                                    -45  -20  -20                         
56 &#34;   &#34;   &#34;  &#34;  &#34;   0.1                                                  
                        51                                                
                          244                                             
                             783 5.0                                      
                                    -19  -5   0                           
57 &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        40                                                
                          310                                             
                             522 3.9                                      
                                    -12  -5   &#34;                           
58 &#34;   &#34;   &#34;  &#34;  &#34;   3.0                                                  
                        37                                                
                          380                                             
                             440 2.2                                      
                                    -14  -4   &#34;                           
59 &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        32                                                
                          410                                             
                             430 2.7                                      
                                    -18  -2   &#34;                           
60 &#34;   &#34;   &#34;  &#34;  &#34;   10.0                                                 
                        35                                                
                          450                                             
                             420 3.5                                      
                                    -36  -15  &#34;                           
glass: BA                                                                 
61 95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        53                                                
                          236                                             
                             820 7.3                                      
                                    -18  -4   0                           
62 &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        64                                                
                          258                                             
                             523 3.1                                      
                                    -5   +4   &#34;                           
63 &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        62                                                
                          277                                             
                             386 4.8                                      
                                    -14  -2   &#34;                           
64 &#34;   &#34;   &#34;  &#34;  &#34;   10.0                                                 
                        57                                                
                          280                                             
                             281 6.7                                      
                                    -18  -5   &#34;                           
*65                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   30.0                                                 
                        21                                                
                          335                                             
                             218 9.8                                      
                                    -25  -13                              
*66                                                                       
   96.0                                                                   
       0.0 &#34;  &#34;  &#34;   1.0                                                  
                         5                                                
                           79                                             
                             8320                                         
                                 11.7                                     
                                    -92  -39                              
67 95.9                                                                   
       0.1 &#34;  &#34;  &#34;   &#34;  34                                                
                          204                                             
                             469 2.4                                      
                                    -16  -4   0                           
68 95.6                                                                   
       0.4 &#34;  &#34;  &#34;   &#34;  57                                                
                          318                                             
                             318 2.0                                      
                                    -7   +2   &#34;                           
69 90.0                                                                   
       6.0 &#34;  &#34;  &#34;   &#34;  58                                                
                          196                                             
                             589 7.6                                      
                                    -13  -3   &#34;                           
*70                                                                       
   86.0                                                                   
       10.0                                                               
           &#34;  &#34;  &#34;   &#34;   4                                                
                           72                                             
                             2160                                         
                                 28.8                                     
                                    -26  -7                               
71 96.0                                                                   
       1.0  0.05                                                          
              &#34;  &#34;   &#34;  71                                                
                          415                                             
                             312 2.6                                      
                                    -19  -5   0                           
72 95.6                                                                   
       &#34;   0.4                                                            
              &#34;  &#34;   &#34;  62                                                
                          304                                             
                             418 2.7                                      
                                    -7   -5   &#34;                           
73 92.0                                                                   
       &#34;   4.0                                                            
              &#34;  &#34;   &#34;  52                                                
                          234                                             
                             520 2.3                                      
                                    -11  +1   &#34;                           
74 86.0                                                                   
       &#34;   10.0                                                           
              &#34;  &#34;   &#34;  41                                                
                          276                                             
                             578 4.6                                      
                                    -17  -2   &#34;                           
*75                                                                       
   66.0                                                                   
       &#34;   30.0                                                           
              &#34;  &#34;   &#34;  35                                                
                          328                                             
                             677 7.2                                      
                                    -24  -4                               
*76                                                                       
   96.0                                                                   
       &#34;   1.0                                                            
              0.0                                                         
                 &#34;   &#34;  45                                                
                          154                                             
                             1080                                         
                                 2.4                                      
                                    -8   -6                               
77  95.75                                                                 
       &#34;   &#34;   0.25                                                       
                 &#34;   &#34;  47                                                
                          198                                             
                             530 2.1                                      
                                    -4   -3   0                           
78 92.0                                                                   
       &#34;   &#34;  4.0                                                         
                 &#34;   &#34;  57                                                
                          271                                             
                             482 6.5                                      
                                    -7   0    &#34;                           
79 86.0                                                                   
       &#34;   &#34;  10.0                                                        
                 &#34;   &#34;  43                                                
                          309                                             
                             512 7.8                                      
                                    -14  -2   &#34;                           
*80                                                                       
   66.0                                                                   
       &#34;   &#34;  30.0                                                        
                 &#34;   &#34;  32                                                
                          344                                             
                             883 18.9                                     
                                    -24  -4                               
*81                                                                       
   97.0                                                                   
       &#34;   &#34;  1.0                                                         
                 0.0 &#34;  51                                                
                          146                                             
                             2430                                         
                                 5.2                                      
                                    -26  -4                               
82 96.9                                                                   
       &#34;   &#34;  &#34;  0.1 &#34;  55                                                
                          147                                             
                             840 4.7                                      
                                    -19  -2   0                           
83 93.0                                                                   
       &#34;   &#34;  &#34;  4.0 &#34;  52                                                
                          288                                             
                             470 3.1                                      
                                    -6   0    &#34;                           
84 87.0                                                                   
       &#34;   &#34;  &#34;  10.0                                                     
                     &#34;  44                                                
                          343                                             
                             258 2.4                                      
                                    -4   -2   &#34;                           
*85                                                                       
   67.0                                                                   
       &#34;   &#34;  &#34;  30.0                                                     
                     &#34;  18                                                
                          983                                             
                              80 20.6                                     
                                    -15  -5                               
glass: BB                                                                 
86 95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        48                                                
                          246                                             
                             770 6.8                                      
                                    - 11 -5   0                           
87 &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        53                                                
                          268                                             
                             652 3.5                                      
                                    -7   +2   &#34;                           
88 &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        47                                                
                          254                                             
                             633 3.2                                      
                                    -12  0    &#34;                           
89 &#34;   &#34;   &#34;  &#34;  &#34;   10.0                                                 
                        41                                                
                          273                                             
                             576 4.9                                      
                                    -15  -3   &#34;                           
*90                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   30.0                                                 
                        27                                                
                          432                                             
                             372 8.8                                      
                                    -22  -9                               
glass: BC                                                                 
91 95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        49                                                
                          248                                             
                             788 7.1                                      
                                    -15  -2   0                           
92 &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        60                                                
                          261                                             
                             486 3.0                                      
                                    -6   +2   &#34;                           
93 &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        58                                                
                          267                                             
                             431 3.1                                      
                                    -7   0    &#34;                           
94 &#34;   &#34;   &#34;  &#34;  &#34;   10.0                                                 
                        46                                                
                          258                                             
                             440 6.2                                      
                                    -11  -4   &#34;                           
*95                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   30.0                                                 
                        41                                                
                          249                                             
                             451 10.4                                     
                                    -19  -11                              
glass: BD                                                                 
96 95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        44                                                
                          224                                             
                             743 5.9                                      
                                    -14  -2   0                           
97 &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        47                                                
                          218                                             
                             421 2.7                                      
                                    -9   0    &#34;                           
98 &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        41                                                
                          198                                             
                             443 3.4                                      
                                    -11  -3   &#34;                           
99 &#34;   &#34;   &#34;  &#34;  &#34;   10.0                                                 
                        38                                                
                          187                                             
                             451 4.7                                      
                                    -15  -5   &#34;                           
*100                                                                      
   &#34;   &#34;   &#34;  &#34;  &#34;   30.0                                                 
                        32                                                
                          234                                             
                             388 9.6                                      
                                    -23  -9                               
glass: BE                                                                 
101                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        51                                                
                          268                                             
                             610 6.1                                      
                                    -13  -5   0                           
102                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        63                                                
                          252                                             
                             453 3.3                                      
                                    -7   -3   &#34;                           
103                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        62                                                
                          248                                             
                             399 3.6                                      
                                    -8   -2   &#34;                           
104                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   10.0                                                 
                        54                                                
                          255                                             
                             432 4.9                                      
                                    -11  -4   &#34;                           
*105                                                                      
   &#34;   &#34;   &#34;  &#34;  &#34;   30.0                                                 
                        42                                                
                          261                                             
                             484 7.5                                      
                                    -18  -21                              
glass: CA                                                                 
106                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        57                                                
                          267                                             
                             610 4.6                                      
                                    -14  -3   0                           
107                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        55                                                
                          320                                             
                             262 2.6                                      
                                    -16  0    &#34;                           
108                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   3.0                                                  
                        41                                                
                          363                                             
                             198 2.7                                      
                                    -19  -4   &#34;                           
*109                                                                      
   &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        36                                                
                          415                                             
                             164 2.9                                      
                                    -38  -16                              
*110                                                                      
   &#34;   &#34;   &#34;  &#34;  &#34;   10.0                                                 
                        23                                                
                          432                                             
                             123 4.7                                      
                                    -75  -48                              
*111                                                                      
   96.0                                                                   
       0.0 &#34;  &#34;  &#34;   0.1                                                  
                         3                                                
                           56                                             
                             3892                                         
                                 30.6                                     
                                    -98  -34                              
112                                                                       
   95.9                                                                   
       0.1 &#34;  &#34;  &#34;   &#34;  31                                                
                          240                                             
                             573 7.8                                      
                                    -19  -4   0                           
113                                                                       
   95.6                                                                   
       0.4 &#34;  &#34;  &#34;   &#34;  49                                                
                          386                                             
                             343 2.5                                      
                                    -17  -2   &#34;                           
114                                                                       
   92.0                                                                   
       4.0 &#34;  &#34;  &#34;   &#34;  46                                                
                          284                                             
                             582 6.7                                      
                                    -19  -3   &#34;                           
115                                                                       
   90.0                                                                   
       6.0 &#34;  &#34;  &#34;   &#34;  43                                                
                          252                                             
                             566 7.4                                      
                                    -20  -5   &#34;                           
*116                                                                      
   86.0                                                                   
       10.0                                                               
           &#34;  &#34;  &#34;   &#34;  41                                                
                          234                                             
                             632 11.5                                     
                                    -48  -20                              
*117                                                                      
   96.0                                                                   
       1.0 0.0                                                            
              &#34;  &#34;   &#34;  38                                                
                          343                                             
                             398 4.6                                      
                                    -84  -26                              
118                                                                       
    95.95                                                                 
       &#34;    0.05                                                          
              &#34;  &#34;   &#34;  39                                                
                          323                                             
                             432 3.9                                      
                                    -20  -5   0                           
119                                                                       
   95.6                                                                   
       &#34;   0.4                                                            
              &#34;  &#34;   &#34;  37                                                
                          315                                             
                             475 3.4                                      
                                    -16  -3   &#34;                           
120                                                                       
   92.0                                                                   
       &#34;   4.0                                                            
              &#34;  &#34;   &#34;  44                                                
                          289                                             
                             534 2.2                                      
                                    -15  -4   &#34;                           
121                                                                       
   86.0                                                                   
       &#34;   10.0                                                           
              &#34;  &#34;   &#34;  36                                                
                          287                                             
                             538 6.6                                      
                                    -19  -5   &#34;                           
*122                                                                      
   96.0                                                                   
       &#34;   1.0                                                            
              0.0                                                         
                 &#34;   &#34;   4                                                
                          124                                             
                             1493                                         
                                 2.8                                      
                                    -99  -35                              
123                                                                       
    95.75                                                                 
       &#34;   &#34;   0.25                                                       
                 &#34;   &#34;  31                                                
                          205                                             
                             837 2.4                                      
                                    -20  -4   0                           
124                                                                       
   95.6                                                                   
       &#34;   &#34;  0.4                                                         
                 &#34;   &#34;  34                                                
                          405                                             
                             215 1.9                                      
                                    -15  -4   &#34;                           
125                                                                       
   92.0                                                                   
       &#34;   &#34;  4.0                                                         
                 &#34;   &#34;  33                                                
                          344                                             
                             373 4.1                                      
                                    -17  -5   &#34;                           
*126                                                                      
   86.0                                                                   
       &#34;   &#34;  10.0                                                        
                 &#34;   &#34;  18                                                
                          291                                             
                             540 32.2                                     
                                    -49  -12                              
*127                                                                      
   97.0                                                                   
       &#34;   &#34;  1.0                                                         
                 0.0 &#34;  18                                                
                          163                                             
                             1184                                         
                                 3.5                                      
                                    -99  -31                              
128                                                                       
    96.95                                                                 
       &#34;   &#34;  &#34;   0.05                                                    
                     &#34;  30                                                
                          274                                             
                             608 3.2                                      
                                    -20  -4   0                           
129                                                                       
   96.6                                                                   
       &#34;   &#34;  &#34;  0.4 &#34;  34                                                
                          332                                             
                             429 2.4                                      
                                    -17  -3   &#34;                           
130                                                                       
   93.0                                                                   
       &#34;   &#34;  &#34;  4.0 &#34;  33                                                
                          304                                             
                             498 5.6                                      
                                    -14  -2   &#34;                           
131                                                                       
   91.0                                                                   
       &#34;   &#34;  &#34;  6.0 &#34;  31                                                
                          300                                             
                             529 7.3                                      
                                    -19  - 5  &#34;                           
*132                                                                      
   87.0                                                                   
       &#34;   &#34;  &#34;  10.0                                                     
                     &#34;   4                                                
                          145                                             
                             1321                                         
                                 26.4                                     
                                    -66  -21                              
glass: CB                                                                 
133                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        48                                                
                          254                                             
                             743 6.7                                      
                                    -15  -4   0                           
134                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        51                                                
                          325                                             
                             705 3.2                                      
                                    -17  +1   &#34;                           
135                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   3.0                                                  
                        38                                                
                          375                                             
                             517 2.8                                      
                                    -20  -5   &#34;                           
*136                                                                      
   &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        27                                                
                          443                                             
                             508 2.6                                      
                                    -32  -18                              
*137                                                                      
   &#34;   &#34;   &#34;  &#34;  &#34;   10.0                                                 
                        21                                                
                          472                                             
                             342 9.7                                      
                                    -76  -43                              
glass: CC                                                                 
138                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        47                                                
                          252                                             
                             774 5.2                                      
                                    -17  -1   0                           
139                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        40                                                
                          330                                             
                             472 4.1                                      
                                    -18  +2   &#34;                           
140                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   3.0                                                  
                        33                                                
                          420                                             
                             437 2.9                                      
                                    -20  -3   &#34;                           
glass: CD                                                                 
141                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        48                                                
                          257                                             
                             730 6.3                                      
                                    -16  -2   0                           
142                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        47                                                
                          298                                             
                             395 2.9                                      
                                    -17  -1   &#34;                           
143                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   3.0                                                  
                        33                                                
                          368                                             
                             304 2.7                                      
                                    -20  -4   &#34;                           
*144                                                                      
   &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        24                                                
                          439                                             
                             273 3.4                                      
                                    -43  -14                              
glass: CE                                                                 
145                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        48                                                
                          263                                             
                             701 5.8                                      
                                    -17  -1   0                           
146                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        45                                                
                          346                                             
                             332 3.9                                      
                                    -19  -3   &#34;                           
147                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   3.0                                                  
                        39                                                
                          412                                             
                             243 2.5                                      
                                    -20  -5   &#34;                           
*148                                                                      
   &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        29                                                
                          464                                             
                             198 3.2                                      
                                    -58  -21                              
glass: CF                                                                 
149                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        51                                                
                          257                                             
                             723 6.4                                      
                                    -18  0    0                           
150                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        44                                                
                          284                                             
                             349 3.3                                      
                                    -18  +1   &#34;                           
151                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   3.0                                                  
                        36                                                
                          323                                             
                             256 2.6                                      
                                    -20  -5   &#34;                           
*152                                                                      
   &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        31                                                
                          365                                             
                             204 3.1                                      
                                    -57  -14                              
glass: DA                                                                 
153                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        53                                                
                          236                                             
                             820 7.3                                      
                                    -18  -4   0                           
154                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        64                                                
                          258                                             
                             523 3.1                                      
                                    -5   +4   &#34;                           
155                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        62                                                
                          277                                             
                             386 4.8                                      
                                    -14  -2   &#34;                           
156                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   10.0                                                 
                        57                                                
                          280                                             
                             281 6.7                                      
                                    -18  -5   &#34;                           
*157                                                                      
   &#34;   &#34;   &#34;  &#34;  &#34;   30.0                                                 
                        21                                                
                          335                                             
                             218 9.8                                      
                                    -25  -13                              
glass: DB                                                                 
158                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        51                                                
                          198                                             
                             793 6.5                                      
                                    -16  -3   0                           
159                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        62                                                
                          196                                             
                             703 2.8                                      
                                    -6   +2   &#34;                           
160                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        56                                                
                          198                                             
                             722 2.2                                      
                                    -9   -1   &#34;                           
161                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   10.0                                                 
                        43                                                
                          197                                             
                             800 4.1                                      
                                    -16  -2   &#34;                           
*162                                                                      
   &#34;   &#34;   &#34;  &#34;  &#34;   30.0                                                 
                        37                                                
                          196                                             
                             845 4.9                                      
                                    -21  -7                               
*163                                                                      
   96.0                                                                   
       0.0 &#34;  &#34;  &#34;   1.0                                                  
                         6                                                
                           85                                             
                             984 46.5                                     
                                    -96  -28                              
164                                                                       
   95.9                                                                   
       0.1 &#34;  &#34;  &#34;   &#34;  45                                                
                          176                                             
                             866 8.6                                      
                                    -18  -5   0                           
165                                                                       
   95.6                                                                   
       0.4 &#34;  &#34;  &#34;   &#34;  58                                                
                          198                                             
                             721 4.1                                      
                                    -7   +3   &#34;                           
166                                                                       
   90.0                                                                   
       6.0 &#34;  &#34;  &#34;   &#34;  42                                                
                          165                                             
                             878 6.9                                      
                                    -14  -1   &#34;                           
*167                                                                      
   86.0                                                                   
       10.0                                                               
           &#34;  &#34;  &#34;   &#34;  36                                                
                          142                                             
                             904 9.1                                      
                                    -28  -6                               
*168                                                                      
   96.0                                                                   
       1.0 0.0                                                            
              &#34;  &#34;   &#34;  76                                                
                          244                                             
                             752 26.2                                     
                                    -88  -5                               
169                                                                       
    95.95                                                                 
       &#34;    0.05                                                          
              &#34;  &#34;   &#34;  68                                                
                          196                                             
                             737 7.6                                      
                                    -19  -3   0                           
170                                                                       
   95.6                                                                   
       &#34;   0.4                                                            
              &#34;  &#34;   &#34;  62                                                
                          192                                             
                             728 5.3                                      
                                    -4   -2   &#34;                           
171                                                                       
   92.0                                                                   
       &#34;   4.0                                                            
              &#34;  &#34;   &#34;  54                                                
                          189                                             
                             745 6.6                                      
                                    -2   -2   &#34;                           
172                                                                       
   86.0                                                                   
       &#34;   10.0                                                           
              &#34;  &#34;   &#34;  41                                                
                          198                                             
                             796 9.4                                      
                                    -11  -4   &#34;                           
*173                                                                      
   96.0                                                                   
       &#34;   1.0                                                            
              0.0                                                         
                 &#34;   &#34;  38                                                
                          181                                             
                             894 10.2                                     
                                    -17  -6                               
174                                                                       
    95.95                                                                 
       &#34;   &#34;   0.25                                                       
                 &#34;   &#34;  45                                                
                          183                                             
                             875 6.3                                      
                                    -8   -3   0                           
175                                                                       
   95.6                                                                   
       &#34;   &#34;  0.4                                                         
                 &#34;   &#34;  53                                                
                          186                                             
                             798 4.8                                      
                                    -4   -2   &#34;                           
176                                                                       
   92.0                                                                   
       &#34;   &#34;  4.0                                                         
                 &#34;   &#34;  62                                                
                          199                                             
                             730 3.6                                      
                                    -2   +1   &#34;                           
177                                                                       
   86.0                                                                   
       &#34;   &#34;  10.0                                                        
                 &#34;   &#34;  41                                                
                          197                                             
                             738 7.1                                      
                                    -14  -4   &#34;                           
178                                                                       
   96.9                                                                   
       &#34;   &#34;  1.0                                                         
                 0.1 &#34;  46                                                
                          174                                             
                             698 5.4                                      
                                    -19  -3   &#34;                           
179                                                                       
   96.6                                                                   
       &#34;   &#34;  &#34;  0.4 &#34;  53                                                
                          187                                             
                             743 5.2                                      
                                    -8   -2   &#34;                           
180                                                                       
   96.0                                                                   
       &#34;   &#34;  &#34;  1.0 &#34;  61                                                
                          196                                             
                             706 4.8                                      
                                    -5   +1   &#34;                           
181                                                                       
   91.0                                                                   
       &#34;   &#34;  &#34;  6.0 &#34;  43                                                
                          199                                             
                             702 5.4                                      
                                    -9   -3   &#34;                           
*182                                                                      
   87.0                                                                   
       &#34;   &#34;  &#34;  10.0                                                     
                     &#34;  10                                                
                          243                                             
                             565 7.9                                      
                                    -12  -6                               
glass: DC                                                                 
183                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        44                                                
                          199                                             
                             689 7.8                                      
                                    -4   -4    0                          
184                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        48                                                
                          192                                             
                             714 3.7                                      
                                    -6   -3   &#34;                           
185                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        45                                                
                          189                                             
                             746 2.7                                      
                                    -8   -4   &#34;                           
186                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   10.0                                                 
                        42                                                
                          198                                             
                             702 4.1                                      
                                    -15  -5   &#34;                           
*187                                                                      
   &#34;   &#34;   &#34;  &#34;  &#34;   30.0                                                 
                        38                                                
                          220                                             
                             670 8.8                                      
                                    -23  -7                               
glass: DD                                                                 
188                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        47                                                
                          198                                             
                             700 6.5                                      
                                    -10  -3   0                           
189                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        46                                                
                          197                                             
                             704 4.2                                      
                                    -5   +2   &#34;                           
glass: DE                                                                 
190                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        50                                                
                          196                                             
                             756 8.5                                      
                                    -7   -3   0                           
191                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        51                                                
                          199                                             
                             774 4.3                                      
                                    -4   +1   &#34;                           
192                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        47                                                
                          198                                             
                             721 3.8                                      
                                    -8   -2                               
glass: DF                                                                 
193                                                                       
   95.0                                                                   
       1.0 1.0                                                            
              1.0                                                         
                 2.0 0.1                                                  
                        48                                                
                          198                                             
                             764 7.4                                      
                                    -14  -4   0                           
194                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   1.0                                                  
                        54                                                
                          199                                             
                             748 4.5                                      
                                    -7   +1   &#34;                           
195                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   5.0                                                  
                        51                                                
                          197                                             
                             776 3.1                                      
                                    -3   -2   &#34;                           
196                                                                       
   &#34;   &#34;   &#34;  &#34;  &#34;   10.0                                                 
                        47                                                
                          192                                             
                             802 5.2                                      
                                    -4   -4   &#34;                           
*197                                                                      
   &#34;   &#34;   &#34;  &#34;  &#34;   30.0                                                 
                        42                                                
                          186                                             
                             854 6.3                                      
                                    -8   -8                               
No.   ZnO                                                                 
         Bi.sub.2 O.sub.3                                                 
             CoO                                                          
                MnO                                                       
                   Sb.sub.2 O.sub.3                                       
                       [glass]                                            
                           α                                        
                             V.sub.i                                      
                                ε                                 
                                    tanδ                            
                                       L   P                              
__________________________________________________________________________
glass equivalents: E series                                               
*198  94.63                                                               
         1.00                                                             
             1.00                                                         
                1.00                                                      
                   2.00                                                   
                       EA  45                                             
                             221                                          
                                715 8.0                                   
                                       -25.2                              
                                           -5.5                           
199   94.64                                                               
         &#34;   &#34;  &#34;  &#34;   EB  50                                             
                             225                                          
                                710 6.0                                   
                                       -15.1                              
                                           -3.5                           
*200  95.55                                                               
         0.05                                                             
             &#34;  &#34;  &#34;   EC   5                                             
                             112                                          
                                500 2.5                                   
                                       --  --                             
201   95.50                                                               
         0.10                                                             
             &#34;  &#34;  &#34;   &#34;   48                                             
                             140                                          
                                450 2.3                                   
                                       -12.2                              
                                           -4.5                           
202   94.60                                                               
         1.00                                                             
             &#34;  &#34;  &#34;   &#34;   58                                             
                             227                                          
                                700 2.0                                   
                                       -16.1                              
                                           -3.2                           
203   92.60                                                               
         3.00                                                             
             &#34;  &#34;  &#34;   &#34;   55                                             
                             175                                          
                                710 1.8                                   
                                       -18.3                              
                                           -4.6                           
*204  90.60                                                               
         5.00                                                             
             &#34;  &#34;  &#34;   &#34;   45                                             
                             160                                          
                                715 8.5                                   
                                       -35.4                              
                                           -15.3                          
*205  95.60                                                               
         1.00                                                             
             0.00                                                         
                &#34;  &#34;   &#34;   46                                             
                             282                                          
                                720 6.5                                   
                                       -25.8                              
                                           -6.2                           
206   95.50                                                               
         &#34;   0.10                                                         
                &#34;  &#34;   &#34;   52                                             
                             264                                          
                                710 2.0                                   
                                       -15.2                              
                                           -5.0                           
207   85.60                                                               
         &#34;   10.00                                                        
                &#34;  &#34;   &#34;   55                                             
                             234                                          
                                705 2.1                                   
                                       -16.3                              
                                           -4.0                           
*208  75.00                                                               
         &#34;   20.00                                                        
                &#34;  &#34;   &#34;   50                                             
                             372                                          
                                700 2.4                                   
                                       -14.7                              
                                           -18.5                          
*209  95.60                                                               
         &#34;   1.00                                                         
                0.00                                                      
                   &#34;   &#34;   38                                             
                             200                                          
                                710 2.3                                   
                                       -25.6                              
                                           -15.4                          
210   95.50                                                               
         &#34;   &#34;  0.10                                                      
                   &#34;   &#34;   50                                             
                             189                                          
                                710 2.4                                   
                                       -13.5                              
                                           -4.5                           
211   92.60                                                               
         &#34;   &#34;  3.00                                                      
                   &#34;   &#34;   60                                             
                             245                                          
                                700 2.5                                   
                                       -14.5                              
                                           -3.5                           
212   90.60                                                               
         &#34;   &#34;  5.00                                                      
                   &#34;   &#34;   62                                             
                             250                                          
                                710 4.8                                   
                                       -15.5                              
                                           -4.5                           
*213  85.60                                                               
         &#34;   &#34;  10.00                                                     
                   &#34;   &#34;   58                                             
                             264                                          
                                715 8.8                                   
                                       -31.2                              
                                           -10.3                          
*214  96.60                                                               
         &#34;   &#34;  1.00                                                      
                   0.00                                                   
                       &#34;   43                                             
                             178                                          
                                2500                                      
                                    3.5                                   
                                       -48.9                              
                                           -15.4                          
215   96.50                                                               
         &#34;   &#34;  &#34;  0.10                                                   
                       &#34;   55                                             
                             175                                          
                                785 3.4                                   
                                       -13.4                              
                                           -4.5                           
216   91.60                                                               
         &#34;   &#34;  &#34;  5.00                                                   
                       &#34;   58                                             
                             275                                          
                                701 3.0                                   
                                       -17.5                              
                                           -3.3                           
*217  85.60                                                               
         &#34;   &#34;  &#34;  10.00                                                  
                       &#34;   15                                             
                             1200                                         
                                200 10.5                                  
                                       --  -8.0                           
218   94.55                                                               
         &#34;   &#34;  &#34;  2.00                                                   
                       ED  51                                             
                             227                                          
                                700 4.0                                   
                                       -16.0                              
                                           -3.6                           
219   94.15                                                               
         &#34;   &#34;  &#34;  &#34;   EE  52                                             
                             284                                          
                                682 1.0                                   
                                       -18.1                              
                                           -4.2                           
*220  93.65                                                               
         &#34;   &#34;  &#34;  &#34;   EF  45                                             
                             300                                          
                                505 2.5                                   
                                       -25.3                              
                                           -4.4                           
*221  94.90                                                               
         &#34;   &#34;  &#34;  &#34;   EG  39                                             
                             225                                          
                                710 6.5                                   
                                       -35.5                              
                                           -10.5                          
222   94.89                                                               
         &#34;   &#34;  &#34;  &#34;   EH  50                                             
                             226                                          
                                650 5.2                                   
                                       -18.0                              
                                           -3.5                           
223   94.85                                                               
         &#34;   &#34;  &#34;  &#34;   EI  55                                             
                             224                                          
                                603 1.0                                   
                                       -19.0                              
                                           -3.4                           
224   94.80                                                               
         &#34;   &#34;  &#34;  &#34;   EJ  54                                             
                             226                                          
                                610 0.5                                   
                                       -18.2                              
                                           -3.6                           
225   93.90                                                               
         &#34;   &#34;  &#34;  &#34;   EK  53                                             
                             220                                          
                                612 1.5                                   
                                       -16.1                              
                                           -4.5                           
*226  92.90                                                               
         &#34;   &#34;  &#34;  &#34;   EL  33                                             
                             205                                          
                                751 2.0                                   
                                       -14.0                              
                                           -9.8                           
*227  94.65                                                               
         &#34;   &#34;  &#34;  &#34;   EM  45                                             
                             225                                          
                                753 3.5                                   
                                       -12.0                              
                                           -10.5                          
228   94.64                                                               
         &#34;   &#34;  &#34;  &#34;   EN  56                                             
                             219                                          
                                724 2.4                                   
                                       -16.0                              
                                           -3.5                           
229   94.55                                                               
         &#34;   &#34;  &#34;  &#34;   EO  57                                             
                             218                                          
                                702 1.0                                   
                                       -12.2                              
                                           -3.7                           
230   94.15                                                               
         &#34;   &#34;  &#34;  &#34;   EP  50                                             
                             180                                          
                                701 1.0                                   
                                       -15.3                              
                                           -3.9                           
*231  93.65                                                               
         &#34;   &#34;  &#34;  &#34;   EQ  42                                             
                             160                                          
                                684 2.5                                   
                                       -40.1                              
                                           -5.5                           
No    ZnO Bi.sub.2 O.sub.3                                                
              CoO                                                         
                 MnO                                                      
                    Sb.sub.2 O.sub.3                                      
                        α                                           
                          V.sub.i                                         
                             ε                                    
                                 tanδ                               
                                    L   P                                 
__________________________________________________________________________
without glass or glass equivalent                                         
232   95.0                                                                
          1.0 1.0                                                         
                 1.0                                                      
                    2.0 42                                                
                          270                                             
                             880 12.0                                     
                                    -98 -28                               
233   &#34;   &#34;   &#34;  &#34;  &#34;   45                                                
                          220                                             
                             712 8.5                                      
                                    -85.0                                 
                                        -20.5                             
234   96.0                                                                
          0.0 1.0                                                         
                 1.0                                                      
                    2.0  3                                                
                           56                                             
                             3950                                         
                                 35.6                                     
                                    -89.5                                 
                                        -38.5                             
235    95.95                                                              
           0.05                                                           
              &#34;  &#34;  &#34;   20                                                
                          110                                             
                             510 30.1                                     
                                    --  --                                
236   95.9                                                                
          0.1 &#34;  &#34;  &#34;   42                                                
                          202                                             
                             650 10.1                                     
                                    -80.3                                 
                                        -30.2                             
237   95.6                                                                
          0.4 &#34;  &#34;  &#34;   40                                                
                          195                                             
                             660 12.1                                     
                                    -79.5                                 
                                        -33.4                             
238   95.5                                                                
          0.5 &#34;  &#34;  &#34;   43                                                
                          214                                             
                             703 10.2                                     
                                    -90.4                                 
                                        -34.5                             
239   93.0                                                                
          3.0 &#34;  &#34;  &#34;   46                                                
                          200                                             
                             724 8.0                                      
                                    -95.0                                 
                                        -25.4                             
240   92.0                                                                
          4.0 &#34;  &#34;  &#34;   43                                                
                          205                                             
                             730 8.1                                      
                                    -91.2                                 
                                        -28.6                             
241   91.0                                                                
          5.0 &#34;  &#34;  &#34;   40                                                
                          210                                             
                             732 8.2                                      
                                    -84.0                                 
                                        -30.5                             
242   90.0                                                                
          6.0 &#34;  &#34;  &#34;   38                                                
                          198                                             
                             725 8.9                                      
                                    -88.5                                 
                                        -32.6                             
243   96.0                                                                
          1.0 0.0                                                         
                 &#34;  &#34;   35                                                
                          345                                             
                             506 8.9                                      
                                    -88.9                                 
                                        -33.5                             
244    95.95                                                              
          &#34;    0.05                                                       
                 &#34;  &#34;   45                                                
                          405                                             
                             748 8.5                                      
                                    -76.5                                 
                                        -20.6                             
245   95.9                                                                
          &#34;   0.1                                                         
                 &#34;  &#34;   40                                                
                          350                                             
                             734 8.4                                      
                                    -84.6                                 
                                        -30.5                             
246   95.6                                                                
          &#34;   0.4                                                         
                 &#34;  &#34;   33                                                
                          270                                             
                             705 7.5                                      
                                    -93.5                                 
                                        -32.4                             
247   95.5                                                                
          &#34;   0.5                                                         
                 &#34;  &#34;   30                                                
                          250                                             
                             722 7.8                                      
                                    -95.4                                 
                                        -32.5                             
248   92.0                                                                
          &#34;   4.0                                                         
                 &#34;  &#34;   32                                                
                          265                                             
                             718 8.0                                      
                                    -76.5                                 
                                        -45.6                             
249   91.0                                                                
          &#34;   5.0                                                         
                 &#34;  &#34;   35                                                
                          234                                             
                             695 7.2                                      
                                    -90.4                                 
                                        -20.2                             
250   86.0                                                                
          &#34;   10.0                                                        
                 &#34;  &#34;   42                                                
                          243                                             
                             680 7.6                                      
                                    -93.2                                 
                                        -35.8                             
251   76.0                                                                
          &#34;   20.0                                                        
                 &#34;  &#34;   43                                                
                          241                                             
                             698 7.2                                      
                                    -76.5                                 
                                        -33.3                             
252   66.0                                                                
          &#34;   30.0                                                        
                 &#34;  &#34;   41                                                
                          275                                             
                             710 8.0                                      
                                    -78.5                                 
                                        -23.5                             
253   96.0                                                                
          &#34;   1.0                                                         
                 0.0                                                      
                    &#34;    4                                                
                          185                                             
                             1005                                         
                                 1.5                                      
                                    -89.5                                 
                                        -33.8                             
254   95.9                                                                
          &#34;   &#34;  0.1                                                      
                    &#34;   33                                                
                          210                                             
                             812 4.6                                      
                                    -83.0                                 
                                        -43.5                             
255    95.75                                                              
          &#34;   &#34;   0.25                                                    
                    &#34;   35                                                
                          195                                             
                             715 13.9                                     
                                    -88.5                                 
                                        -32.5                             
256   95.6                                                                
          &#34;   &#34;  0.4                                                      
                    &#34;   34                                                
                          302                                             
                             702 15.5                                     
                                    -87.6                                 
                                        -29.8                             
257   93.0                                                                
          &#34;   &#34;  3.0                                                      
                    &#34;   43                                                
                          273                                             
                             703 8.8                                      
                                    -76.0                                 
                                        -30.4                             
258   92.0                                                                
          &#34;   &#34;  4.0                                                      
                    &#34;   33                                                
                          300                                             
                             650 10.6                                     
                                    -89.5                                 
                                        -33.5                             
259   91.0                                                                
          &#34;   &#34;  5.0                                                      
                    &#34;   35                                                
                          305                                             
                             670 10.6                                     
                                    -90.5                                 
                                        -34.1                             
260   86.0                                                                
          &#34;   &#34;  10.0                                                     
                    &#34;   34                                                
                          324                                             
                             701 12.4                                     
                                    -83.5                                 
                                        -41.0                             
261   97.0                                                                
          &#34;   &#34;  1.0                                                      
                    0.0 15                                                
                          154                                             
                             2009                                         
                                 18.6                                     
                                    -78.8                                 
                                        -32.1                             
262    96.95                                                              
          &#34;   &#34;  &#34;   0.05                                                 
                        31                                                
                          143                                             
                             2004                                         
                                 13.6                                     
                                    -98.0                                 
                                        -38.2                             
263   96.9                                                                
          &#34;   &#34;  &#34;  0.1 33                                                
                          215                                             
                             730 14.3                                     
                                    -90.0                                 
                                        -36.2                             
264   96.6                                                                
          &#34;   &#34;  &#34;  0.4 32                                                
                          204                                             
                             715 18.5                                     
                                    -79.5                                 
                                        -31.5                             
265   96.0                                                                
          &#34;   &#34;  &#34;  1.0 31                                                
                          205                                             
                             715 19.0                                     
                                    -80.5                                 
                                        -31.2                             
266   93.0                                                                
          &#34;   &#34;  &#34;  4.0 30                                                
                          211                                             
                             713 19.6                                     
                                    -83.4                                 
                                        -30.8                             
267   92.0                                                                
          &#34;   &#34;  &#34;  5.0 32                                                
                          220                                             
                             724 17.8                                     
                                    -80.5                                 
                                        -31.7                             
268   91.0                                                                
          &#34;   &#34;  &#34;  6.0 25                                                
                          245                                             
                             703 13.4                                     
                                    -93.6                                 
                                        -34.6                             
269   87.0                                                                
          &#34;   &#34;  &#34;  10.0                                                  
                         4                                                
                          740                                             
                             653 10.5                                     
                                    -88.5                                 
                                        -32.8                             
__________________________________________________________________________
 
    
     In the above-given Table 4, samples Nos. 232 and 233 are of the same composition and yet showed different results because of the different ambient temperatures. The result of temperature cycle test for the sample No. 232 was -50%. 
     Referring to FIG. 1, the current-voltage characteristic of sample No. 2 is excellent for a wide range of current. The characteristic is excellent particularly with respect to small leakage current in the smaller current range. 
     FIG. 2 shows the voltage nonlinear exponent α, breakdown voltage V 1mA , dielectric constant ε, and loss factor (tanδ) versus the amount of the borosilicate lead-zinc glass as exemplified by samples Nos. 232 and 1-6. FIG. 3 illustrates the load and the large current pulse characteristics versus similar amount of the borosilicate lead-zinc glass. 
     Turning now to FIG. 4, the current-voltage characteristic of sample No. 62 is also excellent like the sample No. 2. FIGS. 5 and 6 are similar to FIGS. 2 and 3 except that samples are Nos. 232 and 61-64. 
     FIG. 7 shows the excellent current-voltage characteristic of sample No. 106. FIGS. 8 and 9 are similar to FIGS. 2 and 3 except that samples are Nos. 232 and 106-110. 
     FIG. 10 again shows the excellent current-voltage characteristic of sample No. 159. FIGS. 11 and 12 are similar to FIGS. 2 and 3 except that samples are Nos. 158-161. 
     It is obvious from Table 4 that the excellent characteristics are obtained by simultaneous addition to the main component of the above-mentioned auxiliary and additional components. Furthermore, it has been confirmed that the additional components, namely, the borosilicate glass and/or its equivalent, may be added to the calcined main and auxiliary components throughout the first through fifth embodiments and that use may be made as the starting materials of carbonates and/or oxalates which become oxides when sintered. The fifth embodiment proves that substitution for the borosilicate lead and/or zinc glass of the additional components corresponding to the glass gives the excellent results. The ranges of the components of the first through fifth embodiments are determined to give the voltage nonlinear exponent α of 30 or more, the breakdown voltage V i  of 500 volts or less, the dielectric constant ε of about 1000 or less, the loss factor (tanδ) of less than 10%, the above-mentioned load characteristics of about 20% or less, and the above-described large current pulse characteristics of about 5% or less. Close inspection of Table 4  will reveal from samples Nos. 34, 44, 49, 54,  and 60 that the nonohmic ceramics according to the first embodiment should include 0.1-5.0%, 0.1-3.0%, 0.1-1.0%, and about 0.1% by weight of the borosilicate lead-zinc glass when the glass frit contains silicon(IV) oxide of about 70% and zinc and lead(II) oxides of about 7% in sum, when the glass first includes the silicon oxide of about 10-30% and the zinc and lead oxides of about 65% in sum, when the glass frit contains the silicon oxide of only about 2% and the lead oxide of about 75%, and the glass frit contains a still smaller amount of about 0.1% of the silicon oxide and the zinc and lead oxides of about 45% in sum, respectively, the percentages of the silicon, zinc, and lead oxides being by weight.