JPS60152003A - Method of producing zinc oxide nonlinear resistor - 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 [Technical Field] This invention relates to a method of manufacturing a zinc oxide non-+FX Mf resistor.

[Conventional technology and problems]

Generally, zinc oxide nonlinear resistor (hereinafter referred to as ZnO element)
As for Bi as the main sacrifice, 0. and several other metal oxide formulations are used. This element undergoes a heat treatment process at 400"C to 900C to improve durability and insulate the outer periphery of the element, but this heat treatment greatly reduces the 1d piezoelectric current nonlinearity of the water. There is a drawback that this characteristic decreases by 1 degree because the B1゜0 and crystal sliding d change due to heat treatment.Also, the above element has a certain current range (normally 100 μA to IAI). Nonlinear characteristics have a nonlinearity index (α) of 20 or more, but if it is less than or more than 20, the characteristics are extremely degraded.Furthermore, the main additive Bi, 03, has a nonlinearity index (α) of 20 or more. is 2XIO
- Poor in Il and bones.

[Purpose of the invention]

An object of the present invention is to eliminate the above-mentioned drawbacks, to provide a method for manufacturing a zinc oxide nonlinear resistor that prevents deterioration of nonlinear characteristics due to heat treatment, and reduces leakage during energization. do.

In order to achieve the above-mentioned object, this invention preliminarily contains pbO,
The powder heat-treated sb, o at 80θ to 1100°C was used as ZnO, MnO, 81,203, Cr20B,
It has a structure in which it is mixed with NiO powder, pressure molded, and the molded product is subjected to t^ treatment.

〔Example〕

An embodiment of the present invention will be described below with reference to the drawings.

First, predetermined amounts of PbO and 5btOs were weighed out at a molar ratio of 2=1, mixed well in a centrifugal ball mill, and then calcined at 1000° C. for 4 hours in an aluminium crucible. The calcined product thus calcined is ground in the ball mill to obtain a reaction product. After that, ZnO: 98. Omo
14b Mn0t: 0.5mol1%, 5l)tOs:
Weigh a predetermined amount of 0.5 mo1%, er, o,: 0.5 mo14 and NiO: 0.5 mob%, add 2 g of the above reactant to these, and mix these powders well, Pressure mold into a disc shape. Thereafter, the molded body was heated to 1100"C in air.

After firing for 6 hours, both end faces of the compact were polished, coated with Ag electrodes, and heat treated at 590''C for 11 hours.

FIG. 1 is a characteristic diagram showing the voltage four current characteristics of the ZnO element manufactured according to the above example and the voltage current characteristics of the ZnO element without NiO added. In the figure, curve A is that of this MIi example. , curve B is for the latter element. As is clear from FIG. 1, the nonlinear characteristics in the current domain of this embodiment do not deteriorate significantly. However, in the latter case, the nonlinear characteristics are extremely poor as described in the prior art.

Figure 2 shows 0.1α1.
Curve A showing 0 value (current is nonlinear index between 0.1 mA and l, QmA) and ΔV after application of 8 × 20 μs pulses of IQKA, voltage change rate 1°0/v□,. It is a characteristic diagram of curve B showing.

FIG. 3 is a characteristic diagram showing the rate of change of {circle around (2)} and {circle around (2)} with respect to the pulse 'α flow value, where curve A is for this example and curve B is for the element without NiO added.

As is clear from FIGS. 1 to 3 above, the resistor prepared according to this example has a characteristic that the rate of voltage change after pulse application is extremely small compared to a resistor to which no NiO is added.

Further, the heat treatment width of the sintered body is preferably 500"C to 850"C; below that, the life expectancy will not be improved, and above 850C, the non-1r-line characteristics/ba will deteriorate.

Furthermore, the heat treatment time varies depending on the thickness of the water droplets, but
The heating and cooling rate is preferably 200° C./hour or less, which is sufficient to prevent distortion of the device due to rapid heating, cooling, etc. Note that the firing temperature is 1000 ~] 300"C is good, and if it is lower than that, a dense sintered body will not be obtained;
If it exceeds 'C, PbO will volatilize and nonlinearity will deteriorate.

The firing time is preferably 1 to 20 hours, but a uniform sintered body cannot be obtained within 1 hour. After 20 hours or more, the volatilization of Pl, 0, and Sbto3 near the surface cannot be ignored.

From the above results, the range of additive components in the ZnO element manufacturing method is PbO, and the F3b20B reactant is 0.2 to 20 Wt.
@%MnO, is O, l -5mol 'Iy, 5btO
s is 0.1-5mol 4y, 0r203 is Q, l
-5 mol %, NiO is preferably 0.1 to 5 mol %; if it is less than this range, no effect will be seen, and if it is more than this, nonlinearity will decrease. Also, NiO is O, ] mo1 %
If the amount is less than 5 mol 4, no effect will be seen, and if the amount is more than 5 mol 4, the cardiac pressure rate after impulse application will increase.

In the above embodiments, a long ball mill, an alumina crucible, etc. were used, but other types of these may be used.

〔Effect of the invention〕

As described above, according to the present invention, the crystal structure does not change even through heat treatment, so the non-linear characteristic does not deteriorate, and the non-linear characteristic value is is high, there is little leakage current during energization, and the increase in leakage current due to energization time is also small, so the durability is significantly increased.Moreover, Bi.

03 series element (Clark number of Bi 2 x Hl-'')
compared to PbO (Clarke number of Pb 1.5 x 1O
-3), it has the advantage of being abundant as a resource.

[Brief explanation of the drawing]

・The first diagram shows Zn manufactured by an embodiment of the present invention.
The average current characteristic of the O element and the voltage-current characteristic diagram of the element without NiO added. Figure 2 is a characteristic diagram showing the nonlinear index and the voltage change rate after pulse application when varying the amount of NiO added.
FIG. 3 is a characteristic diagram showing the rate of change of VAE with respect to pulse current. Figure 1 Figure 2 Nip attachment (mop 0m)

Claims (2)

[Claims] (1) After reacting Pl)0, 81)203 at a predetermined temperature in advance, the reactants are converted into ZnO, Mn01, 5b2
03, 0r203. A method for manufacturing a zinc oxide nonlinear resistor, which comprises cooling and mixing with NiO, pressure molding, and heat-treating the molded product. (2) The PbO, 5b203 reactant is 0.2 to 2
0 wt person. MnO2 from 0.1 to 5 mol 4, 8byon from 01 to 5 mol %, 0r103 from 01 to 5 mol %
mol %, NiO from 01 to 5. Z the mol staff
A method for manufacturing a zinc oxide nonlinear resistor according to claim 1, wherein the zinc oxide nonlinear resistor is added to nO. f3) iii J J. PbO, Sb, O5 having a molar ratio of 2:1 to 2=15 as a reactant, claim 1
il) A method for manufacturing a zinc oxide nonlinear resistor according to item 1.