Solution coated hydrothermal BaTiO3 for low-temperature firing

FIELD OF THE INVENTION

This invention relates to an improved barium titanate based dielectric composition and, more particularly, to a barium titanate composition wherein barium titanate crystallites are coated with a Bismuth metal-organic to achieve both a low-firing temperature and improved dielectric properties.

BACKGROUND OF THE INVENTION

Barium titanate (BaTiO

3

) based compositions are commercially used as capacitor dielectrics, particularly for multilayer ceramic (MLC) capacitors. Present manufacturing techniques produce MLCs with thickness layers of 5-10 μm. Yet, with decreasing operating voltages of MLCs, thickness layers are expected to be less than 5 μm. In order to achieve these thickness layers and produce reliable MLCs, average grain size of the sintered BaTiO

3

ceramics need to be one-tenth the size of the layer thickness (i.e., ˜0.5 μm).

In addition to producing thinner layers for MLCs, manufacturers are actively pursuing methods for lowering the cost of MLCs. In particular, electrode materials make up a significant portion of the production costs for MLCs. Palladium-silver electrodes (e.g., 70/30 Pd-Ag) are substantially lower in price compared to platinum and pure palladium electrodes. Yet, in order to utilize Pd/Ag electrode materials, BaTiO

3

-based dielectric materials must be sintered at or below 1100° C.

In order to prepare BaTiO

3

-based ceramics that can be sintered below 1100° C. and have high densities with average grain sizes of 0.5 μm or less, a combination of hydrothermally-prepared powders with primary crystallites in the nanometer-sized range and a fluxing agent or a low-melting glass powder to promote densification of BaTiO

3

by liquid phase sintering below 1100° C. is needed. Fluxing agents and low-melting glass powders have been used to densify BaTiO

3

at lower sintering temperatures. Fluxing agents that have been used for flux-sintering BaTiO

3

include lithium fluoride, boron oxide, copper oxide, lead germanate, cadmium silicate, and mixtures of cadmium oxide and Bismuth oxide. Also, low-melting glass compounds, such as borosilicate glass powders that contain significant amounts of PbO, BaO, Bi

2

O

3

, CdO, and ZnO modifiers, have been used to promote densification of BaTiO

3

at lower sintering temperatures.

Kumar et al. describe a low-firing BaTiO

3

that is sintered from hydrothermal BaTiO

3

mixed with 3-5 wt % Bi

2

O

3

. (See: Kumar et al., “Preparation of Dense Ultra-Fine Grain Barium Titanate-Based Ceramics”, International Society of Applied Ferroelectrics (ISAF) Conference Proceedings, pp 70-73, 1992). Kumar et al. report that BaTiO

3

ceramics can be sintered to high densities as low as 850° C. using this process. On the other hand, Burn (“Flux-Sintered BaTiO

3

Dielectrics”,

Journal of Materials Science,

17, 1398-1408, 1982) indicates that commercially available BaTiO

3

can be sintered to high densities only around 1100° C. using the fluxing agents mentioned above. Average grain size of the low-firing BaTiO

3

ceramics prepared by Kumar et al. were in the range of 0.15-0.20 μm.

Kumar et al. also did preliminary work on using a Bismuth-based solution to coat hydrothermal BaTiO

3

crystallites so as to form a low-firing BaTiO

3

material. (See: Kumar et al., “Densification and Dielectric Properties of Hydrothermal BaTiO

3

with Different Bi

2

O

3

Sources”,

Ferroelectrics,

Vol. 154, 283-288, 1994). Bismuth oxide powder was also mixed with the hydrothermal BaTiO

3

crystallites, and the sintering results from the conventionally mixed batch was compared with the two solution-coated batches. BaTiO

3

ceramics with 3.0 wt % equivalent Bi

2

O

3

addition could be sintered to >90% theoretical density as low as 800° C. for the two solution-coated batches. Yet, even though sintering results for solution-coated batches looked promising, the two solution-coated BaTiO

3

powders did not show consistent densification results with each other. No details were given regarding the composition of the Bismuth-based solutions

Accordingly, it is an object of this invention to provide an improved BaTiO

3

ceramic that can be fired at a relatively low firing temperature.

It is a further object of this invention to provide an improved BaTiO

3

ceramic that exhibits consistent densification results.

It is another object of this invention to provide an improved BaTiO

3

ceramic that exhibits improved dielectric properties, even when fired at a low temperature.

SUMMARY OF THE INVENTION

Hydrothermal BaTiO

3

crystallites were coated with Bismuth solutions prepared from Bismuth metal-organics and anhydrous solvents. The Bismuth metal-organics were Bi 2-ethylhexanoate and Bi-neodecanoate. Bismuth oxide was also used as a comparison to the Bismuth solutions. BaTiO

3

ceramics with either 3.0 wt % equivalent Bismuth oxide or 5.0 wt % equivalent Bismuth oxide were made by sintering the compacts between 700° C. and 1000° C. BaTiO

3

ceramics that were coated by Bi-neodecanoate densified >90% theoretical as low as 800° C. for 3.0 wt % equivalent Bi

2

O

3

. Average grain sizes of 0.2-0.4 μm were observed for Bi-coated BaTiO

3

ceramics. Dielectric K versus temperature measurements of Bismuth-coated BaTiO

3

ceramics, sintered in the lower temperature ranges, showed consistently superior dielectric characteristics.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1

is a diagram which illustrates the process by which the improved BaTiO

3

ceramics were produced.

FIG. 2

is a plot of dielectric K and tan δ versus temperature for Bi-coated (3.0 wt % Bi

2

O

3

) BaTiO

3

ceramics sintered to 800° C., wherein the Bismuth precursors were: (1) Bi 2-ethylhexanoate (Johnson Matthey Batch 23) and (2) Bi-neodecanoate (Strem, Batch 25). Also, dielectric K and tan δ curves for all figures are plotted at 1.0 kHz frequency.

FIG. 3

is a plot of dielectric K and tan δ versus temperature for Bi-coated (3.0 wt % Bi

2

O

3

) BaTiO

3

ceramics sintered to 900° C., wherein the Bismuth precursors were: (1) Bi 2-ethylhexanoate (Strem, Batch 14); (2) Bi 2-ethylhexanoate (Johnson Matthey, Batch 23); (3) Bi-neodecanoate (Strem, Batch 25) and (4) Bi

2

O

3

(Aldrich, Batch 33).

FIG. 4

is a plot of dielectric K and tan δ versus temperature for Bi-coated (5 wt % Bi

2

O

3

) BaTiO

3

ceramics sintered to 800° C., wherein the Bismuth precursors were: (1) Bi 2-ethylhexanoate (Strem Batch 15); (2) Bi 2-ethylhexanoate (Johnson Matthey, Batch 24); (3) Bi-neodecanoate (Strem, Batch 26); (4) Bi

2

O

3

(Aldrich, Batch 34); and (5) Bi 2-ethylhexanoate (Strem, Batch 47). Note that for Batch 47, BaTiO

3

source is Cabot BT-8, instead of Cabot BT-10.

FIG. 5

is a plot of dielectric K and tan δ versus temperature for Bi-coated (5 wt % Bi

2

O

3

) BaTiO

3

ceramics sintered to 900° C., wherein the Bismuth precursors were: (1) Bi 2-ethylhexanoate (Strem, Batch 15); (2) Bi 2-ethylhexanoate (Johnson Matthey, Batch 24); (3) Bi-neodecanoate (Strem, Batch 26) and (4) Bi

2

O

3

(Aldrich, Batch 34); and (5) Bi 2-ethylhexanoate (Strem, Batch 47). Note that for Batch 47, BaTiO

3

source is Cabot BT-8, instead of Cabot BT-10.

FIG. 6

is a plot of dielectric K and tan δ versus temperature for Bi-coated (5 wt % Bi

2

O

3

) BaTiO

3

ceramics sintered to 1000° C., wherein the Bismuth precursors were: (1) Bi 2-ethylhexanoate (Strem, Batch 15); (2) Bi 2-ethylhexanoate (Johnson Matthey, Batch 24); (3) Bi-neodecanoate (Strem, Batch 26) and (4) Bi

2

O

3

(Aldrich, Batch 34).

DETAILED DESCRIPTION OF THE INVENTION

Two types of Bismuth metal-organics, Bi 2-ethylhexanoate (Strem Chemicals and Johnson Matthey) and Bi-neodecanoate (Strem Chemicals) were investigated as coatings for hydrothermal BaTiO

3

crystallites. Such crystallites exhibit diameters in the range of 0.1 μm to 0.2 μm. By contrast, Bi

2

O

3

crystallites exhibit diameters in the range of 1.0μ. Since it is desired that the end result of the process be hydrothermal BaTiO

3

crystallites with nanometer-thickness coating of a Bi-containing compound, it was realized that such a result could not be achieved through use of Bi

2

O

3

crystallites.

The goals for coating hydrothermal BaTiO

3

powders were to (i) minimize the final amount of Bi

2

O

3

in the densified BaTiO

3

ceramics, (ii) minimize the grain size, and (iii) lower the overall sintering temperatures for the Bismuth-coated BaTiO

3

ceramics. Three different sources of commercially available hydrothermal BaTiO

3

powders were sintered with and without the Bismuth coatings in order to determine if certain powder characteristics (e.g., crystallite size, surface area, Ba/Ti stoichiometry, etc.) in conjunction with the Bismuth coatings enhanced the densification of the hydrothermal BaTiO

3

powders.

BaTiO

3

ceramics with either 3.0 wt % equivalent Bismuth oxide or 5.0 wt % equivalent Bismuth oxide were made by sintering the compacts between 700° C. and 1000° C. BaTiO

3

ceramics that were coated by Bi-neodecanoate densified >90% theoretical as low as 800° C. for 3.0 wt % equivalent Bi

2

O

3

. Average grain sizes of 0.2-0.4 μm were observed for Bi-coated BaTiO

3

ceramics. Dielectric K versus temperature measurements of Bismuth-coated BaTiO

3

ceramics, sintered in the lower temperature ranges, showed consistently superior dielectric characteristics.

EXPERIMENTAL PROCEDURE

Three hydrothermal BaTiO

3

powders were used in the investigation: Cabot BT-10 (i.e. surface area of 10 m

2

/g), Cabot BT-6 (i.e., 6 m

2

/g), and Sakai BT-01 (i.e., crystallite size of 0.1 μm). Bismuth-containing chemicals used to coat the hydrothermal BaTiO

3

powders were Bismuth 2-ethylhexanoate (Strem Chemicals), Bi 2-ethylhexanoate (Johnson Matthey), and Bi-neodecanoate (Strem Chemicals). Bismuth oxide (Bi

2

O

3

, Aldrich Chemicals) was used as a comparison to the Bismuth metal organic compounds, since the objective was to determine if the Bismuth precursors were more effective in coating the hydrothermal BaTiO

3

crystallites than the Bi

2

O

3

particles.

Sources for the various BaTiO

3

powders and Bismuth compounds were as follows:

Designation

Company

Company Address

BaTiO

3

Powders

Cabot BT-10

Cabot Performance

P.O. Box 1608

Materials

County Line Road

Boyertown, PA 19512

Cabot BT-8

Cabot Performance

Boyertown, PA 19512

Materials

Cabot BT-6

Cabot Performance

P.O. Box 1608

Materials

County Line Road

Boyertown, PA 19512

Sakai BT-01

Sakai Chemical

5-1 Ebisujima-cho, Sakai

Industry Company,

Osaka 590, Japan

Ltd.

Bismuth Compounds

Bi-2ethylhexanoate

Strem Chemicals

7 Mulliken Way

Dexter Industrial Park

Newburyport, MA

01950-4098

Bi-neodecanoate

Strem Chemicals

7 Mulliken Way

Dexter Industrial Park

Newburyport, MA

0194098

Bi-2ethylhexanoate

Alfa Aesar

30 Bond Street

Ward Hill, MA 01835

Bismuth oxide

Aldrich Chemical Co.,

1001 West St. Paul Avenue

Inc.

Milwaukee, WI 53233

Bi metal

OM Group, Inc.

2301 Scranton Road

carboxylates

Kokkola Chemicals

Cleveland, OH 44113

Mooney Chemicals,

Inc.

Vasset S.A.

Bi metal

Chemet Technology

19365 Business Center

carboxylates

Drive

Bi alkoxides

Northridge, CA 91324

Bi alkoxide-

carboxylates

Anhydrous solvents used to disperse the Bi-containing chemicals were 1-Butanol, 1-Propanol, and Ethanol. A summary of the various experimental parameters is given in Table I below.

TABLE I

Amount of

Bi

2

O

3

Composition

Addition

Bismuth Source

Solvent

Cabot BT-10B

5.0

Bi 2-ethylhexanoate

1-Butanol

(Batch 15)

(Strem)

Cabot BT-6

5.0

Bi 2-ethylhexanoate

Ethanol

(Batch 10)

(Strem)

Sakai BT-01

5.0

Bi 2-ethylhexanoate

1-Butanol

(Batch 22)

(Strem)

Cabot BT-10B

3.0

Bi 2-ethylhexanoate

1-Butanol

(Batch 14)

(Strem)

Cabot BT-10B

3.0

Bi-neodecanoate

1-Butanol

(Batch 25)

(Strem)

Cabot BT-10B

3.0

Bi

2

O

3

(Aldrich)

None

(Batch 33)

Cabot BT-10

5.0

Bi

2

O

3

(Aldrich)

None

(Batch 34)

Cabot BT-10B

5.0

Bi-neodecanoate

1-Butanol

(Batch 26)

(Strem)

FIG. 1

shows the procedure used for coating and densification of hydrothermal BaTiO

3

powders (box 10) in accordance with the invention. The amount of the Bismuth metal-organic materials was varied, using either 3.0 wt % or 5.0 wt % equivalent Bi

2

O

3

additions to BaTiO

3

powders. The Bismuth-containing solutions (box 12) were prepared in a glovebox by mixing the Bismuth metal-organic with an anhydrous solvent in an argon atmosphere.

The Bismuth-containing solutions were added to hydrothermal BaTiO

3

powders and were mixed for six hours (box 14). After drying off the solvent (box 16), the residual organics in the Bismuth-coated hydrothermal BaTiO

3

powders were decomposed in air at 500° C. for six hours (box 18). The heat-treated powders were mixed with an acryloid resin binder (box 20) (Rohm and Haas), and then uniaxially pressed at 210 MPa in a Carver press to form green ceramic disks (box 22). The acryloid binder was removed from the samples by a 2-step heating profile, first at 300° C. for 3 hours and then at 550° C. for 5 hours (box 24). Samples were then sintered in closed alumina (Al

2

O

3

) crucibles for two hours with temperatures ranging from 700° C. to 1000° C. (box 26).

Uncoated and Bismuth-coated BaTiO

3

powders were analyzed (box 28) for surface area (BET) by a Quantachrome Monosorb BET unit. Weight loss and decomposition of the residual organics in the coated BaTiO

3

powders were analyzed by a Perkin-Elmer Thermogravimetric Analyzer (TGA-7) and a Perkin-Elmer Differential Thermal Analyzer DTA 1700, respectively. Phase analysis of the uncoated and Bismuth-coated BaTiO

3

powders was conducted on a Scintag DMC-105 x-ray diffractometer. Bulk densities of sintered BaTiO

3

samples were measured at room temperature by Archimedes principle by immersing the samples in Xylene.

Microstructures of the sintered samples were observed on fracture surfaces of the samples with an ISI-SKI 130 scanning electron microscope (SEM, Akashi Beam Technology Corporation). Dielectric properties of ceramic disk samples with sputtered gold electrodes were measured on a computer controlled setup consisting of a Hewlett Packard 4274A LCR Bridge and a Delta Design temperature chamber. Measurements were taken on the samples on cooling from 200° C. to −50° C. over a frequency range of 100 to 10,000 Hz, at a cooling rate of 1.0° C./min.

RESULTS

A. Densification and Properties of Hydrothermal BaTiO

3

Powders

Characteristics of the as-received Cabot BT-10, Cabot BT-6, and Sakai BT-01 hydrothermal BaTiO

3

are presented in Table II below.

TABLE II

Characteristics of Uncoated Hydrothermal BaTiO

3

Powders

Spectrorochemical

Surface

Crystallite

BaTiO

3

Analysis

Area (BET)

Size (BET)

Composition

Ba:Ti Ratio

(m

2

/g)

(nm)

Cabot BT-10B

1.01

10.05 (room temp.)

99.2

8.22 (800° C.)

121.3

Cabot BT-8

1.006

8.64 (room temp.)

115.4

Cabot BT-6

0.99

7.39 (room temp.)

134.9

5.39 (800° C.)

184.9

Sakai BT-01

1.00

14.25 (room temp.)

69.9

8.79 (800° C.)

113.4

(1) Crystallite size is calculated from the following equation:

PD = 6(p*SA)

where PD = crystallite size (nm)

p = theoretical density (6.02 g/cc for BaTiO

3

)

SA = surface area (m

2

/g).

Assumption - have spherical crystallites

The BaTiO

3

powders still exhibited a significant surface area after heat treatment at 800° C., ranging from 5.40 m

2

/g for Cabot BT-6 to 8.80 m

2

/g for Sakai BT-01, which indicates that these heat-treated powders still had fine crystallite sizes (10

2

˜10

3

nm).

Chemical analysis of the hydrothermal BaTiO

3

powders showed the Cabot BT-10 powder to have had a slight excess of Barium (0.002-0.010 moles). This excess Barium in Cabot BT-10 composition is important when analyzing the sintering results of the various hydrothermal BaTiO

3

powders.

Densification of Cabot BT-10 was >96% theoretical density at 1100° C. for a 2-hour soak time, which is 100° C. lower than that for Sakai BT-01 and 200° C. lower than that for Cabot BT-6 (see Table III below). A fine grain-size microstructure was observed for BaTiO

3

ceramics of Cabot BT-10 composition that are sintered at 1100° C.; however, large grains (>5.0 μm) were observed in the BaTiO

3

ceramics of this composition when sintered above 1200° C.

Results of densification and dielectric properties of ceramics that were sintered from Bismuth-coated (5.0 wt % equivalent Bi

2

O

3

) Cabot BT-10, Cabot BT-6, and Sakai BT-01 powders are shown in Table IV below. The Bismuth metal organic used to coat these hydrothermal BaTiO

3

powders is a Bismuth 2-ethylhexanoate from Strem Chemicals. Ceramics of Bismuth-coated Cabot BT-10 composition densified as low as 800° C., compared to 900° C. for Bismuth-coated Cabot BT-6 and >1000° C. for Bismuth-coated Sakai BT-01 samples. The reason for Bismuth-coated Cabot BT-10 hydrothermal powder densifying at a lower temperature than the other hydrothermal BaTiO

3

powders was the probable formation of a liquid phase due to combination of Bi

2

O

3

flux and the Barium-rich surface layer of hydrothermal BaTiO

3

powder.

When this liquid phase does occur during sintering, it is likely to cause a glassy grain boundary phase that surrounds the pure BaTiO

3

grains, which is typical for core-shell microstructures that are observed in BaTiO

3

-based dielectric compositions. Indirect evidence of the formation of this Bismuth-containing glassy phase was illustrated by limited grain growth for Bismuth-coated BaTiO

3

ceramics of Cabot BT-10 composition below 1000° C. and

TABLE III

Density and Dielectric Properties of Uncoated BaTiO

3

Sintered at Different Temperatures

Sintering

Bulk

%

Grain

Weight

Dielectric

BaTiO

3

Temp.

Density

Theoretical

Size

Change

K

RT

tanδ

RT

K

max

T

max

Composition

(° C.)

(g/cm

3

)

Density

(μm)

(%)

(1.0 kHz)

(1.0 kHz)

(1.0 kHz)

(° C.)

Cabot BT-10B

1000

4.74

78.7

—

−0.9

—

—

—

—

1100

5.81

96.5

0.5-5.0

−1.1

3055

0.027

6235

121

1200

5.87

97.5

4.0-8.0

−1.2

2695

0.023

8960

121

1300

5.87

97.5

5.0-20.0

−1.3

2295

0.025

9250

123

Cabot BT-8

1100

5.23

86.9

—

−0.69

4950

0.064

—

—

1200

5.78

96.0

—

−0.69

5340

0.015

10,005

125

1300

5.84

97.0

—

−0.75

3825

0.010

10,340

127

Cabot BT-6

1100

3.97

69.7

—

−0.4

—

—

—

—

1200

5.11

84.9

0.5-1.0

−0.5

4085

0.012

5980

122

1300

5.92

98.3

—

−0.5

3760

0.006

9470

126

1400

5.85

97.2

10.0-40.0

−1.2

1980

0.016

12,820

127

Sakai BT-01

1000

3.83

63.6

0.49

−0.9

1775

0.015

2820

123

1100

4.49

74.6

0.77

−0.9

3180

0.019

5580

123

1200

5.92

98.3

—

−1.0

—

—

—

—

1300

5.93

98.5

—

−1.0

2725

0.035

13,530

128

TABLE IV

Density and Dielectric Properties of Various Solution-Coated BaTiO

3

Compositions

(+5.0 wt % Bi

2

O

3

) Sintered at Different Temperatures

Sintering

Bulk

%

Grain

Weight

Dielectric

BaTiO

3

Temp.

Density

Theoretical

Size

Change

K

RT

tanδ

RT

K

max

T

max

Composition

(° C.)

(g/cm

3

)

Density

(μm)

(%)

(1.0 kHz)

(1.0 kHz)

(1.0 kHz)

(° C.)

Cabot BT-10B

700

5.19

84.3

0.23

−0.26

1200

0.029

1450

98

800

5.72

92.9

0.24

−0.45

1805

0.030

2330

113

900

5.93

96.3

0.39

−0.50

2575

0.044

7910

127

1000

5.82

94.5

3.44

−0.52

3650

0.234

17,345

129

Cabot BT-8

800

5.61

91.1

0.21

−0.65

1535

0.013

2270

109

900

5.69

92.4

0.23

−0.67

1750

0.012

2855

113

Cabot BT-6

700

4.57

74.2

0.20

0.00

790

0.018

1145

109

800

5.21

84.6

0.23

−0.15

1250

0.012

1960

104

900

5.39

87.6

0.22

−0.22

1340

0.010

2215

107

1000

5.52

89.7

0.24

−0.31

1770

0.009

3340

110

Sakai BT-01

700

3.52

57.2

—

−0.07

—

—

—

—

800

4.29

69.7

0.11

−0.32

525

0.031

600

89

900

4.68

76.0

0.13

−0.48

710

0.025

865

96

1000

5.19

84.3

0.17

−0.70

980

0.015

1295

103

(1) Bismuth precursor used to coat the BaTiO

3

compositions is Bismuth 2-ethylhexanoate from Strem Chemicals.

(2) Bismuth precursor is dispersed in 1-Butanol for Cabot BT-10B and Sakai BT-01 compositions, and it is dispersed in ethanol for Cabot BT-6 composition.

the lowering and the broadening of cubic to tetragonal transition peak (Table IV). It has been reported that Bismuth does not rapidly diffuse to form a homogeneous composition with BaTiO

3

, so that concentration gradients result in an average of localized Curie points broadening the dielectric anomaly, instead of a single transition peak.

Increasing the sintering temperature to 1000° C. for Bismuth-coated Cabot BT-10 BaTiO

3

composition resulted in large grain growth and an increase in the Curie temperature to 129° C. The core-shell microstructure was most likely gone by 1000° C. in the BaTiO

3

ceramics of this composition, since higher sintering temperature promoted a more homogeneous distribution of the Bismuth.

B. Densification and Dielectric Properties of Bismuth-Coated Cabot BT-10 BaTiO

3

Using Different Bismuth Sources

As indicated above, the Bismuth-coated Cabot BT-10 composition exhibited better densification and dielectric properties than the other two Bismuth-coated hydrothermal BaTiO

3

powders. Next, two other Bismuth sources, i.e., Bismuth oxide (Bi

2

O

3

) from Aldrich and Bismuth neodecanoate from Strem Chemicals, were compared to Bismuth 2-ethylhexanoate, in coating the Cabot BT-10 BaTiO

3

powder. The solvent used to disperse the Bismuth neodecanoate and the Bismuth 2-ethylhexanoate was 1-Butanol, because Bismuth metal organics readily go into solution and remain so for an extended period of time.

Thermal gravimetric analysis shows the Bismuth-coated Cabot BT-10 BaTiO

3

powders that were coated with either of the Bismuth metal-organics to have small weight losses (5.0˜8.0 wt %) and to have their weight loss finished by 500° C. Differential thermal analysis (DTA) of the Bismuth-coated BaTiO

3

compositions also showed the decomposition of the organics to be complete by 500° C.

Theoretical densities and dielectric properties of Cabot BT-10 hydrothermal BaTiO

3

, coated with different Bismuth sources at 3.0 wt % equivalent Bi

2

O

3

and at 5.0 wt % equivalent Bi

2

O

3

, are shown in Table V and Table VI (below), respectively.

Bismuth-coated Cabot BT-10 BaTiO

3

coated with Bismuth neodecanoate, sintered to high densities as low as 800° C. for a 2-hour soak time for a 3.0 wt % Bi

2

O

3

addition, and as low as 700° C. for the same amount of time for a 5.0 wt % Bi

2

O

3

addition. Comparing the fracture surfaces of 3.0 wt % addition Bismuth-coated BaTiO

3

ceramics that were sintered at 800° C., a uniform fine-grain size microstructure (i.e., 0.2˜0.4 μm) was observed for Cabot BT-10 BaTiO

3

coated with Bismuth neodecanoate. On the other hand, hydrothermal BaTiO

3

crystallites were still being sintered together for Cabot BT-10 BaTiO

3

powders that were either coated with Bismuth 2-ethylhexanoate or mixed with Bi

2

O

3

.

X-ray dot maps of fracture surfaces of Bismuth-coated BaTiO

3

ceramics showed the Bismuth ions to be dispersed throughout the microstructure for these ceramics that were sintered at 800° C. from Cabot BT-10 BaTiO

3

powders coated with any one of the Bismuth sources. An X-ray dot map of the fracture surface of a BaTiO

3

ceramic that was prepared from Cabot BT-10 BaTiO

3

powder, coated with Bismuth neodecanoate and sintered to 1000° C., indicates that the Bismuth had not remained evenly distributed in the microstructure after a 2-hour soak time. Furthermore, the corresponding scanning electron micrograph of the Bismuth-coated BaTiO

3

ceramic showed large grain growth. This grain growth was typical for BaTiO

3

ceramics that were sintered at 1000° C. from Bismuth-coated Cabot BT-10 BaTiO

3

powders. On the other hand, this large grain growth was not observed for other Bismuth-coated BaTiO

3

compositions (i.e., Cabot BT-6 and Sakai BT-01) unless they were sintered well above 1000° C.

TABLE V

Density and Dielectric Properties of Solution-Coated BaTiO

3

(3.0 wt % Bi

2

O

3

) Using Different

Bismuth Sources and Sintered at Different Temperatures

Sintering

Bulk

%

Grain

Weight

Dielectric

Temp.

Density

Theoretical

Size

Change

K

RT

tanδ

RT

K

max

T

max

Bismuth Source

(° C.)

(g/cm

3

)

Density

(μm)

(%)

(1.0 kHz)

(1.0 kHz)

(1.0 kHz)

(° C.)

Bi-2ethylhexanoate

700

3.37

55.3

—

−0.24

—

—

—

—

(Strem)

800

4.29

70.4

0.22

−0.53

755

0.021

930

96

900

5.63

92.3

0.41

−0.84

2335

0.035

3340

112

1000

5.83

95.6

2.29

−0.90

2960

0.098

13,560

122

Bi-neodecanoate

700

4.95

81.2

0.21

−0.39

860

0.045

975

93

(Strem)

800

5.77

94.6

0.24

−1.62

2115

0.026

2875

98

900

5.91

96.9

1.86

−1.80

4370

0.067

7760

108

1000

5.84

95.8

2.87

−2.00

3490

0.255

18,080

110

Bi

2

O

3

800

4.04

66.3

0.21

−0.64

—

—

—

—

(Aldrich)

900

5.72

93.8

0.49

−1.13

2695

0.081

5730

117

1000

5.85

95.9

2.86

−1.17

2590

0.037

9570

121

1100

5.76

94.5

6.53

−1.70

2160

0.078

12,555

124

(1) BaTiO

3

composition used here is Cabot BT-10B.

(2) Solvent used to disperse the Bismuth precursors is 1-Butanol.

TABLE VI

Density and Dielectric Properties of Solution-Coated BaTiO

3

(5.0 wt % Bi

2

O

3

) Using Different

Bismuth Sources and Sintered at Different Temperatures

Sintering

Bulk

%

Grain

Weight

Dielectric

Temp.

Density

Theoretical

Size

Change

K

RT

tanδ

RT

K

max

T

max

Bismuth Source

(° C.)

(g/cm

3

)

Density

(μm)

(%)

(1.0 kHz)

(1.0 kHz)

(1.0 kHz)

(° C.)

Bi-2ethylhexanoate

700

5.19

84.3

0.23

−0.26

1200

0.029

1450

98

(Strem)

800

5.72

92.9

0.24

−0.45

1805

0.030

2330

113

900

5.90

96.3

0.39

−0.50

2575

0.044

7910

127

1000

5.76

94.5

3.44

−0.52

3650

0.234

17,345

129

Bi-neodecanoate

700

5.61

91.1

0.21

−1.21

2715

0.246

—

—

(Strem)

800

5.83

94.7

0.26

−1.38

1990

0.053

2745

107

900

5.68

92.3

1.81

−1.44

5930

0.349

19,860

111

1000

5.83

94.7

—

−1.84

2200

0.318

—

—

Bi

2

O

3

700

4.32

70.8

—

−0.62

—

—

—

—

(Aldrich)

800

5.46

88.7

0.29

−0.95

1765

0.027

2290

112

900

5.62

91.3

0.28

−0.99

2010

0.028

2710

109

1000

5.60

91.0

3.19

−1.29

3470

0.220

16,255

123

(1) BaTiO

3

composition used here is Cabot BT-10B.

(2) Solvent used to disperse the Bismuth precursors is 1-Butanol.

Dielectric properties of Bismuth-coated BaTiO

3

ceramics that were sintered at 800° C. from Cabot BT-10 BaTiO

3

coated with Bismuth neodecanoate were better than those for BaTiO

3

ceramics that were sintered from Cabot BT-10 BaTiO

3

powders coated with the other two Bismuth sources. Bismuth-coated BaTiO

3

ceramics that were sintered at 800° C. from powders coated with Bismuth neodecanoate have a room temperature dielectric K value of 2115 and a tan δ value of 0.026 for 3.0 wt % equivalent Bi

2

O

3

addition, and also a room temperature dielectric K value of 1990 and a tan δ value of 0.053 for 5.0 wt % equivalent Bi

2

O

3

addition.

Dielectric K and tan δ vs. temperature curves for Bismuth-coated BaTiO

3

ceramics at 3.0 wt % addition and at 5.0 wt % addition are shown in

FIGS. 2

,

3

and

4

,

5

,

6

, respectively. For Bismuth-coated BaTiO

3

ceramics that were sintered at 900° C. and 1000° C. from BaTiO

3

powders that were coated with Bi-2-ethylhexanoate, the loss (tan δ) curves show a sharp decrease at the Curie temperature and then sharply increase above the Curie temperature.

CONCLUSIONS

Bismuth-coated hydrothermal Cabot BT-10 BaTiO

3

densifies to high densities as low as 800° C. for a 2-hour soak for a 3.0 wt % equivalent Bi

2

O

3

addition. Bismuth-coated BaTiO

3

ceramics densify at lower temperatures than those for non-coated BaTiO

3

ceramics, due to the formation of a Bismuth glassy phase surrounding the hydrothermal BaTiO

3

crystallites, which is similar to formation of core-shell microstructures in BaTiO

3

-based dielectric ceramics. Indirect evidence of this formation of core-shell microstructures in Bismuth-coated BaTiO

3

ceramics is observed in the lowering and the broadening of the cubic to tetragonal transition peak for these BaTiO

3

ceramics, which indicates a distribution of local Curie temperatures resulting from localized distribution of Bismuth. Bismuth neodecanoate results in BaTiO

3

ceramics densifying as low as 800° C. for 3.0 wt % equivalent Bi

2

O

3

addition and as low as 700° C. for 5.0 wt % equivalent Bi

2

O

3

addition. Uniform fine-grain size microstructure (0.2˜0.4 μm) was observed in these Bismuth-coated BaTiO

3

ceramic materials. Above sintering temperatures of 900° C., large grain growth occurs in BaTiO

3

ceramics that were sintered from Cabot BT-10 hydrothermal BaTiO

3

powders which were coated with Bismuth neodecanoate. Hydrothermal BaTiO

3

powders which were coated with Bismuth 2-ethylhexanoate also sintered to high densities, while exhibiting fine grain size microstructures.

It should be understood that the foregoing description is only illustrative of the invention. Various alternatives and modifications can be devised by those skilled in the art without departing from the invention. For instance, while the above discussion has considered the pre-fired shapes (i.e., masses) as preforms, it is to be understood that such masses can also take the form of a paste or a liquid. Accordingly, the present invention is intended to embrace all such alternatives, modifications and variances which fall within the scope of the appended claims.

Solution coated hydrothermal BaTiO3 for low-temperature firing

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