JPH044723B2 - - Google Patents
Info
- Publication number
- JPH044723B2 JPH044723B2 JP60044558A JP4455885A JPH044723B2 JP H044723 B2 JPH044723 B2 JP H044723B2 JP 60044558 A JP60044558 A JP 60044558A JP 4455885 A JP4455885 A JP 4455885A JP H044723 B2 JPH044723 B2 JP H044723B2
- Authority
- JP
- Japan
- Prior art keywords
- bismuth oxide
- centered cubic
- oxide
- nonlinear resistor
- voltage nonlinear
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 27
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 27
- 239000013078 crystal Substances 0.000 claims description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000011787 zinc oxide Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 238000010586 diagram Methods 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000003303 reheating Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 229910000410 antimony oxide Inorganic materials 0.000 description 2
- 229910000423 chromium oxide Inorganic materials 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 1
- -1 Sb 2 O 3 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Thermistors And Varistors (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は、酸化亜鉛避雷器に使用する電圧非
直線抵抗体に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a voltage nonlinear resistor used in a zinc oxide lightning arrester.
従来、避雷器等に使用される酸化亜鉛電圧非直
線抵抗体には、その具備すべき能力として電圧非
直線性にすぐれ、サージ吸収能力が大きく、かつ
課電劣化を起しにくく長寿命である等が要求され
てきている。
Conventionally, zinc oxide voltage nonlinear resistors used in lightning arresters, etc., have the following characteristics: excellent voltage nonlinearity, large surge absorption capacity, and resistance to deterioration caused by electrical charge and long life. is being demanded.
この内、サージ吸収能力を制限するものとして
素子側面部における外部閃絡がある。素子端面で
の微小放電をトリガとする場合が多く、このため
通常第２ａ図に示すような電極１を持つ電圧非直
線抵抗体本体２の側面部に高抵抗層７を形成して
これを防止する方法がとられている。高抵抗層の
形成には、従来大きく分けて２つの方法が知られ
ている。１つの方法は、SiO2，Sb2O3，Bi2O3の
粉末を有機バインダと混合してペースト状とし成
形体に塗布、同時に焼結して、高抵抗層である電
圧非直線抵抗体２を形成するものである。他の方
法は、一担焼成した電圧非直線抵抗体１の側面に
低融性ガラスフリツトを有機バインダと共にペー
スト状として塗布し、これを加熱してガラス化し
て高抵抗層とするものである。 Among these, external flash shorting at the side surface of the element limits the surge absorption ability. In many cases, the trigger is a micro discharge at the end face of the element, and therefore, a high resistance layer 7 is usually formed on the side surface of the voltage nonlinear resistor main body 2 having the electrode 1 as shown in Fig. 2a to prevent this. A method is being taken to do so. Conventionally, there are two known methods for forming a high-resistance layer. One method is to mix powders of SiO 2 , Sb 2 O 3 , and Bi 2 O 3 with an organic binder to form a paste, apply it to a molded body, and simultaneously sinter it to form a voltage nonlinear resistor, which is a high-resistance layer. 2. Another method is to apply a low-melting glass frit together with an organic binder in the form of a paste to the side surface of the voltage nonlinear resistor 1 that has been fired once, and then heat it to vitrify it to form a high-resistance layer.
一方、電圧非直線抵抗体の微細構造を第２ｂ図
に模式的に示すが、酸化亜鉛粒子４、スピネル粒
子５、それらの空隙をうめるように粒界層に
Bi2O3（酸化ビスマス）８が存在する。この粒界
層に存在するBi2O3の結晶相が電圧非直線性、寿
命特性に強く影響することが近年明らかになつて
きた。すなわち寿命特性で言えば８の酸化ビスマ
スの結晶相の違いが、一定電圧を印加した場合の
電流、いわゆるもれ電流の変化率に大きく影響す
るのである。第３図に寿命特性の１例すなわち課
電率80％、周囲温度130℃の場合のもれ電流比
（初期電流で正規化）の経時変化を示す。 On the other hand, the fine structure of the voltage nonlinear resistor is schematically shown in Fig. 2b. Zinc oxide particles 4, spinel particles 5,
Bi 2 O 3 (bismuth oxide) 8 is present. In recent years, it has become clear that the Bi 2 O 3 crystal phase present in this grain boundary layer has a strong influence on voltage nonlinearity and lifetime characteristics. In other words, in terms of lifetime characteristics, the difference in the crystal phase of bismuth oxide in No. 8 greatly affects the rate of change in current when a constant voltage is applied, so-called leakage current. Figure 3 shows an example of the life characteristics, that is, the change over time in the leakage current ratio (normalized by the initial current) when the charging rate is 80% and the ambient temperature is 130°C.
図中曲線Ａは体心立方晶の酸化ビスマスが３
％、曲線Ｂは同じく７％、曲線Ｃは同じく60％、
曲線Ｄは同じく95％それぞれ含有している場合で
ある。 Curve A in the figure shows body-centered cubic bismuth oxide with 3
%, curve B is the same 7%, curve C is the same 60%,
Curve D is the case where the content is 95%.
一方、体心立方晶の酸化ビスマスを電圧非直線
抵抗体に形成するには、添加物の配合、焼成雰囲
気等の焼成条件、一担焼成した抵抗体を再加熱す
る方法が、配合を含めた製造方法を規定した場
合、厳密にその体心立方晶の生成割合を調整する
のに有効であることがすでに示されている（特開
昭60−4202号公報）。すなわち、第４図に示すよ
うな再加熱温度と体心立方晶酸化ビスマスへの転
化率との関係がみられる。よつて、第３図、第４
図からもれ電流比の小さい再加熱温度は500−
600゜付近に限定されてくる。 On the other hand, in order to form body-centered cubic bismuth oxide into a voltage nonlinear resistor, the combination of additives, firing conditions such as the firing atmosphere, and the method of reheating the once-fired resistor are important, including the composition. It has already been shown that it is effective to strictly control the proportion of body-centered cubic crystals produced by specifying the manufacturing method (Japanese Patent Application Laid-open No. 4202/1983). That is, there is a relationship between the reheating temperature and the conversion rate to body-centered cubic bismuth oxide as shown in FIG. Therefore, Figures 3 and 4
From the figure, the reheating temperature with a small leakage current ratio is 500−
It is limited to around 600°.
従来、側面高抵抗層の形成と酸化ビスマスの体
心立方晶への転化率の制御は、別個の工程で行わ
れているのが通常であるが、工数の増加の点から
並びに歩留りの点からみて問題があつた。
Conventionally, the formation of the side high-resistance layer and the control of the conversion rate of bismuth oxide to body-centered cubic crystals have been carried out in separate processes, but this has been done from the viewpoint of increased man-hours and yield. I saw a problem.
この発明は、上記のような工程の繁雑化をさけ
工程を減少させ、歩留りを向上させることを目的
とするものである。 The object of the present invention is to avoid the above-mentioned process complexity, reduce the number of steps, and improve the yield.
すなわちこの発明は、酸化亜鉛を主成分とし少
なくとも酸化ビスマスを含む原料を焼成して電圧
非直線抵抗体素子を造り、酸化ビスマスの所定量
を体心立方晶に転化することから本質的になる電
圧非直線抵抗体の製造方法において、酸化ビスマ
スの所定量を体心立方晶に転化する転化温度域と
同じ温度範囲の焼結温度域をもち、且つ電圧非直
線抵抗体の膨張係数と±10％以内で一致する膨張
係数を有するガラスフリツトを前記素子の側面に
施し、加熱により側面高抵抗層の形成と酸化ビス
マスの体心立方晶への転化とを同時に行なう電圧
非直線抵抗体の製造方法に存する。
That is, this invention produces a voltage nonlinear resistor element by firing a raw material containing zinc oxide as a main component and at least bismuth oxide, and converts a predetermined amount of bismuth oxide into a body-centered cubic crystal, thereby producing a voltage that essentially becomes In the method for manufacturing a nonlinear resistor, the sintering temperature range is the same as the conversion temperature range for converting a predetermined amount of bismuth oxide into a body-centered cubic crystal, and the expansion coefficient is ±10% of the voltage nonlinear resistor. A method of manufacturing a voltage nonlinear resistor comprises applying a glass frit having an expansion coefficient that matches within a range of 1 to 3 on the side surface of the element, and simultaneously forming a lateral high resistance layer and converting bismuth oxide into a body-centered cubic crystal by heating. .
この発明は電圧非直線抵抗体の寿命を安定させ
るのに必要な酸化ビスマスの体心立方晶への転化
率を得るための温度と同じ温度範囲のガラスフリ
ツトを使用することにより、電圧非直線抵抗体の
製造に対し、側面高抵抗層の形成と、酸化ビスマ
スの結晶相の制御、すなわち体心立方晶への転心
率の調整とを一回の加熱工程で行なうとするもの
である。
This invention is capable of forming a voltage nonlinear resistor by using a glass frit in the same temperature range as the temperature to obtain the conversion rate of bismuth oxide to body-centered cubic crystal necessary to stabilize the life of the voltage nonlinear resistor. For the production of , the formation of the side high resistance layer and the control of the crystal phase of bismuth oxide, that is, the adjustment of the centroid to body-centered cubic crystal, are performed in a single heating step.
この発明で使用するガラスフリツトは低融性酸
化物ガラスフリツト例えばPbO−SiO2−B2O3、
ZnO−SiO2−B2O3系などである。これらは作業
温度の点だけでなく、その膨張係数が電圧非直線
抵抗体の焼結体の膨張係数に近い（±10％以内）
ため好適に使用できる。膨張係数が±10％を越え
ると、ガラスの付着が困難になつたり、素子が変
形するために好ましくない。 The glass frit used in this invention is a low melting oxide glass frit such as PbO- SiO2 - B2O3 ,
Examples include ZnO- SiO2 - B2O3 system. These are not only effective in terms of working temperature, but also in that their expansion coefficient is close to that of the sintered body of the voltage nonlinear resistor (within ±10%).
Therefore, it can be used suitably. If the expansion coefficient exceeds ±10%, it is not preferable because adhesion of glass becomes difficult or the element becomes deformed.
以下実施例に基づきこの発明を説明する。 The present invention will be explained below based on Examples.
実施例 １
酸化亜鉛を主成分とし、添加物としてそれぞれ
0.5モル％の酸化クロム、酸化ニツケル、酸化コ
バルト、酸化マンガン、酸化珪素、酸化ビスマ
ス、および1.0モル％の酸化アンチモンを加えた
ものを十分混合し、造粒後成形する。1200℃で焼
成した50〓×25t程度の大きさの素子すなわち第１
ａ図中２の電圧非直線抵抗体本体に、線膨張係数
が焼成体線膨張係数（約60×10-71/℃）の±10％
以内で、作業温度域が550℃付近のガラスフリツ
トを選び、この粉末をニトロセルロースなどのバ
インダを含む溶剤と混合塗布し、これを加熱しガ
ラス層すなわち第１ａ図中３の低融点ガラスフリ
ツトの側面高抵抗層の形成と酸化ビスマスの結晶
の転化を同時に行つた。加熱時間は１〜２時間程
度とし、十分酸素の供給し得る状況で行うことが
肝要である。Example 1 Zinc oxide is the main component, and each additive is
A mixture containing 0.5 mol% of chromium oxide, nickel oxide, cobalt oxide, manganese oxide, silicon oxide, bismuth oxide, and 1.0 mol% of antimony oxide is thoroughly mixed, granulated, and then molded. The first element was fired at 1200°C and had a size of approximately 50 mm x 25 tons .
The linear expansion coefficient of the voltage nonlinear resistor body shown in 2 in the figure a is ±10% of the linear expansion coefficient of the fired body (approximately 60×10 -7 1/℃).
Select a glass frit whose working temperature range is around 550℃, apply this powder mixed with a solvent containing a binder such as nitrocellulose, and heat it to increase the side height of the glass layer, that is, the low melting point glass frit shown in 3 in Figure 1a. The formation of a resistive layer and the conversion of bismuth oxide crystals were performed simultaneously. It is important to set the heating time to about 1 to 2 hours and to carry out the heating under conditions where sufficient oxygen can be supplied.
次に得られた電圧非直線抵抗体のＸ線回折によ
る分析結果を第５図に示すが、このようにβ形
（正方晶形）の酸化ビスマスとγ形（体心立方晶
形）の酸化ビスマスの混晶となることがあきらか
になつた。得られた電圧非直線抵抗体の微細構造
を第１ｂ図に示す。実際に寿命試験を行つたとこ
ろ、第３図曲線Ａに示すような安定した電流の経
時変化を示した。一方側面高抵抗層の効果を見る
ため、４×10μs、100KAのサージ電流を２回通
電したところ、十分に耐えることが出来、閃絡等
は見られなかつた。 Next, the analysis results of the obtained voltage nonlinear resistor by X-ray diffraction are shown in Figure 5, and as shown in Figure 5, it is clear that the β-form (tetragonal) bismuth oxide and the γ-form (body-centered cubic) bismuth oxide. It became clear that it was a mixed crystal. The microstructure of the obtained voltage nonlinear resistor is shown in FIG. 1b. When a life test was actually conducted, a stable change in current over time was shown as shown by curve A in FIG. 3. On the other hand, in order to see the effect of the side high resistance layer, we applied a surge current of 4 x 10 μs and 100 KA twice, and it was able to withstand sufficiently, with no flashovers or the like.
実施例 ２
実施例１は交流通電時の例であるが、直流通電
に対して安定な電流の経時変化を示す場合は、体
心立方晶の転化割合が実施例とは必ずしも一致し
ない。１例として実施例１とわずかに異なる配合
すなわちそれぞれ0.5モル％の酸化ビスマス、酸
化クロム、酸化マンガン、酸化珪素と、1.0モル
％の酸化アンチモン、酸化コバルト、及びホウ酸
0.04モル％を含む場合を示す。同様にこれらの粉
末を十分混合し、造粒して成形後1200℃で焼成し
た。これを予備的に加熱処理し、その後寿命特性
（第６図）と、体心立方晶の転化率との関連を求
めた（第７図）。第６図は課電率80％、周囲温度
100℃での直流もれ電流の経時変化を示す図であ
り、それぞれ曲線Ｅは熱処理なし、曲線Ｆは600
℃での熱処理、曲線Ｇは650℃での熱処理、曲線
Ｈは700℃での熱処理の場合である。第７図は２
時間加熱した場合のアニール温度（℃）とＸ線回
折より求めた体心立方晶酸化ビスマスへの転化率
との関係を示す図である。この場合には600℃以
上の加熱処理条件で80％以上の体心立方晶への転
化率が望ましいことが分る。この場合には、この
条件に適した作業温度域が650℃程度のガラスフ
リツトを使用する。素子の膨張係数はこの場合実
施例１とほとんどかわらないので作業温度の100
℃程度高いものが必要となる。第５図と同様な直
流に対する寿命特性が得られ、耐量に対しても十
分なものであることが確認された。Example 2 Example 1 is an example when AC current is applied, but when a stable current change over time is shown with respect to DC current, the conversion ratio of the body-centered cubic crystal does not necessarily match that of the example. As an example, a slightly different formulation from Example 1, i.e. 0.5 mol% each of bismuth oxide, chromium oxide, manganese oxide, silicon oxide, and 1.0 mol% of antimony oxide, cobalt oxide, and boric acid.
The case containing 0.04 mol% is shown. Similarly, these powders were thoroughly mixed, granulated, molded, and then fired at 1200°C. This was preliminarily heat treated, and then the relationship between the lifetime characteristics (Figure 6) and the conversion rate of body-centered cubic crystals was determined (Figure 7). Figure 6 shows charging rate of 80% and ambient temperature.
It is a diagram showing the change in DC leakage current over time at 100°C, where curve E is for no heat treatment and curve F is for 600°C.
Curve G is for heat treatment at 650°C, and curve H is for heat treatment at 700°C. Figure 7 is 2
FIG. 3 is a diagram showing the relationship between the annealing temperature (° C.) and the conversion rate to body-centered cubic bismuth oxide determined by X-ray diffraction when heated for a certain period of time. In this case, it can be seen that a conversion rate to body-centered cubic crystals of 80% or more is desirable under heat treatment conditions of 600° C. or higher. In this case, use a glass frit whose working temperature range is approximately 650°C, which is suitable for these conditions. In this case, the expansion coefficient of the element is almost the same as in Example 1, so it is
It is necessary to use something as high as ℃. It was confirmed that life characteristics against direct current similar to those shown in FIG. 5 were obtained, and that the durability was sufficient.
なお、この方法ではガラス粉末を有機バインダ
で溶かしたものを塗布し加熱後ガラス化する方法
を示したが、ガラスの構成法はこれに限るもので
はなく、望ましくない作業工程数の増加を伴う点
を除けば必要な体心立方晶の形成に必要な温度域
でガラス化なり固着化し高抵抗層を形成するもの
であればよい。方法としては粉末をバインダと混
ぜテープ状にしたものを巻きつける方法もあろう
し、溶融したガラス浴に浸漬せしめる方法でも良
い。 Although this method shows a method in which glass powder is melted with an organic binder and vitrified after being heated, the method of constructing the glass is not limited to this, and there is the point that it involves an undesirable increase in the number of work steps. Other than that, any material that vitrifies or solidifies to form a high-resistance layer in the temperature range necessary to form the necessary body-centered cubic crystals may be used. Possible methods include mixing powder with a binder and wrapping it in a tape shape, or immersing it in a molten glass bath.
以上のようにこの発明によれば、側面高抵抗層
の形成と酸化ビスマスの体心立方晶の転化率を調
整するのを同時に行うため工数の低減、歩留り向
上に大きく寄与する。
As described above, according to the present invention, the formation of the side high resistance layer and the adjustment of the conversion rate of the body-centered cubic crystal of bismuth oxide are performed simultaneously, which greatly contributes to reducing the number of steps and improving the yield.
第１ａ図はこの発明による電圧非直線抵抗体の
断面図、第１ｂ図はこの発明による電圧非直線抵
抗体の抵抗体本体の微細構造の模式図、第２ａ図
は従来の電圧非直線抵抗体の断面図、第２ｂ図は
従来の電圧非直線抵抗体の抵抗体本体の微細構造
の模式図、第３図は従来の電圧非直線抵抗体のも
れ電流比の経時変化を示す線図、第４図は再加熱
温度と体心立方晶酸化ビスマスへの転化率との関
係を示す線図、第５図は実施例における電圧非直
線抵抗体のＸ線回折パターンを示す図、第６図は
直流もれ電流の経時変化を示す線図、第７図はア
ニール温度とＸ線回折より求めた体心立方晶酸化
ビスマスへの転化率との関係を示す線図である。
図中、１は電極、２は電圧非直線抵抗体本体、
３は低融性ガラスフリツトの側面高抵抗層、４は
酸化亜鉛粒子、５はスピネル粒子、６は酸化ビス
マスを主成分とする境界層（体心立方晶の割合か
ら規定されている）、７は側面高抵抗層、８は酸
化ビスマスを主成分とする境（粒）界層である。
FIG. 1a is a cross-sectional view of a voltage nonlinear resistor according to the present invention, FIG. 1b is a schematic diagram of the fine structure of the resistor body of the voltage nonlinear resistor according to the present invention, and FIG. 2a is a conventional voltage nonlinear resistor. 2b is a schematic diagram of the fine structure of the resistor body of a conventional voltage nonlinear resistor, and FIG. 3 is a diagram showing the change over time in the leakage current ratio of a conventional voltage nonlinear resistor. FIG. 4 is a diagram showing the relationship between reheating temperature and conversion rate to body-centered cubic bismuth oxide, FIG. 5 is a diagram showing the X-ray diffraction pattern of the voltage nonlinear resistor in the example, and FIG. 7 is a diagram showing the change in direct current leakage current over time, and FIG. 7 is a diagram showing the relationship between the annealing temperature and the conversion rate to body-centered cubic bismuth oxide determined by X-ray diffraction. In the figure, 1 is an electrode, 2 is a voltage nonlinear resistor body,
3 is a high-resistance layer on the side surface of a low-melting glass frit, 4 is a zinc oxide particle, 5 is a spinel particle, 6 is a boundary layer mainly composed of bismuth oxide (defined from the proportion of body-centered cubic crystals), and 7 is a The side high resistance layer 8 is a boundary (grain) boundary layer containing bismuth oxide as a main component.
Claims (1)
スを含む原料を焼成して電圧非直線抵抗体素子を
造り、酸化ビスマスの所有量を体心立方晶に転化
することから本質的になる電圧非直線抵抗体の製
造方法において、酸化ビスマスの所有量を体心立
方晶に転化する転化温度域と同じ温度範囲の焼結
温度域をもち、且つ電圧非直線抵抗体の膨張係数
と±10％以内で一致する膨張係数を有するガラス
フリツトを前記素子の側面に施し、加熱により側
面高抵抗層の形成と酸化ビスマスの体心立方晶へ
の転化とを同時に行なうことを特徴とする電圧非
直線抵抗体の製造方法。1. A voltage non-linear resistor element that essentially becomes a voltage non-linear resistor element by firing a raw material containing zinc oxide as a main component and at least bismuth oxide, and converting the amount of bismuth oxide into a body-centered cubic crystal. In the manufacturing method, the sintering temperature range is the same as the conversion temperature range for converting the amount of bismuth oxide into a body-centered cubic crystal, and the expansion coefficient matches the expansion coefficient of the voltage nonlinear resistor within ±10%. A method for manufacturing a voltage nonlinear resistor, characterized in that a glass frit having an expansion coefficient is applied to the side surface of the element, and heating forms a side high resistance layer and simultaneously converts bismuth oxide into a body-centered cubic crystal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60044558A JPS61204902A (en) | 1985-03-08 | 1985-03-08 | Manufacture of voltage non-linear resistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60044558A JPS61204902A (en) | 1985-03-08 | 1985-03-08 | Manufacture of voltage non-linear resistor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61204902A JPS61204902A (en) | 1986-09-11 |
| JPH044723B2 true JPH044723B2 (en) | 1992-01-29 |
Family
ID=12694825
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60044558A Granted JPS61204902A (en) | 1985-03-08 | 1985-03-08 | Manufacture of voltage non-linear resistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61204902A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5321509A (en) * | 1976-08-11 | 1978-02-28 | Nippon Telegr & Teleph Corp <Ntt> | Digital signal two-way repeater unit |
| JPS5598802A (en) * | 1979-01-24 | 1980-07-28 | Hitachi Ltd | Nonnlinear voltage resistor |
| JPS5858704A (en) * | 1981-10-05 | 1983-04-07 | 株式会社明電舎 | Method of producing nonlinear resistor |
-
1985
- 1985-03-08 JP JP60044558A patent/JPS61204902A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5321509A (en) * | 1976-08-11 | 1978-02-28 | Nippon Telegr & Teleph Corp <Ntt> | Digital signal two-way repeater unit |
| JPS5598802A (en) * | 1979-01-24 | 1980-07-28 | Hitachi Ltd | Nonnlinear voltage resistor |
| JPS5858704A (en) * | 1981-10-05 | 1983-04-07 | 株式会社明電舎 | Method of producing nonlinear resistor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61204902A (en) | 1986-09-11 |
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