JPS6074404A - Voltage/current 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 of the Invention] The present invention relates to a voltage-current non-linear resistor made of a sintered body containing lead (ZnO) as a main component, and in particular, to This invention relates to a voltage-current non-linear resistor with excellent performance.

[Technical background of the invention and its problems]

Conventionally, various voltage-current nonlinear resistors (←-4Je4-
varistors), one of which is ZnO.
There is one that uses a sintered body whose main component is

In products using a sintered body containing ZnO as a main component, attempts have been made to add various subcomponents to obtain desired characteristics.

Recently, research and development on direct current power transmission has been carried out, but unlike in the case of alternating current power transmission, a unidirectional electric field is always applied to a non-removable km resistor, resulting in extremely harsh conditions. DC lifespan t# that can withstand such harsh conditions! At present, a voltage/current nonlinear resistor that violates the j property has not been obtained. For example, ZnO shown in JP-A-49-119188
KB 1203, Cod, 5b2o3. Nip
.

MnO added, ZnO with B T B 1'z 4 added as shown in Japanese Patent Publication No. 46-19472, and glass containing boron oxide added to ZnO shown in Japanese Patent Publication No. 56-33842. There have been discussions about adding additional materials, but none of them have been able to provide sufficient characteristics. For example, when direct current is applied, the current increases over time, resulting in thermal runaway, resulting in poor direct current life characteristics.

Furthermore, as power transmission becomes more intense (UHV) in recent years, the required characteristics, such as voltage-current non-linear characteristics and life characteristics, are becoming more severe.

As described above, the demand for improvement in mechanical properties such as life properties and nonlinearity has been increasing year by year9, and research is being carried out in various places to satisfy these demands.

[Purpose of the invention]

This invention has been made in consideration of the above points, and aims to provide a voltage-current nonlinear resistor with excellent DC life characteristics. A further object of the present invention is to provide a voltage-current non-linear resistor with excellent voltage-current non-linear characteristics.

[Summary of the invention]

The main component of the present invention is zinc oxide, and the subcomponents are bismuth, cobalt, manganese, ammonium, and nickel, respectively.
s.

Converted to NiOVc, Bi2030.1~5mo1%, 0o20s O,1
~5mo#%.

Mn0 0.1-5mo7%, 5b2030.1-5m
0A'%.

NiOo, i~smoA% A voltage-current nonlinear resistor characterized by being made of a sintered body containing 0.001 to 1 wt% of boron in terms of B2O3 based on the basic composition contained. be.

As above < B 120s, 0o203, M
nO,5b2o3. By adopting a composition including Ni0I/cB, the DC life characteristics are greatly improved by V. In particular, it has excellent life characteristics and non-linear characteristics when AC is still applied.

In the VC of the present invention, B 1203 , Co2O3, M
nO, 5b203°NiO, 0.1 to 5 ma each
The reason why it is set at 11% is because if it deviates from this range, the nonlinear characteristics and life characteristics will deteriorate. By adding B to this basic composition, various properties are improved, and in particular, the DC life is significantly improved. In other words, with only the basic composition, when applying a 1α current, the leakage current increases over time r(
B20311'il: converted to 0.0
By containing 01 to 1 wt%, the change in leakage current over time is small, so that the DC life characteristics are improved in a UQId manner. If the amount is less than 0.001 wt %, the effect of adding B will not appear, and by adding 0.001 wt % or more (7JI), the multi-current Vc1 current life characteristics will be improved. If it exceeds 1wt%, it will not only deteriorate the DC life characteristics, but also
This will deteriorate the lifespan of the AC and even the non-direct factory special operation.

Each of the above amounts is a converted value, and can be added in various forms such as carbonate. For example, various types of exemptions can be considered for Yuge Hogan, such as B2O3゜HsBOs, HB
O2, Bt (OR)4. ZnB1O7, AgBO2
tAg2B407, BaB407, Mg (
BO2) 2 ・8 B20, klnB407 ・8
H20°B 1BO3, N i3 (BO3)2,
N 1213. , o, etc.

When mixing the raw materials uniformly, it is preferable to use a boron component that is easily soluble in water and mix it as an aqueous solution. For example, 1(, B03. HBO2, B2(OH)4゜ZnB4O7, Am/monium, AgJ302,
Ag2B407 etc. are listed as easily soluble in water.

Furthermore, by adding Ic A6 , In , and Ga, it is possible to obtain the same nonlinear l characteristic as above.

In other words, the main component is lead oxide, and the secondary components are bismuth, cobalt, manogan, and antimono.

Nickel is B ;, 03. Co2O3, Mn
e, 5b203゜Ni0VCa calculated 1 B t203 o, t~5moA %, Co2O30
, 1-5 mo1%.

Mn0 0.1-5mo1%, 5b2030.1-5m
o7q6゜NiO0,1~5moA! % Furthermore, for the basic composition in which at least one selected from aluminum, i/dium, and gallium is contained at 0.05 mall% or less in terms of All, In, and Ga, boron is 0001 to 0001 in terms of B2O3. l w
This is a ``Narita''-style nonlinear resistor characterized in that it is made of a sintered body containing t.

Al”, In”, Ga3+ is 0.05 mai
It is effective in a range of 1% or less. 1'J% can be effective by adding a small amount, but especially 0.0001 mai1
Excellent effects can be achieved by adding more than %. In addition, if there are too many laxities, the characteristics will deteriorate on the contrary. In particular, the effect of inclusion of A1 etc. on non-linear characteristics is great. In this case as well, as described above, since the effect of improving the properties can be obtained with a very small amount, it is preferable to mix and brew as an aqueous solution of a compound easily soluble in water, such as nitrate salt.

When the crystal structure of 20 g of Bi in the voltage/current nonlinear resistor according to the present invention was examined, it was found that an α phase (orthorhombic system) was formed. The ratio of this α phase to the total Bi2O changes depending on the packaging conditions such as temperature and composition.

When we investigated the change in characteristics due to the ratio 4VC of this α phase, all B
It has been found that DC life characteristics are particularly excellent when the number of α phases during i20a service is IO or more, preferably 30 or more. This tendency was the same in the composition range of the present invention, and was also the same in systems containing Al, In, and Ga. However, when the basic components were different, the α phase did not occur. For example, Zn0-B i20. -00
203-MnO-Nio-8b20s K:Or
Even when B2O3 was added to the basic components including 20's and Sin, an α phase was not generated, and neither the nonlinearity nor the life characteristics were improved.

Moreover, this α phase changes into another phase by heat treatment. Therefore, it is desirable not to add a process that includes heating to an extent that changes this crystal phase.

〔Effect of the invention〕

As explained above, according to the Kinoe F3A, it is possible to obtain a voltage-current non-direction resistor with excellent DC life characteristics.

-1: The resistor of the present invention also has excellent nonlinear characteristics and AC life characteristics.

Therefore, lightning arrester v as a surge absorber for DC high voltage power transmission
c is valid. It is also effective for AC power transmission. It is particularly suitable for UHV applications. In addition, since both DC and AC devices can be manufactured on the same line, there are great manufacturing advantages such as cost reduction. [Embodiments of the Invention] An actual rj example of the present invention will be described below.

H1203, Co2O3, Mn0 as ZnOK subcomponents
．． 81) 203.

NiO, Al(NOs)s・9H20 are prepared in the desired composition ratio, an aqueous solution in which H and BO are dissolved in the desired ratio as B-containing compounds is added, and after mixing, PVA is added as a binder and granulated. , formed into a disc-shaped plate material.

1100~1300°02 hours after drying this board material
After firing for about 30 minutes, both sides were polished to form a sintered body with a diameter of 2 mm and a thickness of 2 mm.

Stain poles were formed by thermal spraying VCAl on both sides of this sample to form a voltage-current nonlinear resistor, and the valley characteristics were measured.

The results are shown in Table 1. In Table 1, compositions outside the scope of the present invention are also shown as comparative examples. 1st
In the table, the voltage '1 current nonlinear characteristic is V2KA/VIm
A, the life characteristics are shown as B4O0 and Bf is B20
．． 'It is expressed as a weight ratio to the basic component in terms of WC.

I(400) is the leakage current measured at room temperature after continuously applying a voltage of 0.75 X-VlmA for 400 hours when the ambient temperature is 90°C,
In the case of , the leakage current was measured at room temperature after applying a voltage of 0.85 x VlmA for 400 hours. ■(0
) is 6.0 by default, and L4GG is I (400) and 1 (0
) expressed as a ratio.

Note that the X mark f'i in the table indicates that thermal runaway occurred within 400 hours.

As is clear from Table 1 below, it can be seen that the examples of the present invention are superior in each characteristic, particularly in DC life characteristics. As can be seen from the comparative examples (samples Nn 20 to 29), if the basic composition is outside the range of the present invention, the effect of B addition cannot be achieved, and both the DC and AC lifespans are very poor. Further, as can be seen from the comparative example (sample positive 30), if the amount of B is small, the effect of addition will not appear, and thermal runaway will occur when direct current is applied.

If there is too much excess (sample Nn31), each characteristic will deteriorate on the contrary.

Changes in leakage current over time were investigated using the composition of Ushida sample No. 16. The change in leakage current over time is expressed as I(t)/I(0),
The measurement method is the same as I(400)/I(0) described in 11u. The results are shown in Figure 1. In the same figure: A line (
A) Shows the case of beam, C mark Karo, broken line (B) A, 0
The case of application is shown.

As is clear from Figure 1, in the case of C, A, and O mark Calo, IC
t) ACO) shows a substantially constant value, and even when D and O are applied, solidification occurs in the 300 hr-process type, indicating that the gold exhibits excellent properties. Since there is little change in leakage current as described above, the product has excellent life characteristics.

For comparison, the case where boron is added as glass is also shown in FIG. 1-wave bismuth caras was added, and the total VC and A ratio were the same as sample floor 16, * starvation (C) is the H'l jlt waste life, and the broken line (D) is the AC life.

As is clear from the figure, one phase of DC, one AIj not
'KameυIC will accumulate VC over time, and in the future it will become 2
There must be a tendency to act out of control. Also, in the case of electric current, it shows an increase of about 1 after about 300 hours.

Thus, as uninvented, l/'CB is j other than glass.
It is better to add it in its natural state to make it more concentrated. This is thought to be because when it is added as glass, it contains a large amount of components other than boron, so it is unlikely to have an adverse effect on the physical properties.

As described above, according to the present invention, it is possible to obtain a varistor which is particularly well-characterized by the direct-piston C-conductor characteristics. It also affects line characteristics and AC life.

Next, Example V in which Al is mixed with η will be explained.

B 1203 , 0o203 ,
IQlnO,8b203゜NiO,AA(NOs)3
- A varistor was manufactured using a compound containing 9H20 and B prepared and mixed in a desired composition ratio in the same manner as shown above. Table 2 shows the measurement results of each characteristic.

As is clear from Table 2 in the margin below, it can be seen that in the system with A4'' added, the non-direct a% property is improved compared to the case in Table 1. As well as things,
If the B value is small, the O opening force (If;j) will cause thermal runaway. If there are too many reeds, the IC life and non-linearity will deteriorate.

Although the improvement in nonlinear characteristics seems small in terms of equation (11), in practice, even a slight improvement can have a significant effect.

Further, FIG. 2 shows the evolution of the life characteristics (¥ line DO, broken line AC) when 13203 is changed in a sample having the composition of sample N+132.

As is clear from Figure 2, l3203[( is 0.00
1-1. Owt% range, and the VC life characteristics are degraded for O, A, and O. If it is less than 0.001wt%,
A.

Although the C life is slightly inferior, i) the deterioration of the C life is noticeable. When the amount exceeds 1 wt%, both characteristics deteriorate significantly. This tendency was the same in the system not containing A13+.

The same effect as i can be obtained with In, Ga.

Similar to the examples in Table 2, All (NO
3) s ・9 H2O, I n (NOa) s ・3
Table 3 shows all the characteristics of J(20,Ga(NOs)a.XH2O) prepared by blending at least one of them.

Margin below As is clear from Table 3, ZnO, B i20. .

00203, MnO,5b2o3, l' to Nio
In the yarn VC containing at least one of the basic components V, Ga, and In, B2O3τ has the effect of improving life characteristics, especially DC life characteristics, by including B2O3, as well as improving nonlinear characteristics. The same effect as above can be obtained.

However, when there are many Alt, Ga, and In fireflies, each characteristic deteriorates (sample direction 118
~120).

The Bi2O3 phase in the thin VC sintered body was investigated. Ei, 03 in the sintered body consists of α phase (orthorhombic system), β phase (tetragonal crystal thread), γ phase (body-centered cubic system), δ phase (face-centered cubic system), and various other phases. It exists as The ratio of each phase varies depending on the composition of the sintered body and the lining material.

Figure 3 VC, with ZnO as the main component and Bi2 as a subcomponent
O3゜0o20B, MnO, 5b2o3. NiO
0.1 to 5 mail each, AIj CNO
s) Exchange s・9H20 to Ad from 0.0001
The composition KH, BO, consisting of 0.05 mo1% is B,
0. 0 to 1 in terms of vc. Add Owt Chi and use it as a whole, and use it as described above to make a barista! i-manufactured and shows the relationship between α phase and life characteristics. The solid line in the figure is the DC life, and the broken line is 9. Shows flowing young seedlings.

α Aido was defined by Ra shown below.

As is clear from Figure 3, as Ra increases, the DC
It can be seen that the life characteristics have been improved for both AC and AC.

In particular, in the case of 1-salt application, L40G is improved when Ra>10, and settles to a nearly constant value when Rα≧30. If α is small, thermal runaway will occur. If B is not added, Rα is 20, and by adding B, an α phase begins to form. Looking at Blot, it is 0.02 to 0.0 in terms of B2O3.
1) It is preferable that α is approximately 100 in the range of VT.

In this way, the α phase of 5Bi203 begins to form due to the microshape of B, but if there is an excess of 9, B I 203 becomes amorphous.

For A, CL400, D, O'L 4oo
Although it is not a serious problem, the characteristics are improved especially at Ra230 due to the increase in α phase as described above.

In this way, Ra210. Especially Itα? A varistor with very good life characteristics can be obtained within the range of 30. This tendency was the same for yarns that did not contain AA3+.

Table 4 shows 1tα (%) for each composition. The sample direction is determined by the numbers of the above-mentioned Examples and Comparative Examples. Note that A, O
For L400, D, 0L40G, as mentioned above and as is clear from Table 4, there was no mo α of 10φ or more.

[Brief explanation of drawings]

Kan T Section 1, Figures 2 and 3 are 11 Mori 1 raw curve diagrams. Fig. t (time use) Fig. 2 θθ0/ θθ/ θ/ /θ B203 (by cwt Fig. 3 2θ 4θ Otsu θ 8θ /ρθ β Display Patent Application No. 180171 of 1980 2 Name of the invention Voltage current non-linear resistor 3 Relationship to the case of the person making the amendment Patent applicant (307) Tokyo Shibaura Electric Co., Ltd. 4 Agent address 100 Uchisaiwai-cho, Chiyoda-ku, Tokyo 1-1-6 Detailed explanation of the invention column 6 of the specification, contents of amendment (1) Specification, page 9, line 8 [-1Al(N03)3.9
H20j, delete the text. (2) On page 13, line 11 of the specification, I amend No. 16 J to [No. 17 J. (3) “N0116” on page 14, line 5 of the specification is corrected to “No, 17J.” (4) “N0116” on page 14 of the specification, line 5 is corrected to “No, 17J.” (4) “N0116” is corrected as “No, 17J” on page 14 of the specification, negative lines 6 to 9. (5 ) Page 26, line 6 of the specification is corrected to read, "[C.230 improves the characteristics and makes the electric strength particularly excellent." I”

Claims (1)

[Claims] (1) The main component is zinc oxide, and the subcomponents are bismuth, cobalt, mag/ga/, antimono, and nickel, H1203, 00203, MnO, 5b203.
, Ni. In terms of J3i20s 0.1-5moA%, Co2O30,
1-5 mo1%gMn0 0.1-5 mo1%, 5b
2030.1-5mo1%. 1. A voltage/current nonlinear resistor comprising a sintered body containing 0,000 to 1 wt of boron (calculated as 8203 iC) to the basic composition containing NiOO, 1 to 5 mo1%. (2J i! The main component is zinc oxide, and the subcomponents are bismuth, cobalt, ma/ga/, antemo/, and nickel, respectively.
3. In terms of NiO, Bi2O30.1~5rno1%, 0o2030.1~
5mo7%. MnO0.1-5mo7%, 5b2030.1-5mo
1%. Ni0 0.1-5moA%, plus aluminum, indium and gallium or 3+
At least one selected from 3+ 3+ is AA, -In, C
Boron is 0.001 in terms of B2O3 for the basic m component containing 0.05 mo1% or less in terms of +a.
A voltage/current nonlinear resistor comprising a sintered body containing ~1 wt%.