JPS58176176A - Ceramic composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention The present invention provides a porcelain composition that can be sintered at a low temperature of 4IK 1050°C or lower, has a high 11 electric conductivity, has high insulation resistance at room temperature and high temperature, and has high mechanical strength. Things K
I'll do it.

Conventionally, baricum titanate (B
aTi0. ) is widely used in practical use. However, those whose main component is palicum titanate (BaTi0.) have a sintering temperature of usually 1300 to 1400°C. For this reason, this is used as the internal electrode of the laminated capacitor TK.A material 1 that can withstand the heating WL, such as platinum,
The drawback is that expensive precious metals such as palladium must be used, resulting in high manufacturing costs. In order to make multilayer capacitors cheaply, inexpensive metals mainly containing silver, nickel, etc. can be used for the internal electrodes.

Porcelain that can be sintered at a temperature as low as 1% and below 105θ°C is required.

In addition, the electrical properties of the porcelain composition include high a electrical conductivity <, a
Basically, low electrical loss and high insulation resistance are required. Furthermore, the insulation resistance value is 1/C@L.

This is a U.S. Department of Defense standard that requires highly reliable parts.
Specification) MIL-C-556
In 818.

In order to obtain a highly reliable porcelain capacitor, KFi, *Not only the value at room temperature, but also the value at 125°C is specified.

It is also necessary to have a high insulation resistance at the maximum operating temperature.

First, in the case of multilayer chip capacitors, when the chip capacitor is mounted on a board, mechanical strain is applied to the chip capacitor due to the difference in thermal coefficient K between the board and the porcelain that makes up the chip capacitor. , the chip capacitor may crack, or the chip may be damaged.

Also, for dip capacitors coated with epoxy resin, etc.

Dip condensation due to stress in exterior resin? Cracks may occur. In either case, the lower the mechanical strength of the porcelain that forms the capacitor, the more likely it is to crack and break.

Reliability decreases. Therefore, it is of practical importance to increase the mechanical strength of porcelain as much as possible.

By the way, Pb (Mg, AW) 0. -PbTJO
, N.N., Kutenik, A.I., Maglanovskaya N., N.Krai.
nik madA, I+mu grarovskaya
(Figiko Tverdogo Te1a, Vo
, 2°No, 1. pp 70-72, J fin va
RA 1960) Yoshi proposal is as, 9 (8rx P
b, ,TiO,), (PbML,s”e,5Os)b
[However, x=0 to 0.10. a is 0.35 to 0.5.
b is 0.5 to 0.65, and heat + b = 1)
Even with K.

A monolithic capacitor and a method for manufacturing the same are disclosed in JP-A-52-21662, and an i-9 dielectric powder composition is disclosed in JP-A-52-21699. However, none of them discloses the use of base paper, and the practicality of these porcelain compositions was not clear. It was.

The inventors have already been able to sinter at temperatures of 910-950°C.

Consisting of two components: Pb (Mg, AW, A'IO, and PbTi0).

This is expressed as [Pb(MgWv, )Os], [
When expressed as P bTr O * ) + −x,
A composition in which x is in the range of 0.65 <x'l, 1.00 is proposed. This composition has excellent electrical properties such as a high product of electrical constant and specific resistance and low dielectric loss. However, since all of the above compositions have low mechanical strength, their applications have had to be limited to a narrow range.

tft, Pb(Mg, AW, A)0. -PbTtO
, for ternary systems containing I! ! 111115
5-111011 in Pb(MgViW,A)
O, PbTtO, Pb(MgNb&/,)O, system is 9
Pb(Mg,,W
, A) 0. - PbTi0. −Pb(MgTζ−
〇.

system has been disclosed. however.

None of them discloses any specific resistance or mechanical strength, and the practicality of these ceramic compositions remains unclear.

9. The present inventors have already identified Krd(Mg,w,A)Os-
have already proposed a ternary composition of PbTiO,-Pb(NiLANb,A)Q. This composition contains 900
It can be sintered in the low temperature range of ~1050℃, and the electric conductivity is high.
It has excellent properties such as low electrical loss and high insulation resistance at room and high temperatures. However, since the mechanical strength of this composition is low, the users of this composition have had to define it within a narrow range.

Considering the point K of 1 or more, the present invention can be sintered in the low temperature range of 900 to 1050°C, has excellent electrical properties such as high a electrical conductivity, small S electrical loss, and high insulation resistance at room temperature and high temperature. The purpose is to provide a highly reliable porcelain composition that has a high mechanical strength and also has a high mechanical strength.
, lead titanate (PbTiO,) and nickel lead niobate CPb (Ni,ANb)0. ] consisting of 3
The constituent components were [Pb (Mg, W)0. ].

(PbTiO,)a(P b (N t , ANb)
0. J, When expressed as 1, K (where x + y
+ z 31.00) In this three-component composition diagram, the following composition points (x=0.693. y=0.297. !=0.
01) (x=0.495.y=0.495.z
=o, ol) (x=0.195, y=0.455.
! =0.35) (x=0.10, y=0°40, z=0.50) (X=0.06,
y = 0.24, z = 0.70) and in the composition range surrounded by these five points, manganese lead tantalate CP b is added as a subcomponent.
(Mn, ATa LA) 0, ') is added to the main component in an amount of 8 mo1% of O,OS.

The present invention will be described below with reference to Examples.

Lead oxide (PbO) with a purity of 99.9% or more as a starting material
.

Magnesium oxide (MgO), tungsten oxide (W)
O,).

Titanium oxide (Tie), Nickel oxide (Nip)
and niobium oxide (Nb, 0.), tantalum oxide (
Ta, 0. ) and manganese carbonate (MnCO, ) were weighed so as to have the compounding ratio shown in Table 1.The weighed materials were wet mixed in a ball mill and mixed at a temperature of 750 mm.
Pre-baked at ~800℃, crushed this powder in a mail mill, divided into 0 parts, dried, added an organic binder, sized and pressed to form 4 discs with a diameter of 16cm and a thickness of about 2wm, and a diameter of 4 discs. 1
A sample having a composition within the composition range of the present invention, in which a cylinder having a thickness of about 6 cm and a thickness of about 10 cm was prepared, was sintered in air at a temperature of 900 to 1050°C for 1 hour. Burn electrodes on the top and bottom surfaces of four sintered disks at 600℃, and measure the frequency IK with a digital LCR meter.
Hz, voltage 1vr, m, s.

The capacitance and dielectric loss were measured at a temperature of 20℃, and the B electric constant was calculated.A voltage of 50V was applied for 1 minute using a zero-order super insulation resistance meter, and the insulation resistance was measured at a temperature of 20℃ and 125℃. The resistance was calculated.

In order to evaluate the mechanical properties in terms of bending strength, ten rectangular plates with a thickness of 0.5 tan, INl 2 mm and a length of about 13 m were cut out from nine sintered cylinders. The distance between the fulcrums is 9
-, the breaking load pmcKp) was measured using the two-point method.

3)-m! According to f-(red), the FX folding strength τ""lWt correction CKg/cd was determined. However, l is the distance between the fulcrums.

t is the thickness of the sample, and W is the width of the sample. The electrical properties were determined from the average value of 4 disk samples, and the bending strength was determined from the average value of 10 rectangular plate samples. The main component of the porcelain thus obtained [P b (Mg +ytW, 1) 0. ], CP
bTl03]A[Pb(NiL/, Nb, A)0. ]2
Mixing ratio of X, y+! and steel component addition amount and dielectric constant,
11 Electrical loss, specific resistance at 20'C and 125°C,
The relationship between flexural strength and bending strength is shown in the table below.

(As is clear from the results shown in the table below, Pb(MgL/
kW, A) 0. - Pb'f'i0. - Pb (NiNb) 0. As component # in the three-component composition, Pb(M
fi, ATm, )0. Those within the scope of the present invention that contain added have a high m-electricity of 3090 to 13510, and 1
Single electric loss is small at 0.3 to 3.1 arc, and resistivity is 20℃
3.5xlO'1-2. I X 10”Q・e
x as high as 8 but 4125℃ & even 7.5 x 1
An extremely versatile porcelain composition that exhibits a high value of 0"-3,8X 10"Ω0 and also has a bending strength of 980 to 1410 Kv'al, which is sufficiently high for practical use. It can be seen that it is. The porcelain of the present invention, which exhibits these excellent properties, has a low sintering temperature of 1050°C or less, which makes it possible to reduce the cost of the internal electrodes of laminated air conditioners/suctions, as well as save energy and furnace materials.
5 Very good effects also occur.

Note that the main component composition of the present invention is CPb (Mg, Wv,)
0, ) [PbTi0. ) (Pb(Ni,,Nb
, A) 0. ], expressed as
l) (x=0.495.y=0.495.!
=0.01)(x=0.195.y=0.455
．． ! =0.35) (x=0.10, y=
0.40, z=0.50) (x=0.06
, y=0.24, ! =0.7
It is limited to the composition range on the line connecting (1) and surrounded by these five points, and the added content of the m component is 0.0% relative to the main component.
It is set at 05 to 8 mo1%. 0 composition point 2, 6 and composition point 1 in the three-component composition diagram representing the main component composition range
Outside the line connecting 7.19, the specific resistance at ^ temperature becomes small, and outside the line connecting 0 composition point 6, which is not practical, and 13.17, one point of Curie is within the practical range), and it shifts greatly toward the temperature side. Therefore, the ll electric rate becomes smaller and the 1 composition point becomes 19.
Outside the line connecting 2, the Curie point deviates significantly to the lower temperature side than the practical range, so the Il electric rate becomes small, making it less than the practical range &lA.

Pb (Mn, AT'5va) which is a component of mamaru steel 0. If the amount added is less than 0.05 mal1, the effect of improving bending strength is small.

If it exceeds 8 mo1%, the bending strength decreases, which is not practical.

Note that the numbers shown in Figure 0, which shows the main component composition range of the present invention in Figure 2, correspond to the numbers of the main component blending ratios shown in Table 9.

[Brief explanation of the drawing]

The figure is a diagram showing the main component composition range of the present invention and nine composition points shown in Examples. Procedural amendment 61 to Pb(MyhWy,)0-SPbT7
M) Commissioner of the Patent Office 1, Indication of the case 1981 Patent Application No. 058
No. 564 2. Title of the invention a. 6. Composition 3. Relationship to the amended case. Applicant: Shiba H, Minato-ku, Tokyo.
No. 33-1 (423) NEC Co., Ltd. Representative: Tadahiro Sekimoto 4, Agent 5, Column 6 of detailed expropriation of the invention in the statement of contents of the amendment, and the table on page 10 on the side of the details of the amendment as attached. Correct to. ν” Mackerel

Claims (1)

[Claims] Magnesium lead tungstate (Pb (MgW, A
)O, ), lead titanate (PbTi0. ) and lead nickel niobate (pb (N t , s Nb , A
)(1,), (Pb(Mgw,
, )o, ], (pbTto,). [pb(Ni,,Nbv,3o, ), expressed as 9, (circled x+y+i-1,00) This 3
The weight composition ■KTh, the following OII weight (x-0,693,7=0.297.z=0.01
) (! Engineering α495.y”0.495.Tax = 0
．． 01) (l-α195.7=0.455.g-
0,35) (x=0.10, 7=0.40,
1-0.50) (xmo, 06, yxO,
24, xmo, 70) and these five points Xa
As a steel ingredient in the main ingredient silver oxide in Sureken Shigenori■! Ngan mental acid brass (Pb (Ma, ATa, %)
A porcelain composition characterized in that it contains 0.05 to 8 malleum of O, ] to the main component.