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BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a dielectric ceramic which is
advantageously used in a laminated ceramic electronic element such as a
laminated ceramic capacitor having an internal conductor formed of a base
metal such as nickel or nickel alloy, and to a method for producing the
dielectric ceramic. The present invention also relates to a laminated
ceramic electronic element which is formed of the dielectric ceramic and
to a method for producing the same.
2. Description of the Related Art
Miniaturization and cost reduction of laminated ceramic electronic elements
is in progress. For example, the ceramic layer has been thinned and a base
metal has been employed as an internal conductor in such a ceramic
electronic element. In the case of a laminated ceramic capacitor, which is
one type of laminated ceramic electronic element, the dielectric ceramic
layer has been formed as thin as about 3 .mu.m and a base metal such as Cu
or Ni has been employed as a material for producing an internal conductor,
i.e., an internal electrode.
However, when the ceramic layer becomes thin, the strength of an electric
field applied to the layer increases and causes a problem in that the
ceramic layer dielectric exhibits a great change in dielectric constant
induced by the electric field. Decrease of the size of ceramic grains in
the thickness direction of the ceramic layer also causes a problem in
reliability.
In order to cope with such situations, Japanese Patent Application
Laid-Open (kokai) Nos. 9-241074, 9-241075, etc. have proposed ceramic
materials which enable enhanced reliability by increasing the size of
ceramic grains in the thickness direction of the dielectric ceramic layer.
Thus, controlling the grain size of ceramic grains allows a reduction in
change of dielectric constant induced by an electric field or temperature.
However, in the above-described conventional art, although reliability is
maintained when the thickness of a dielectric ceramic layer is about 1
.mu.m or less, variation in temperature-dielectric constant
characteristics increases to thereby make it difficult to obtain products
having stable temperature-dielectric constant characteristics with high
reproducibility. In order to ensure stable temperature-dielectric constant
characteristics, field intensity must be lowered and the rated voltage of
the resultant laminated ceramic electronic elements has to be lowered.
Therefore, realization of a thin layer having a thickness as thin as about
1 .mu.m or less is difficult or impossible so long as the above-described
conventional art is employed to solve the problem.
SUMMARY OF THE INVENTION
In view of the foregoing, the present invention is directed to a dielectric
ceramic which is advantageously used in a laminated ceramic electronic
element including a thin ceramic layer having a thickness as thin as about
1 .mu.m or less and to a method for producing the dielectric ceramic. The
present invention is also directed to a laminated ceramic electronic
element which is formed of the dielectric ceramic and to a method for
producing the same.
In one aspect of the present invention, there is provided a dielectric
ceramic which is obtained by firing barium titanate powder having a
perovskite structure in which the c-axis/a-axis ratio in the perovskite
structure is in the range of about 1.003 to about 1.010 and the amount of
OH groups in the crystal lattice is 1 wt. % or less.
In another aspect of the present invention, there is provided a method for
producing the dielectric ceramic, which method comprises the steps of
providing the above barium titanate powder in which the c-axis/a-axis
ratio in the perovskite structure is in the range of about 1.003 to 1.010
and the amount of OH groups in the crystal lattice is 1 wt. % or less; and
firing the barium titanate powder.
The amount of OH groups is determined based on the loss at 150.degree. C.
or more as measured during thermogravimetric analysis of specimens.
The barium titanate powder preferably has a maximum particle size of about
0.5 .mu.m or less and an average particle size of about 0.1-0.3 .mu.m.
Also, each particle of the above-described barium titanate powder
preferably comprises a low-crystallinity portion and a high-crystallinity
portion, the diameter of the low-crystallinity portion being less than
about 0.65 times the particle size of the powder. As shown in FIG. 1,
which is a transmission electron microscopic photograph of barium titanate
powder, and FIG. 2, which is an explanatory sketch therefor, the term
"low-crystallinity portion" 21 used herein refers to a domain containing a
number of lattice defects such as a void 22, whereas the term
"high-crystallinity portion" 23 used herein refers to a domain containing
no such lattice defects.
Also, when the ratio (average grain size of fired dielectric
ceramic)/(average particle size of provided barium titanate powder) is
represented by R, R preferably falls within the range of about 0.90-1.2.
Grains that constitute the dielectric ceramic of the present invention may
have a core-shell structure in which the composition and crystal system
differ between the core and the shell or a homogeneous structure having a
uniform composition and crystal system.
The term "crystal system" used herein refers to the crystal system of
perovskite crystals, i.e., to a cubic system having a c-axis/a-axis ratio
in the perovskite structure of 1 or to a tetragonal system having a
c-axis/a-axis ratio in the perovskite structure of 1 or more.
In yet another aspect of the present invention, there is provided a
laminated ceramic electronic element including a laminate formed of a
plurality of ceramic layers and an internal conductor formed along a
specific interface between adjacent dielectric ceramic layers.
Specifically, in the present invention, the dielectric ceramic layer
included in the laminated ceramic electronic element is constituted by a
dielectric ceramic obtained by firing barium titanate powder having a
perovskite structure in which the c-axis/a-axis ratio in the perovskite
structure is in the range of about 1.003 to about 1.010 and an amount of
OH groups in the crystal lattice is about 1 wt. % or less.
In the above-described laminated ceramic electronic element, the internal
conductors preferably contain a base metal such as nickel or nickel alloy.
The laminated ceramic electronic element may further include a plurality of
external electrodes at different positions on a side face or faces. In
this case, the internal conductors are formed such that one end of each of
the internal conductors is exposed to the side face so as to be
electrically connected to one of the external electrodes. Such a structure
is typically applied to laminated ceramic capacitors.
In a still further aspect of the present invention, there is provided a
method for producing a laminated ceramic electronic element, which method
comprises the steps of providing a barium titanate powder in which the
c-axis/a-axis ratio in the perovskite structure is in the range of about
1.003 to 1.010 and the amount of OH groups in the crystal lattice is about
1 wt. % or less; fabricating a laminate in which a plurality of ceramic
green sheets containing the barium titanate powder and internal electrodes
are laminated so that the internal electrodes are present along specific
interfaces of the ceramic green sheets; and firing the barium titanate
powder to thereby provide a dielectric ceramic.
BRIEF DESCRIPTION OF THE DRAWINGS
Various other objects, features, and many of the attendant advantages of
the present invention will be readily appreciated as the same becomes
better understood with reference to the following detailed description of
the preferred embodiments when considered in connection with the
accompanying drawings, in which:
FIG. 1 is a transmission electron microscopic photograph of barium titanate
powder provided for producing a dielectric ceramic according to the
present invention;
FIG. 2 is an explanatory sketch of the electron microscopic photograph
shown in FIG. 2; and
FIG. 3 is a cross-sectional view showing a laminated ceramic capacitor 1
according to one embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The barium titanate powder used in the present invention has a composition
represented by formula: (Ba.sub.1-x X.sub.x).sub.m (Ti.sub.1-y
Y.sub.y)O.sub.3. The composition is not further limited specifically. X
may comprise Ca, single species of rare earth elements, and a combination
of two or more thereof. Y may comprise single species such as Zr or Mn and
a combination of two or more thereof. In general, m is preferably about
1.000-1.035, depending on the composition of the barium titanate powder,
in order to obtain a non-reducing dielectric ceramic.
The barium titanate powder which is advantageously used has a perovskite
structure in which the c-axis/a-axis ratio is in the range of about 1.003
to 1.010. Moreover, the amount of OH groups in the crystal lattice is
about 1 wt. % or less; the maximum particle size is about 0.5 .mu.m or
less; and the average particle size is about 0.1-0.3 .mu.m. Such barium
titanate powder can be obtained by thermally treating barium titanate
powder which is produced through a wet synthesis method, such as a
hydrothermal synthesis method, a hydrolysis method, or a sol-gel method.
For synthesis there may also be employed a solid phase method in which a
carbonate, an oxide, etc. of elements constituting barium titanate powder
are mixed and thermally treated.
In the above-described thermal treatment, the conditions for moderate grain
growth are selected so as to realize a c-axis/a-axis ratio of as high as
about 1.003 to 1.010. For example, effective thermal treatment can be
performed in an atmosphere containing H.sub.2 O. Of course, the above
range can be met by proper adjustment of temperature and time of the
thermal treatment. When a solid-phase method is used, because the
c-axis/a-axis ratio might decrease depending on conditions for
disintegration of the synthesized powder, the disintegration conditions
must be controlled.
The diameter ratio of the low-crystallinity portion 21, i.e., the ratio of
the diameter of the low-crystallinity portion 21 to the particle size of
the powder, after the above-described thermal treatment, is predetermined
to be less than about 0.65 in each particle of the barium titanate powder
shown in FIG. 1 and FIG. 2. Such a diameter ratio may be obtained through
thermal treatment at a temperature elevation rate of 1.degree. C./min or
less.
The relationship between the average particle size of the thus-provided
barium titanate powder and the average grain size of the fired dielectric
ceramic, i.e., the ratio of (average grain size of fired ceramic)/(average
particle size of provided barium titanate powder), which is represented by
R, is preferably about 0.90-1.2. Briefly, considerable grain growth is
preferably prevented during sintering for producing ceramics. For example,
for this purpose an Mn component and/or an Mg component, an Si-base
sintering aid, etc. are added to barium titanate powder. In general, these
additives may be incorporated into barium titanate powder in the form of
oxide powder or carbonate powder. Alternatively, there may be used a
method in which barium titanate powder is coated with a solution
containing these additives and then thermally treated.
Such barium titanate powder is fired to thereby produce a dielectric
ceramic, which is used in a laminated ceramic electronic element, e.g., a
laminated ceramic capacitor 1 illustrated in FIG. 3.
As shown in FIG. 3, the laminated ceramic capacitor 1 comprises a laminate
3 containing a plurality of laminated dielectric layers 2 and a first
external electrode 6 and a second external electrode 7 which are provided
on a first side face 4 and a second side face 5 of the laminate 3,
respectively. The laminated ceramic capacitor 1 in its entirety
constitutes a rectangular parallelepiped-shaped chip-type electronic
element.
In the laminate 3, first internal electrodes 8 and second electrodes 9 are
alternately disposed as internal conductors. The first internal electrodes
8 are formed along specific interfaces between dielectric ceramic layers 2
such that one end of each of the internal electrodes 8 is exposed to the
first side face 4 of the laminate 3 so as to be electrically connected to
the first external electrode 6, while second internal electrodes 9 are
formed along specific interfaces between dielectric ceramic layers 2 such
that one end of each of the internal electrodes 9 is exposed to the second
side face 5 of the laminate 3 so as to be electrically connected to the
second external electrode 7.
In the laminated ceramic capacitor 1, the dielectric ceramic layers 2
included in the laminate 3 comprise the above-mentioned dielectric
ceramic.
In order to produce the laminated ceramic capacitor 1, there are provided
starting materials comprising a primary component such as barium titanate
and an additive to improve characteristics, etc. The materials are weighed
in predetermined amounts and wet-mixed to form a mixed powder.
Then, an organic binder and a solvent are added into the mixed powder to
thereby obtain a slurry, and a ceramic green sheet of the dielectric
ceramic layer 2 is produced by use of the slurry.
Subsequently, electrically conductive paste films forming internal
electrodes 8 and 9 are formed on the specific ceramic green sheets. The
conductive paste film contains a base metal such as nickel or copper, or
an alloy thereof, and is formed through a method such as screen printing,
vapor deposition, or plating.
A plurality of ceramic green sheets, including those on which conductive
paste film has been formed as described above, are laminated, pressed, and
cut if necessary. Thus, there is produced a green laminate 3 in which
ceramic green sheets and the internal electrodes 8 and 9 formed along
specific interfaces between ceramic green sheets, one end of each of the
internal electrodes 8 and 9 being exposed to the side face 4 or 5.
The laminate 3 is then fired in a reducing atmosphere to thereby transform
barium titanate powder into dielectric ceramic. In this step, the
above-described grain size ratio R is controlled so as to fall within the
range of 0.90.ltoreq.R.ltoreq.1.2.
The first external electrode 6 and the second external electrode 7 are
formed on the first side face 4 and on the second side face 5 of the
laminate 3, respectively, so as to contact with the exposed ends of the
first internal electrodes 8 and second internal electrodes 9 in the fired
laminate 3.
No particular limitation is imposed on the composition of the materials for
producing the external electrode 6 and 7. Specifically, there may be used
the same materials as those of the internal electrodes 8 and 9. The
external electrodes may also be constructed of a sintered layer comprising
an electrically conductive metal powder such as powder of Ag, Pd, Ag--Pd,
Cu or a Cu alloy; or a sintered layer comprising the above conductive
metal powder blended with glass frit such as B.sub.2 O.sub.3 --Li.sub.2
O--SiO.sub.2 --BaO, B.sub.2 O.sub.3 --SiO.sub.2 --BaO, Li.sub.2
O--SiO.sub.2 --BaO, or B.sub.2 O.sub.3 --SiO.sub.2 --ZnO. The composition
of the materials for producing the external electrode 6 and 7 is
appropriately determined in consideration of factors relating to the
laminated ceramic capacitor 1, such as use or environment of use.
As described above, the external electrodes 6 and 7 may be formed by
applying the metal powder paste forming them on the fired laminate 3 and
burning. The electrodes may also be formed by applying the paste on the
unfired laminate 3 and burning simultaneous with firing the laminate 3.
The external electrodes 6 and 7 may be coated with plating layers 10 and 11
formed of Ni, Cu, an Ni--Cu alloy, etc., respectively, in accordance with
need. The plating layers 10 and 11 may further be coated with second
plating layers 12 and 13 formed of solder, tin, etc., respectively.
The present invention will next be described in detail by way of examples,
which should not be construed as limiting the invention.
EXAMPLES
The laminated ceramic capacitor produced in this Example is a laminated
ceramic capacitor 1 having a structure shown in FIG. 3.
Different barium titanate materials having compositions shown in Table 1
were prepared by hydrolysis. The resultant material powders have a
particle size of 50 to 70 nm and a cubic structure containing many OH
groups in lattices of a perovskite structure. Through heat-treatment of
these materials under a variety of conditions, e.g., in an atmosphere
containing H.sub.2 O, barium titanate powders A to N having different
"c/a" values (c-axis/a-axis ratio), average particle sizes, maximum
particle sizes, amounts of OH groups, and diameter ratios were prepared.
Aggregations produced during heat-treatment were disintegrated after
heat-treatment.
TABLE 1
Average Maximum Amount
particle particle of OH
BaTiO.sub.3 (Ba.sub.1-x Ca.sub.x).sub.m TiO.sub.3 size size
groups Diameter
powder x m c/a (.mu.m) (.mu.m) (%) ratio
A* 0.00 1.005 1.002 0.07 0.20 1.40 0.8
B* 0.00 1.005 1.005 0.09 0.25 1.20 0.7
C 0.00 1.015 1.005 0.13 0.30 0.60 0.4
D 0.00 1.015 1.007 0.20 0.40 0.20 0.2
E 0.00 1.015 1.009 0.25 0.45 0.10 0.1
F* 0.00 1.015 1.011 0.25 0.50 0.10 0.1
or less
G* 0.00 1.015 1.009 0.35 0.50 0.10 0.1
or less or less
H* 0.00 1.015 1.009 0.25 0.70 0.10 0.1
or less
I 0.05 1.010 1.005 0.15 0.30 0.80 0.4
J* 0.05 1.010 1.002 0.15 0.30 0.90 0.7
K 0.10 1.015 1.009 0.25 0.45 0.20 0.1
L* 0.10 1.015 1.011 0.25 0.45 0.10 0.1
or less
M* 0.10 1.010 1.007 0.35 0.60 0.10 0.1
or less or less
N* 0.10 1.010 1.005 0.15 0.30 0.85 0.7
The "c/a" values shown in Table 1 were determined by X-ray diffraction of
barium titanate powders. That is, the results obtained from X-ray
diffraction were subjected to X-ray profile fitting using Rietveld
analysis to precisely determine lattice constants. The average particle
size and the maximum particle size were measured by observation of barium
titanate powders under a scanning electron microscope. The amount of OH
groups was measured by way of a loss weight at a temperature of
150.degree. C. or higher as measured by thermal gravimetric analysis of
barium titanate powders.
The diameter ratio shown in Table 1 is a ratio of the diameter of the
low-crystallinity portion to the particle size of the powder and was
determined by subjecting the powder to cut-processing so as to obtain a
thin film specimen and observation under a transmission electron
microscope. When the film-like specimen of the powder is prepared by
cut-processing, the particle size of the powder and the diameter of a
low-crystallinity portion in the powder vary. In particular, since a
low-crystallinity portion is not always located in the center of a powder
particle, the size of the portion must be observed several times depending
on the cutting site upon preparation of thin film. Thus, for observation
there were selected particles having a particle size similar to the
particle size observed by scanning electron microscopy. The diameter ratio
was determined by observation of 10 or more such particles and calculating
the average diameter ratio.
In the "BaTiO.sub.3 powder" column in Table 1, with respect to powders A to
H, "x"s of the materials (Ba.sub.1-x Ca.sub.x).sub.m TiO.sub.3 are 0.00,
so that powders A to H contain no Ca, but powders I to N contain Ca, as is
understood from their "x"s being 0.05 or 0.10.
As additives to be added to the barium titanate powders shown in Table 1,
those having the compositions shown in Tables 2 and 3 were provided.
Specifically, with respect to Sample Nos. 1 to 17 shown in Table 2, RE (RE
represents any one of Gd, Dy, Ho, and Er), Mg and Mn were provided as
additives to be added to BaTiO.sub.3 in the form of one of the
above-mentioned samples A to H. A sintering aid containing Si as a primary
component was also provided. With respect to Sample Nos. 18 to 29 shown in
Table 3, Mg and Mn were provided as additives to be added to (Ba.sub.1-x
Ca.sub.x)TiO.sub.3 in the form of any one of the above-mentioned samples I
to N. A sintering aid containing (Si, Ti)--Ba as a primary component was
also provided.
TABLE 2
Si-
BaTiO.sub.3 + .alpha.RE + .beta.Mg + .gamma.Mn containing
Type .beta. (parts .gamma. (parts
sintering
Sample of .alpha. (parts by mole) by by aid (parts
No. BaTiO.sub.3 Gd Dy Ho Er mole) mole) by
mole)
1 A 0.02 0.020 0.005 3
2 B 0.02 0.020 0.005 2
3 B 0.02 0.020 0.005 4
4 C 0.02 0.020 0.005 3
5 C 0.02 0.020 0.010 3
6 C 0.02 0.015 0.005 3
7 C 0.02 0.015 0.005 4
8 C 0.02 0.010 0.020 6
9 D 0.02 0.010 0.005 2
10 D 0.02 0.020 0.005 3
11 E 0.02 0.010 0.005 3
12 E 0.02 0.020 0.005 3
13 E 0.02 0.010 0.005 3
14 E 0.02 0.010 0.005 4
15 F 0.02 0.010 0.005 4
16 G 0.02 0.010 0.005 4
17 H 0.02 0.010 0.005 4
TABLE 3
(Si,Ti)--Ba--
(Ba.sub.1-x Ca.sub.x)TiO.sub.3 + .beta.Mg + .gamma.Mn containing
Sample Type of sintering aid
No. BaTiO.sub.3 .beta. (parts by mole) .gamma. (parts by mole) (parts
by mole)
18 I 0.02 0.005 2
19 I 0.02 0.005 2
20 I 0.02 0.005 4
21 I 0.02 0.005 6
22 J 0.02 0.005 2
23 J 0.02 0.005 3
24 K 0.01 0.003 2
25 K 0.01 0.003 2
26 K 0.01 0.003 6
27 L 0.01 0.003 2
28 M 0.01 0.003 4
29 N 0.02 0.005 4
Respective additives shown in Tables 2 and 3 were transformed into alkoxide
compounds, which are soluble in organic solvent, and then were added to
the barium titanate powders which had been dispersed in organic solvent.
Specifically, with respect to Sample Nos. 1 to 17, respective additives
were added to the barium titanate powders such that ".alpha.," ".beta.,"
".gamma.," and "Si-containing sintering aid," all based on parts by mole,
in "BaTiO.sub.3 +.alpha.RE+.beta.Mg+.gamma.Mn" were as shown in Table 2.
With respect to Sample Nos. 18 to 29, respective additives were added to
the barium titanate powders such that ".beta.," ".gamma.," and "(Si,
Ti)--Ba-containing sintering aid," all based on parts by mole, in
"(Ba.sub.1-x Ca.sub.x)TiO.sub.3 +.beta.Mg+.gamma.Mn" were as shown in
Table 3.
In order to dissolve the above-mentioned additives in organic solvent, they
may be transformed into alkoxides as described above, or may be
transformed into acetylacetonates or metal soaps.
The resultant slurries were subjected to evaporation of organic solvent to
dryness and further heat-treatment, to thereby remove the organic
components.
Subsequently, to each sample of the barium titanate powders to which
respective additives had been added, a polyvinyl butyral binder and
organic solvent such as ethanol were added, and the ingredients were
subjected to wet milling so as to prepare a ceramic slurry. The resultant
slurry was molded into a sheet by use of a doctor blade to thereby obtain
a rectangular green sheet having a thickness of 1.5 .mu.m. Then, on the
resultant ceramic green sheet, a conductive paste containing Ni as a
primary component was applied by way of printing to form a conductive
paste film for forming internal electrodes.
Subsequently, a plurality of the thus-obtained ceramic green sheets were
laminated such that leading ends of the above-mentioned conductive paste
films on the sheets were arranged alternately, to thereby obtain a
laminate. The resultant laminate was heated at 350.degree. C. in an
atmosphere of N.sub.2 so as to burn the binder, and then fired for two
hours at a temperature shown in Table 4 in a reducing atmosphere of
H.sub.2 --N.sub.2 --H.sub.2 O gas with a partial pressure of 10.sup.-9 to
10.sup.-12 MPa oxygen.
To the opposite side faces of the fired laminate, a silver paste containing
B.sub.2 O.sub.3 --Li.sub.2 O--SiO.sub.2 --BaO glass frit was applied,
followed by burning in a nitrogen atmosphere at 600.degree. C. to obtain
external electrodes electrically connected with the internal electrodes.
The outer size of the resultant laminated ceramic capacitor was 5.0 mm
width, 5.7 mm length and 2.4 mm thickness, and the thickness of the
dielectric ceramic layer existing between internal electrodes was 1 .mu.m.
The total number of effective dielectric ceramic layers was five, and the
area of the opposite electrodes per layer was 16.3.times.10.sup.-6
m.sup.2.
The electrical properties of the resultant samples were measured as
follows.
Electrostatic capacity (C) and dielectric loss (tan.delta.) were measured
by use of an automatic bridge instrument according to JIS 5102, and
dielectric constant (.epsilon.) was determined by use of the resultant
electrostatic capacity.
In order to measure insulation resistance (R), an insulation tester was
used; by application of 10 V DC for two minutes, insulation resistance (R)
at 25.degree. C. was obtained, and resistivity was calculated.
Regarding the rate of change in electrostatic capacity with respect to
temperature change, the rate of change (.DELTA.C/C.sub.20) within a range
of -25.degree. C. to +85.degree. C. with reference to the electrostatic
capacity at 20.degree. C. and the rate of change (.DELTA.C/C.sub.25)
within a range of -55.degree. C. to +125.degree. C. with reference to the
electrostatic capacity at 25.degree. C. are shown.
In a high temperature loading test, time-course change of insulation
resistance upon application of 10 V DC at 150.degree. C. was measured. In
this test, average lives of the samples were evaluated, wherein the life
of a sample was considered to be equal to time until breakdown when the
insulation resistance (R) of each sample dropped to 10.sup.5 .OMEGA. or
less.
Breakdown voltage was measured by applying DC voltage at a voltage
elevation rate of 100 V/sec.
The average grain size of dielectric ceramic contained in the resultant
laminated ceramic capacitor was obtained by chemically etching polished
cross-sectional surfaces of the laminate and observation of the surfaces
under a scanning microscope. By use of the results and average particle
sizes of the starting raw materials shown in Table 1, a ratio R; i.e.,
(average grain size of the dielectric ceramic)/(average particle size of
the starting raw material) was measured. The results are shown in Table 4.
TABLE 4
Rate of Rate of
capacitance
capacitance change with
respect
Dielectric change to temperature
Breakdown
Firing Size loss .DELTA.C % change
Resistivity voltage Average
Sample temperature ratio Dielectric tan .delta. DC3kV/mm
.DELTA.C/C.sub.20 .DELTA.C/C.sub.25 log .rho. DC life
No. (.degree. C.) R constant (%) (%) (%) (%)
(.OMEGA. .multidot. cm) (kV/mm) (h)
1* 1100 1.30 1300 1.8 -6.0 -12.6 -30.7 13.1 76
96
2* 1100 1.05 1530 2.3 -8.0 -10.5 -18.9 13.1 84
25
3* 1100 1.55 1470 2.1 -24.6 -5.6 -40.8 12.9 88
54
4* 1100 0.80 1160 2.7 -6.5 -11.6 -20.5 13.1 78
86
5 1150 1.05 1680 2.4 -9.0 -7.5 -12.6 13.1 88
93
6 1150 1.10 1750 2.3 -8.8 -7.6 -11.5 13.1 84
90
7 1150 1.18 1720 2.4 -10.2 -7.5 -12.4 13.1 86
92
8* 1150 1.40 1260 2.5 -21.4 -18.4 -35.2 13.2 74
46
9* 1100 0.75 1160 2.2 -6.0 -9.6 -28.4 13.2 74
105
10 1150 1.10 1850 2.4 -10.0 -8.8 -13.7 13.2
85 85
11* 1125 0.80 1160 2.3 -11.0 -9.2 -24.6 13.2 75
96
12 1200 1.05 2020 2.5 -11.3 -8.5 -13.6 13.2
88 91
13 1150 1.10 1860 2.5 -11.5 -8.2 -13.5 13.1
75 93
14* 1300 1.35 2360 3.4 -26.6 -8.7 -25.2 12.9 74
93
15* 1175 1.05 2140 2.4 -11.3 -8.2 -12.4 13.2 85
16
16* 1175 1.10 2250 2.5 -13.5 -8.9 -13.7 13.2 88
25
17* 1150 1.05 2070 2.4 -11.4 -12.6 -19.7 13.2 77
12
18* 1100 0.75 870 1.7 -8.0 -8.8 -28.7 13.2 75
105
19 1130 1.00 1670 2.4 -10.0 -5.5 -13.4 13.1
91 84
20 1100 1.15 1540 2.5 -8.0 -4.5 -11.6 13.2
86 78
21* 1130 1.25 1220 2.3 -17.6 3.4 67.8 12.8
78 23
22* 1100 1.05 1120 2.4 -9.0 -1.4 -30.8 13.1 74
65
23* 1100 1.25 1480 3.6 -25.5 3.6 36.7 13
75 18
24* 1150 0.70 1060 8.7 -7.0 -8.5 -28.5 13.2 96
88
25 1150 1.10 2160 2.5 -15.5 -4.2 10.3 13.1
88 84
26 1150 1.18 2340 2.5 -21.2 -4.5 13.5 13.2
87 83
27* 1250 1.05 2060 3.4 -15.0 -2.3 25.5 12.6
75 16
28* 1200 1.05 2150 2.8 -17.0 -3.3 21.6 12.8
75 18
29* 1100 1.10 1360 2.4 -7.5 -6.7 -14.7 13 88
90
The dielectric ceramic of the present invention is characterized by the
following features. Firstly, it is obtained by firing barium titanate
powder having a perovskite structure in which the c-axis/a-axis ratio in
the perovskite structure is in the range of about 1.003 to 1.010 and the
amount of OH groups in the crystal lattice is about 1 wt. % or less.
Preferably, the barium titanate powder serving as the raw material has a
maximum particle size of about 0.5 .mu.m or less, an average particle size
of about 0.1 to about 0.3 .mu.m. Also preferably, individual particles of
the barium titanate powder comprise a low-crystallinity portion and a
high-crystallinity portion in each particle, and the diameter of the
low-crystallinity portion is less than about 0.65 times the particle size
of the powder. Further, a ratio R, i.e., (average grain size of the
dielectric ceramic)/(average particle size of barium titanate powder) is
about 0.90 to about 1.2, so that there is no occurrence of considerable
grain growth during sintering ceramic.
The sample numbers marked with * in Table 4, and the powders marked with *
in Table 1 fall outside the scope of the present invention or the
above-stated preferable ranges.
First, regarding Sample Nos. 1 to 17 shown in Table 4 obtained through use
of o | | |
