JPS60153104A - 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] 14LF J The present invention relates to a method for manufacturing a zinc oxide nonlinear resistor.

[Conventional technology and difference]

In general, as a zinc oxide nonlinear resistor (hereinafter referred to as a zT10 element), an element containing 7Jl as the main additive, Bi2O2, and several other 41tN14 oxides is used. This element is made of 4001C to 90% for durability and insulation coating on the outer periphery of the element.
A heat treatment step at 0° C. is performed, but this heat treatment has the disadvantage that the voltage-current nonlinear characteristics of the device are greatly reduced. The reason for this decrease in properties is that the BL20g crystal 44 undergoes a diversion due to heat treatment. In addition, the above element has a non-surface line index of 20 or more in a certain torrential flow range (f of 100 μA to IA), but if There is a drawback that the characteristics are extremely deteriorated.Furthermore, the 8120g that comes with 1 main attachment LI item is B
The number of t-redundant Clarks is 2×10, which is a poor resource.

[Purpose of the invention]

The present invention eliminates the above-mentioned drawbacks, and provides a method that does not deteriorate the nonlinear characteristics due to heat treatment.
The overall object of the present invention is to provide a method for manufacturing a lead oxide nonlinear resistor with a reduced flow rate.

[4 Summary of the Invention] In order to achieve the above-mentioned objective ra, this invention
, 5b20sk800~] 100'C, Zllo, vnozl Sl: 120!
JO2 to l + Cr2O5.

r3tO2 and Aj? 20g Hf02, borosilicate non-complex glass, and 8102, A/2o, and zinc borosilicate glass were mixed separately and molded together by extrusion molding, and the formed cedar body was heat-treated to form the structure. It is in.

Examples] Figure 1 button below? An embodiment of the present invention will be described with reference to the drawings.

First, PiQ, 5h203k I! with a molar ratio of 2=1! j
At 118, the sample was weighed at a constant temperature of 1,000 liters, and then calcined in a centrifugal ball mill for 4 hours at a temperature of IOOO'C in an aluminum crucible.゛暚扮r The reaction product τ is obtained by pulverizing it in the Zeel mill.

Its bite, ZnO: 98. Omoi! Trillion, MnO2:
0.5 mOl<%*'9b20g:0,5 +u
oi1%* Cr2O5: 0.5 mol N, 8
LC12: O, /imolj% given -#H),
Add 2% of the 111th reactant to these powders, mash the powder, and press-form into a circular shape. Hand wheat, 1100 degrees Celsius in IJ brother's body, 0:00 1st bite, IJy:, Nosugi's 1 Mukaoka dry l't, UF m, Ag, <qik Nanbushi , 590, heat treatment τ for 1 hour is performed.

FIG.
In the figure, curve A is for the device according to this embodiment, and curve B is for the device not added to 5t02. As is clear from this first figure, the non-direct #iI% property in the υIL region of this embodiment does not become extremely distorted, but the latter element is the same as that described as the prior art. As shown, the non-linear characteristics are related to @L (
Become.

Figure 2 shows B L n 2's attached sword 0 spears & eteta sushi 0.
．． ]α1,0 value (current or 01・IIA and 1.(lIln
The non-[ifM index)t curve A between A and V+InA/
FIG. 3 is a characteristic diagram of a curve B representing a change in -.

Figure 8 U 181) 'Gc/)v1+m in a constant 1M tank
This is a characteristic diagram of xiangtLdL accent increase-sensation 11/1° when ``%'s direct pressure ff1l = 11■.In the figure, @-
A is the L element in the 41st embodiment, and straight line B is 5LO2? l: It is an element as soon as it is added.

As is clear from FIGS. 1 to 8 above, the element with the actual flaw ν11 has a weak WJ compared to the element without fo2 if addition.
It has non-IIJ line characteristics and is custom-made.

In addition, the heat treatment temperature of the sintered body is preferably 500°C to 850"G; below that, the spinning properties will be poor, and above 8511°C, the lineability will deteriorate. The time should vary by ↓9 depending on the size of the element, or preferably 1 hour or more.
The rate of temperature increase and decrease is preferably 2011° C./hour or less, which prevents insects from entering the device during rapid heating and cooling. Note that if the firing temperature is below 1000 to 1800°C, it will not produce a dense sintered body, and if it is higher than 1800°C, the rhoO
The elongation of Mk leads to poor non-1 negative linearity (1- is 1 to 1 during firing)
A uniform sintered body cannot be obtained within 1 hour after 20:04J. And for more than 20 hours, Ph02S near the surface
b203 volatilization cannot be ignored.

From the above results, the range of each additive component in the Miyako O Seiko production method is pho l Bb2011 reaction ((0,2~2
0wt,%,MnO2,((0,1~511IO/,
A, 5h2o, 2o, t~51nO/%, Cr
2O3f O,l ~51noA%,,dt02 (f
It is preferable to set the content to 0.1 to 5 mO/%; if the content is less than this range, the young fruit will become mounded, and if it is more than this, the non-greenness will decrease.

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

To briefly describe the second embodiment of this invention, Ph0
The means for obtaining the 1Sh2031/r-Eli reactant is the first
This is similar to the example. pl-, o I Bh2O5 reactants were obtained, ZnO: 97.997 mo/%, M
]102: 0.5 mo7! %, 5b20s:
0.5 +no/”%%Cr2O*: 0.5 ln
o/('%I 5107 :Q5mo/'!%, A/2
0B: '/1no/%r predetermined amount 000, add 2% of the above reactants at a volume ratio of 000, mix with the powder of Cn et al., and press-form into a disk shape. .

The funds are processed in the same manner as in the previous embodiment.

Figure 4 shows the 1-voltage current characteristics of the 2°O element manufactured by the second embodiment IC, and the +3□02 or A I420
This is a characteristic diagram showing the -pressure characteristics of the ZT10 element with 11A) Ju. In the figure, curve A is for the element according to this example, and curve B is for the element with t added by 8t02. C may be that of an element with t layers of Al120s. In the second embodiment, FIG.
7,) is fixed at t, and curve A showing the non-IIj line index α value of the element manufactured by changing the addition amount of 8102 (+--), and the α value of the element manufactured by changing the addition amount of 5tO2. FIG. 2 is a characteristic diagram of a curve aB shown in FIG.

Figure 6 shows 85% of vllnA in a 180°C temperature bath.
When applying a DC voltage of 7 Jl] Silkworm/Engineering.

In the diagram, straight line A indicates the element according to the second embodiment, 1
α・-B hani/! This is an element added to 20s'. Note that the element to which only S L O2 was added had the same characteristics as the second example.

As is clear from FIGS. 4 to 6 above, the device according to this example has improved non-linear characteristics and hemorrhoid characteristics compared to the devices in which JO2 and A/203K are individually impregnated. have

Note that the heat treatment temperature, time, etc. of the element in the second example were carried out in the same manner as in the first example. In addition, the range of each additive component u pho + 5bzOs reactant 'k 0.2 ~ 2
(1w +, %, M, 0.1 to 51nO1%, 1
3620% i 0.1~5 rno/%, 0r203
'f: 0.1~5 In011%, 0, 1 in I02
~5 mol! %, Al120s'c"2/100
It is preferable to set it to 0~''/10100O/%, and if this range Lv is small, no effect will appear, and if it is large, non-linearity will decrease.

To briefly describe the eighth embodiment of this invention, pbo
, Bb20q The means for obtaining the K-engineered reactant is the first method described above.
This is similar to the example. , Pl-, O, 5b203, and then ZnO: 9'8. Omo/%, M
r) 02: 0.5 mo/%, 13120s: 0
．． 5 mob! %, cr2o8: 0.5 no/%,
8t02: 0.5'mo1%, crawling silicon tlRm W
tl glass: 0.2 w ↑ 1% tJ'9r Weigh the amount, add 2% of the above reactant to the fiber, mix well, and form into a disk shape. Pressure mold. Thereafter, processing is performed in the same manner as in the previous embodiment.

Figure 7 shows the Z manufactured by the 8th generation 1. This is a characteristic diagram showing the positive current characteristics of an O element and the voltage and current characteristics of a 2°02 element with fm added only to 5102 or zinc borosilicate glass. Curve B is for an element in which only JO2 is c th= /J11.9 curve C is for an element in which only d+Shun zinc glass is made by km.

FIG. 8 shows the silicate-capable lead glass tv in the eighth embodiment.
, curve A showing the non-linear index α value of the device manufactured by fixing 5t02 @separately, and curve B showing the α11L relationship of the device manufactured by adding 8j02. Figure 9 is a characteristic diagram of α1 direct current curve C of devices manufactured by changing the amount of zinc silicate glass added. AJ 'a"4
In the diagram, the straight line B is the element according to the third embodiment, and the straight line B is the element using JO2'. Incidentally, the element made of silicic acid* and msarastrslJu' was custom-made as in the eighth embodiment ψ11.

7 to 8, the element shown in this example has a vague non-conformance up to the human WL range when compared with the element VC to which 5tO2 or borosilicate non-complex glass was added individually. It has a straight line characteristic flE'r.

2. Heat treatment temperature # and 1 yen of the element in the 8th example
1k41st grade Hm14mN! Proceed in the same manner as +, and
Each silkworm 1IbX, minute range is Ph09l11b205 reactant 70.2~20wt,%, MnO2k (1,1~
51nol! %, gb20A k O-1~5 lno
/%+ Cr2O5k 0.1~5+m○r%, 81
02'l (0゜1~5m012%, it is preferable that the amount of lead glass is 0.2 wt%, and this range L
If it is too small, the effect will not be strong, and if it is too large, the non-directness will be reduced.

To briefly describe the fourth embodiment of this invention, PhO
+ S h2 +] L9 reactant in 3? The means for obtaining 1" is the same as in the first embodiment. Pbo + 5h20B
After obtaining the reactant, zn〇 2 97.997'+no
I! %,)14n02: 0. 5 no#
% 1Sh20s: 0.5 +no1%, 0r20
s: 0.5 unoj? %, JO2: 0, 5 m
o71! %, Au2os: 8/1ooo 1n, tsu/! %, zinc silicate glass: 0.2 w/3% was weighed in a predetermined amount, and 2% of the above reactant was added thereto,
These powders are crushed and pressed into a circular shape. Thereafter, processing is performed in the same manner as in the previous embodiment.

FIG. 10 shows the voltage-current characteristics of the 2°0 element manufactured according to the fourth example, and the voltage-current characteristics of the 2°0 element manufactured according to the fourth example.
X + 8102 kl120s F'6 This is a 1-characteristic diagram showing the voltage-current characteristics of the Z and fl elements that have been removed separately.
it < lead glass r removed element 1 song + YMC is 5to2
The curve of element 9 removed in 1 is that of the element with AIt, o, k removed.

FIG. 11 shows a curve A showing the nonlinear index α value of a device manufactured by adding 1jt' of 5102, and a curve A showing the nonlinear index α value of the device manufactured by adding 1jt' of 5102 in Example 4 except for S 102. Zinc silicate glass? With the removed formulation, d102
Attachment 7: α1 straight t curve B of the device fabricated with JII radiation τ changed, and curve B of the device fabricated with the same formulation in which pJO2i was removed from the fourth embodiment, but with the addition of zinc silicate glass changed to #r. α1 straight (11-Boss song #C, same as 4th example j
jQ A/20. For the formulation with i removed, sL('+2
FIG. 3 is a characteristic diagram of the α1 straight t curve of the device manufactured by changing the addition Jli.

Figure 12 shows 85% of vl[n in 180°C constant temperature 1 soda
When the DC voltage t1:lJ is applied, the increase rate of the current is 6.
1/. In the characteristic diagram shown in the figure, straight line A indicates the element of this example,
Line 11 B shows the element with the borosilicate glass removed.

This is clearly shown in Figures 10 to 12 above.
The element based on 1 is ki420B + silicic acid non-complex glass) Ju element or Aj? 20g 1, :1102
Compared to the element with which the capacitor was applied, the non-inverter characteristic and the life characteristic are pseudo-n, and t3jo2. Added silica fluoride glass JJ
The non-llj line characteristics at IOA or higher are significantly higher than those of the other elements.

Note that the heat treatment temperature, time, etc. of the element in the fourth example are the same as in the first example. In addition, each additive component 4n
The box is PbOl ah20s reaction '1111 i 0.2
~20 w t,%-MnO2'! ! ? 0.1~5m
o/! %, 8h20g k 0.1-5mo/%, c
r2o8k 0.1~5 mo/%, JD2'f)0
．． 2 0.1-5mO/%, Aj? 20g2 / ~2”/3
11001 (+00 1no/%, silicic acid non-complex glass is preferably 0.01 to 5wt%. If the amount is small in this range, the effect A will not be noticeable, and if it is too large, the non-il radiation property will decrease.) /2r) If 3 is less than the above range, there will be no effect, and if it is more than 3, the life characteristics will be reduced. Effects of the Invention] As stated above, if the present invention is applied, heat treatment will also cause changes in the crystal structure. Therefore, the non-linear characteristic value is high due to the low current of 10μA, and the current is small even when the current is applied, and the leakage current due to one hour of application is low. (Durability is significantly increased because there are fewer days to increase strength) JD L, and B12O3 yarn element (
P compared to Clark number 2
h (11 (Clarke number of Ph 1.5 x 10-')) Since it is used throughout the term, it has the advantage of being abundant as a resource.

[Brief explanation of the drawing]

FIG. 1 shows Zn produced according to an embodiment of the present invention.
(rt piezoelectric characteristic of one element 5tO2'f voltage-current characteristic diagram of znO element without addition u, Figure 2 is i3 +02
A characteristic diagram showing the change in the nonlinear index and V + mA / qa of the n2ゎO element due to the manufacturing process when different cans of
The figure shows the quotient jL current increase in figure 1,
The figure is a voltage-electric phase characteristic diagram of a 2ゎO element built and left over from the second implementation of this invention, and a ZnO element with 8t02 and only Ax2oB of 110, Figure 45 Its Al,
+o = k hard v, n2ゎ0 element fabricated with 5102 addition 11-change, ZnO# fabricated with 8102 only addition It change, and ki20. Non-Z00 elements manufactured by changing the amount of addition T! [Digitary furrow sex diagram, nest 6
The figure shows a characteristic diagram of the increasing feeling of solder flow in the second embodiment, and FIG. Zn with only lead glass applied/jLI
81! Figure 8 shows how to fix the evening music button glass'# on the e-like
Manufactured by changing the material of 5t02'2! rshita2,
0 element, ZnO element manufactured by changing only the size of B to 2 by τ, and the fused IW! If! Lead glass employment 〃0
Figure 49 shows the non-direct-finger type timing diagram of the 2ゎ() element, which was pickled only by the side dish.
11 Characteristic diagram showing Kaka, Figure 10 σ 17 of this invention!
4 Z0 elements manufactured in the center, zinc silicate glass, 5tO2, A/! 20s k each removed 2
The voltage-current characteristic diagram of the o0 element, FIG.
A ZnO element manufactured by changing the silicic acid + l11 reduced glass was removed, a 2n0 element manufactured by changing the d102 seat 7JII, and a formulation in which 5tO2f was removed and the addition of borosilicate ml glass was changed. 5tO by removing the 2ゎO element and Idl 2 o 5-
Figure A12 is the non-linear exponential characteristic diagram of the ZnO element manufactured with 11tL of force of 2; Figure A12 is the characteristic diagram of the 1tc force increase in the 4th embodiment. □@1Ginkai Figure 4 (A) Fig. 5 Si 02 A force Di (mo? ' / J Fig. 9 Section V 后 7 盞 DIFFERENCE (A) Fig. 8 5iO24 Force 117t (moF ``mu) Glue wo Poem M Fig. 10 View ((A) @11 Figure 5i024 force Di (mo7 °n)

Claims (1)

[Claims] 111 PhO + B12O3 is reacted in advance at foot temperature, and then the reactant k Z) 10 + M102
*131') A method for manufacturing a zinc oxide non-Im-wire resistor, characterized in that the mixture is added to 20M+Cr20M+F3tO2, then I pressure molded, and the molded product is processed and molded. (21 pho + 8b7OA reactant 70.2 to 20 wt.% + M, n02k (11 to 5 + nO/%, 8b
20g k 0.1 to 5 cno12%, C120x
, T (11 to 5 rno/1%, J02 kO8
1 to 5 tnoA%, 2 having touched zno
Claim 1: A method for manufacturing a lead-free single-wire resistor according to claim 1. (31 ago"L Pbo * 13b205) Claim 1 states that the opening is a reaction/proboscis in which the molar ratio is from 2=1 to 2:1.5. Method for producing abrasive antibody. (4) Pbo, 8620g k Fir' in advance
1 LA degree of M - (゛After reacting, the reactant k zn
o + Mr, o,, l 5h2f) A rCr2(
'15 + 8102 + A/20x to R+> )
A method for producing a non-bloody abrasive antibody made of zinc oxide, which is characterized in that Ju L is mixed, pressed, and the molded product is heat-treated and molded. +F) + t+Hc: pho + 5b2o3* 0
．． 2 Kara 211 wt, X. MrU02 z 0.1 Kara5 moe 9i,
5h2Us k O,l 5 mo/%,”r2
0s 'r 0.1 to 5 nno/! %, 5 (02f
O8l to 5 +no/%, A/20g i ”2/1
o00 ” et 2°/xooorno/%τznOni silkworm〃
Claim 4. Claim 4. A method for manufacturing wire resistors using curved lead oxide in LA. f61 Itki P1-. 0,81-120g of reactants in a molar ratio of 2=1 to 2:1.5! F, oxidation I11 according to claim 4! A method for manufacturing a lead nonlinear resistor. (7) After reacting in advance at a temperature of PbO+ 8h20s rl') r, the reactant k Z, O+ MHO2+
A method for manufacturing a zinc oxide nonlinear resistor, characterized in that Bb20s, Cr2')S + 5tO2, is added to silicic acid glass, mixed, pressure molded, and the molded product is heat treated and molded. -8) The pbo, Bh20S i 0.2 to 20 wt, %. MnO2z 0.1 to 5 +11o1%, Sh20g
'it 0.1 to 5 nno/, %, cr2o!
= o, i to 5[n01%, 5tO2i 0.1
From 5 mrJr % + Insulation is zinc glass t0.0
1 to 5w↑1%rzr] The ratio is molar ratio 2 =
A method for manufacturing a zinc oxide non-i[wire resistor] according to claim 7, wherein the reactants have a ratio of 1 to 2:1.5. uol PbO+ 8b203 'c After reacting at a constant temperature of Par, the reactant? tZnO, MnO2
,'h20a,Cr2O,,5i02 + A/203
Added to lead glass, mixed and pressure molded, the molded product was heat treated and molded.
i A method for manufacturing a lead nonlinear resistor. till N1ne Pbo %5b20s t 0.
2 to 2 (1wt, ,%. MoO2'i 0.1 to 5 Ina11%, t3(-
,20s (II" 0.1 to 5 +noA%, cr
2o5 r o, l to 5 ma1g%, 8 t02
f O, I Xl) U5 mol! X-A/20s
k” / Kara000 2071 Floo “Oi! Zinc oxide non-11 according to claim 10, characterized in that it is stratified into %, silicon @ lead glass 0601 5wt, and %znO.
Method for producing Iwato antibody. U force Ail tj self p1-, Q l bh20M's ratio is 2:1 to 221.5 in molar ratio.Claim 10.1c. A method of manufacturing a nonlinear resistor.