JPH0283902A - Voltage-dependent nonlinear resistor and manufacture thereof - Google Patents
Voltage-dependent nonlinear resistor and manufacture thereofInfo
- Publication number
- JPH0283902A JPH0283902A JP63236792A JP23679288A JPH0283902A JP H0283902 A JPH0283902 A JP H0283902A JP 63236792 A JP63236792 A JP 63236792A JP 23679288 A JP23679288 A JP 23679288A JP H0283902 A JPH0283902 A JP H0283902A
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- Japan
- Prior art keywords
- terms
- mol
- voltage
- nonlinear resistor
- sintering
- 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.)
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Links
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 230000001419 dependent effect Effects 0.000 title abstract 3
- 238000005245 sintering Methods 0.000 claims abstract description 29
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 239000011268 mixed slurry Substances 0.000 claims abstract description 8
- 238000000465 moulding Methods 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- -1 Zinc borosilicate compound Chemical class 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 abstract description 30
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 abstract description 6
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052787 antimony Inorganic materials 0.000 abstract description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000002075 main ingredient Substances 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- CXOFVDLJLONNDW-UHFFFAOYSA-N Phenytoin Chemical compound N1C(=O)NC(=O)C1(C=1C=CC=CC=1)C1=CC=CC=C1 CXOFVDLJLONNDW-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003752 zinc compounds Chemical class 0.000 description 1
Landscapes
- Thermistors And Varistors (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【発明の詳細な説明】
Ａ、産業上の利用分野
本発明は、ギャップレス避雷器に適用される２ｎｏを主
成分とする電圧非直線抵抗体の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION A. Field of Industrial Application The present invention relates to a method of manufacturing a voltage nonlinear resistor having 2no as a main component and applied to a gapless lightning arrester.
Ｂ１発明の概要
本発明は、ＺｎＯを主成分とし、池の添加原料を含んだ
混合スラリーと造粒、成型、焼結して成る電圧非直線抵
抗体の製造方法において。B1 Summary of the Invention The present invention is a method for manufacturing a voltage nonlinear resistor, which comprises ZnO as a main component, granulation, molding, and sintering with a mixed slurry containing additive raw materials.
前記添加原料としてビスマスｅＢｉ２Ｏに換算して０．
１〜３． Ｑ＋＋ｏｌ”、、、コバルトをＣｏ２Ｏ３に
換算して０．０５〜３．０ｉｏ１％：、アンチモンをＳ
ｂ２Ｏ３に換算して０．１〜５．０ｍｏ ｌ’％、ケイ
素をＳ ｉ ０２に換算して０．０５〜５．０ｉｏ１’
；、クロムをＣｒ２Ｏ３に換算しテ０．０２〜３、０ｉ
ｏ１＄、ニッケルをＮｉＯに換算して０．１〜５．０ｍ
ｏ １ ％ 、マンガンをＭｎＯ２に換算して０．５５
〜０．７０ｍ。As the additive raw material, the amount of bismuth eBi2O is 0.
1-3. Q++ol”, Cobalt converted to Co2O3 0.05-3.0io1%: Antimony converted to S
0.1-5.0mol'% in terms of b2O3, 0.05-5.0io1' in terms of silicon
;, Chromium is converted to Cr2O3 Te0.02~3,0i
o1$, 0.1 to 5.0m when converting nickel to NiO
o 1%, manganese converted to MnO2 is 0.55
~0.70m.
１を配合し、かつ焼結温度を１１００〜１３００℃とす
ること、または前記添力■原料にホウケイ酸亜鉛化合物
（Ｂ２Ｏ３０＄、 Ｓ ｉ ０２１０％、 Ｚ ｎｏ
６０：） ０．０２〜０．５ｗｔ＄と、Ａ Ｉ ２Ｏ０
．００１〜０．０５ｍｏｌ＄ｅ加えることにより、
電圧非直線抵抗体のサージの吸収性を高め、かつ瀾れ電
流と小さくして、電力の損失と低減すると共に、熱暴走
による短絡事故を防止するようにしたことを特徴とする
。1 and the sintering temperature is 1100 to 1300°C, or the additive (1) is a borosilicate zinc compound (B2O30$, Si0210%, Z no
60:) 0.02~0.5wt$ and A I 2O0
．． By adding 0.001 to 0.05 mol$e, it increases the surge absorption of the voltage nonlinear resistor, reduces the stagnation current, reduces power loss, and prevents short circuit accidents due to thermal runaway. It is characterized by the following.
Ｃ０従来の技術
従来の電圧非直線抵抗体は、ＺｎＯ粉末にＢｉ２Ｏ３、
Ｃ０２Ｏ，Ｓ ｂ ２Ｏなどの粉末ｅ０．１〜数鼠ｏｌ
ｚ混合したものを、金型で円板状に成型し、これｅ １
２５０℃前後で焼結した後、焼結体の上下両面に対向電
極を形成することにより製造される。C0 Conventional technology A conventional voltage nonlinear resistor is made of ZnO powder with Bi2O3,
Powder such as C02O, Sb2O etc. e0.1~several ol
The mixture of z is molded into a disc shape with a mold, and this is e 1
It is manufactured by sintering at around 250° C. and then forming counter electrodes on both upper and lower surfaces of the sintered body.
ところで、電圧非直線抵抗体の特性を評価するための指
凛として、一般に非直線指数と制限電圧比が用いられて
いる。非直線指数αは、■を印加電圧、■を電流、Ｃを
通常の抵抗体の抵抗直に相当する量（非直線抵抗）とす
ると、Ｉ＝（Ｖ／Ｃ）’となる値である。この非直線指
数は、抵抗体に流れる涌ｉｔ流と少なくするためには大
きな値であることが望ましい、また、制限電圧比とは、
抵抗体に１ｍＡが流れた場合の端子間電圧ＶＩＨＡに対
する池の電流値における端子間電圧の比である。この制
限電圧比は、大電流領域における電圧の非直線性含水す
ものであり、避雷器ではサージの侵入の際に装置を保護
する上で小さいことが望ましい。By the way, a nonlinear index and a limiting voltage ratio are generally used as indicators for evaluating the characteristics of a voltage nonlinear resistor. The non-linear index α is a value such that I=(V/C)', where ■ is the applied voltage, ■ is the current, and C is the amount directly equivalent to the resistance of a normal resistor (non-linear resistance). It is desirable that this nonlinear index has a large value in order to reduce the flow of current flowing through the resistor, and the limiting voltage ratio is
This is the ratio of the voltage between the terminals at the current value of the pond to the voltage VIHA between the terminals when 1 mA flows through the resistor. This limiting voltage ratio includes voltage non-linearity in a large current region, and in a lightning arrester, it is desirable that it be small in order to protect the device in the event of a surge.
Ｄ０発明が解決しようとする課閃
上記従来の方法により製造した電圧非直線抵抗体と避雷
器に用いると、常時わずかながら漏れ電流が流れる。こ
のため、抵抗体が発熱し、放熱と平衡する温度で一定と
なる。しかし、この種の抵抗体においては、小電流域で
温度係数が負であるために、例えば短時間に連続的な開
閉サージや雷サージ等の大きなエネルギを処理した場合
や素子自体が劣化した場合に、発熱が放熱能力を上回っ
て、温度が著しく上昇し、これに流れる漏れ電流が過大
なものになる。こうなると、電力損失が増すばかりでな
く、いわゆる熱暴走と呼ばれる状聾に至り、短絡事故を
招く危険がある。D0 Problems to be Solved by the Invention When used in voltage nonlinear resistors and lightning arresters manufactured by the above-mentioned conventional method, a small amount of leakage current always flows. For this reason, the resistor generates heat, and the temperature remains constant at a level that is in balance with the heat radiation. However, this type of resistor has a negative temperature coefficient in the small current range, so if it handles large energy such as continuous switching surges or lightning surges in a short period of time, or if the element itself deteriorates. In this case, the heat generated exceeds the heat dissipation capacity, the temperature rises significantly, and the leakage current flowing therein becomes excessive. If this happens, not only will power loss increase, but there will also be a condition called thermal runaway, which may lead to a short-circuit accident.
従って、本発明は、サージの吸収性を高め、また、浦り
電流を少なくして電力の損失を低減すると共に、熱墨走
による短絡事故を防止するようにした電圧非直線抵抗体
を提供することを課趙としている。Therefore, the present invention provides a voltage non-linear resistor that improves surge absorption, reduces surge current, reduces power loss, and prevents short circuit accidents caused by thermal marking. This is what I am responsible for.
６１課題を解決するための手段
ＺｎＯを主成分とし、池の添加原料と含んだ混合スラリ
ー念造粒、成型、焼結して成る電圧非直線抵抗体の製造
方法において、前記電力「原料としてビスマス３Ｂｉ２
Ｏに換算して０．１〜３．０ｍｏｆ％。61 Means for Solving the Problem In a method for manufacturing a voltage nonlinear resistor comprising ZnO as a main component and a mixed slurry containing an additive raw material, fine granulation, molding, and sintering, 3Bi2
0.1 to 3.0 mof% in terms of O.
コバルトをＣｏ２Ｏ３に換算しテ０．０５〜３．Ｏｗｏ
ｌ：、 ７ンチモンｆ！：５ｂ２ｏ３にｍ算して０．１
〜５．（ｂ＋＋ｏｌ？、 ’ｙイ素を５ｉ０２に換算し
て００５〜５．０ｍｏｌ’ｏ、クロム３Ｃｒ２Ｏに換算
して０．０２〜３．０ｍｏ１％、ニッケルをＮｉＯにｆ
ｉｊ！して０．１〜５．０ｍｏ１％：、マンガンをＭｎ
Ｏ２に換算して０．５５〜０．７０１１ｏ１＄配合Ｌ、
カッ１１ Ｍ 温度を１１００〜１３００℃とし、また
は、前記添加原料にホウケイ酸亜鉛化合物（Ｂ２Ｏ３０
：、 Ｓ ｉ ｏ２ｔ。Cobalt is converted to Co2O3 and is 0.05 to 3. Owo
l:, 7inchmon f! :5b2o3 plus m and 0.1
~5. (b++ol?, 'y 005 to 5.0 mol'o in terms of 5i02, 0.02 to 3.0 mol'o in terms of chromium 3Cr2O, f to nickel in NiO)
ij! 0.1-5.0mo1%: Manganese, Mn
0.55 to 0.7011 o1$ blended L in terms of O2,
11 M The temperature is set at 1100 to 1300°C, or a zinc borosilicate compound (B2O30
:, Si o2t.
％、Ｚｎ０６０％） ０．０２−０．５ｗｔ＄と、Ａ
ｌ ２ｏ３ｏ、ｏ。%, Zn060%) 0.02-0.5wt$ and A
l 2o3o, o.
１〜０．０５ｍｏｌ＄と添加する方法を採用した。A method of adding 1 to 0.05 mol $ was adopted.
Ｆ、市川
本発明の電圧非直線抵抗体は、主成分となるＺｎＯにＢ
ｉ ２Ｏ０．１〜３．抛ｏ１：、 Ｃｏ２Ｏ０．０５
〜３．０ｍｏｌ”、、 Ｓ ｂ ２Ｏ０．１〜５．０＋
＋ｏｌ：、 Ｓ ｉ ０２０．０５〜５．ＯｍｏｌＳ、
Ｃｒ２Ｏ０．０２〜３．ＯｍｏｌＳ、 Ｎ ｉ ＯＯ
６１〜５．０ｍｏＨ，Ｍ ｎ○２０．５５〜０．７０＠
ｏｌ＄、またはこｈニ（８２Ｏ３０％、 Ｓ ｉ ２１
０％、 Ｚ ｎ Ｏ６０＄）０．０２〜０、５Ｗｔ：、
Ａ Ｉ ２Ｏ０．００１〜０．０５ｉｏ１％ｅ添加し
て混合スラリーをつくり、これを造粒し、加圧成型した
後、１１００〜１３００°Ｃで焼結する。こうして得た
抵抗体は、非直線指数が大きく漏れ電流が小さい。F. Ichikawa The voltage nonlinear resistor of the present invention contains B as the main component ZnO.
i2O0.1-3.抛o1:, Co2O0.05
〜3.0mol'',, S b 2O0.1~5.0+
+ol:, S i 020.05~5. OmolS,
Cr2O0.02-3. OmolS, N i OO
61~5.0moH, M n○20.55~0.70@
ol$, or kohni (82O30%, S i 21
0%, Z n O60$) 0.02~0,5Wt:,
A mixed slurry is prepared by adding 0.001 to 0.05io1% of A I 2 O, which is granulated, pressure molded, and then sintered at 1100 to 1300°C. The resistor thus obtained has a large nonlinear index and a small leakage current.
従って、電力損失が少なく、戸な温度上昇が抑制される
ので、熱暴走を生じない。しかも制限電圧比が小さいの
で、サージ吸収性に優れる。Therefore, power loss is small and temperature rise is suppressed, so thermal runaway does not occur. Moreover, since the limiting voltage ratio is small, it has excellent surge absorption properties.
Ｇ、実施例
本発明の詳細な説明する。この実施例において非直線抵
抗体と製造するには、先ず、純度９９％以上のＺｎＯを
９５．ＯｍｏｌＳ、 Ｂ ｉ ２０Ｂを０．５ｉｏ１％
；、 Ｃ、）２Ｏを０．５＠ｏＬ％、Ｓｔｇ０３を１．
０ｍｏｌ＄、 Ｓ ｉ ０２を１．０＠ｏＬｔ、 Ｃ
ｒ ２Ｏを０．５ｍｏｌ？；、 Ｎ ｉ○を１．０＋ｉ
ｏｌ＄。G. Examples The present invention will be described in detail. In order to manufacture the non-linear resistor in this example, first, ZnO with a purity of 99% or more is 95% pure. OmolS, B i 20B at 0.5io1%
;, C,)2O at 0.5@oL%, Stg03 at 1.
0mol$, S i 02 1.0@oLt, C
0.5 mol of r2O? ;, N i○ is 1.0+i
ol$.
ＭｎＯ２を０．４＠ｏ１％Ｊｉり収り、ボールミルで混
合する。この混合スラリーを乾燥させて造粒する。この
粉本含焼結？まの直径が３０＋ｎｍとなるように円板法
に加圧成型した後、１２５０℃で焼成する。こうして得
られた焼結体を厚さ５鴫に研磨した後、対向両面に直径
２７ｕ＋の銀電極な焼き付けて抵抗体が出来上がる。Add MnO2 at 0.4@o1%Ji and mix with a ball mill. This mixed slurry is dried and granulated. Is this powder sintered? After pressure molding in a disk method so that the diameter of the tube becomes 30+ nm, it is fired at 1250°C. After polishing the sintered body thus obtained to a thickness of 5 mm, silver electrodes with a diameter of 27 U+ were baked on both opposing surfaces to complete a resistor.
上記の工程のうちＭｎＯ２の添加量と焼結温度と各種変
えて損失、非直線指数、制限電圧比を測定したところ第
１図乃至第６図に示す拮果がでた。When the loss, nonlinear index, and limiting voltage ratio were measured by varying the amount of MnO2 added and the sintering temperature in the above process, the results shown in FIGS. 1 to 6 were obtained.
先ず、焼結温度を１２５０℃一定としたときのＭｎＯ２
の添加量に対する損失の変化は、第１図に示すグラフに
なる。このグラフに示されるようにＭｎＯ２の添加量が
０．５５〜０．７０ｍｏｌ＄の範囲に極小値が現れる。First, when the sintering temperature is kept constant at 1250°C, MnO2
The change in loss with respect to the amount added is shown in the graph shown in FIG. As shown in this graph, a minimum value appears when the amount of MnO2 added is in the range of 0.55 to 0.70 mol$.
ＭｎＯ２の添加量を０．６５ｉｏ１”、、一定としたと
きの焼結温度に対する損失の変化は、第２図に示すグラ
フになる。このグラフに示されるように焼結温度は１１
００〜１３００℃の範囲で損失が少なくなる０ＭｎＯ２
の添加量に対する非直線指数αの変１ヒは、第３図に示
すグラフになる。このグラフに示されるようにＭｎＯ２
の添加量が０．５５〜０．７０ｍｏｌ＄ノ範囲に極大値
が現れる。焼結温度に対する非直線指数αの変１ヒは、
第４図に示すグラフになる。このグラフに示されるよう
に焼結温度は１１００〜１３００℃の範囲で非直線指数
が大きくなる。ＭｎＯ２の添加量に対する制限電圧比の
変化は、第５図に示すグラフになる。このグラフに示さ
れるように制限電圧比はＭｎＯ２の添加量を増力■する
程小さくなる。焼結温度に対する制限電圧比の変化は第
６図に示すグラフになる。このグラフに示されるように
焼結温度は１１００〜１３００℃の範囲で制限電圧比が
大きくなる。The change in loss with respect to sintering temperature when the amount of MnO2 added is constant at 0.65io1" is shown in the graph shown in Figure 2. As shown in this graph, the sintering temperature is 11".
0MnO2 with low loss in the range of 00 to 1300℃
The variation of the non-linear index α with respect to the amount of addition is shown in the graph shown in FIG. As shown in this graph, MnO2
The maximum value appears in the range of 0.55 to 0.70 mol$. The variation of the nonlinear index α with respect to the sintering temperature is
The graph shown in FIG. 4 is obtained. As shown in this graph, the nonlinear index becomes large when the sintering temperature ranges from 1100 to 1300°C. The change in limiting voltage ratio with respect to the amount of MnO2 added is shown in the graph shown in FIG. As shown in this graph, the limiting voltage ratio becomes smaller as the amount of MnO2 added is increased. The graph shown in FIG. 6 shows the change in the limiting voltage ratio with respect to the sintering temperature. As shown in this graph, the limiting voltage ratio increases when the sintering temperature ranges from 1100 to 1300°C.
なお、第１．３．５図における変１ヒ旦はＭ ｎ ０２
を０．５０ｍｏＬ％としたときの値に対する比率で示し
、第２．４．６図における変化量は焼結温度を１２５０
℃としたときの値に対する比率で示した。In addition, change 1 Hidan in Figure 1.3.5 is M n 02
The amount of change in Figure 2.4.6 is expressed as a ratio to the value when the sintering temperature is 0.50mol%.
It is expressed as a ratio to the value in °C.
この結果、ＭｎＯ□を添加することにより、損失。As a result, by adding MnO□, loss.
非直線指数、制限電圧比が改善されることが分かる。但
し、この傾向は、添加原料３Ｂ ｉ ２Ｏ０．１〜３．
０ｉｏｌ＄、 Ｃｏ２Ｏ０．０５〜３．０ｍｏｌ＄、
Ｓ ｂ２Ｏ０．１〜５．０ｍｏｌ＄、 Ｓ ｉ ＯＸ
０．０２〜３．Ｏｍｏｌｌ：、 Ｃｒ２Ｏ０．０５〜５
．０＠ｏｌ：、 Ｎ ｉ Ｏ０，１〜５．０ｍｏｌ：、
Ｍ ｎ ０２０．５５〜０．１０ｍｏ１％の範囲で認
められる。It can be seen that the nonlinear index and limiting voltage ratio are improved. However, this tendency was observed when the additive raw material 3B i 2O was 0.1 to 3.
0iol$, Co2O0.05-3.0mol$,
S b2O0.1~5.0mol$, S i OX
0.02~3. Omoll:, Cr2O0.05~5
．． 0@ol:, N i O0,1-5.0 mol:,
M n 02 is observed in the range of 0.55 to 0.10 mo1%.
また、他の実施例は、上記実施例の添加原料にホウゲイ
酸亜鉛１ヒ合物（Ｂ２Ｏ３０＄、 Ｓ ｉ Ｏ□１０＄
、 Ｚ ｎ Ｏ６０：） ０．０２〜０．５ｖｔ：、及
びＡＩ（Ｎｏ３）９Ｈ２０をＡｌ２Ｏ３に換算して０．
Ｏ０５ｍｏｌｏ３ ？２加し、同一の工程により製造
したものて′ある。そして、ＭｎＯ２の添加量と焼結温
度に対する損失、非直線指数、制限電圧比の各変１ヒを
示すグラフを第７図乃至第１２図に示す、この実施例に
おいても上記実施例と同様な結果が得られた。In addition, in another example, zinc borosinate compound (B2O30$, SiO□10$
, Z n O60:) 0.02 to 0.5vt:, and 0.0 when converting AI(No3)9H20 to Al2O3.
O05molo3? In addition, there are products manufactured by the same process. Graphs showing changes in loss, nonlinear index, and limiting voltage ratio with respect to the amount of MnO2 added and the sintering temperature are shown in FIGS. 7 to 12. This example is similar to the above example. The results were obtained.
なお、本発明の実施例においてはマンガン等をＭｎＯ２
の形で添加したが、硝酸マンガン等の塩さらにはその水
溶液の形で添加しても同様に作用する。In addition, in the examples of the present invention, manganese etc. are replaced with MnO2
Although it was added in the form of , the same effect can be obtained even if it is added in the form of a salt such as manganese nitrate or an aqueous solution thereof.
Ｈ９発明の効果
以上のように本発明は、Ｚｎ○を主成分とし、池の添加
原料を含んだ混合スラリ−３造粒、成型、焼結して成る
電圧非直線ｔｆ１抗体の製造方法において、前記添加原
料としてビスマスをＢｉ２Ｏ３に換算して０．１〜３．
０躍ｏ １％、コバルトをＣｏ ２０．に換算して０．
０５〜３．０ｉｏ１％、アンチモンｔ！−８ｂ２Ｏに換
算しテ０．１〜５．０＠ｏｌ？、 ”イ索をＳｉＯ２Ｃ
：換１４して０．０５〜５、Ｑｍｏ１＄、クロムをＣｒ
２Ｏ３に換算して０．０２〜３．０ｍｏｌ％，ニッケル
３ＮｉＯに換算して０．１〜５゜０ｉｏｌ＄、マンガン
をＭｎＯ２に換算して０．５５〜０．７０ｍｏｂ；配合
し、かつ焼結温度を１１００〜１３００℃とし、または
、前記添加原料にホウケイ酸亜鉛化合物（Ｂ２Ｏ３０”
Ｘ、 Ｓ ｌ ０２１（１％、 Ｚ ｎ Ｏ６０％）
０．０２〜０．５ｗｔ、％及びＡ Ｉ ２Ｏ０．００１
〜０．０５ｍｏｌ＄ｅ添力１する方法を採用したため、
電圧非直線抵抗体の制限電圧比を小さくしてサージの吸
収性を高めることができ、また非直線指数と大きくして
漏れ電流を少なくし、電力の損失と低減することができ
ると共に、熱暴走による短絡事故と防止することができ
るという効果を奏する。Effects of the H9 Invention As described above, the present invention provides a method for producing a voltage non-linear tf1 antibody, which comprises granulating, molding, and sintering a mixed slurry containing Zn○ as a main component and additive raw materials. The amount of bismuth used as the additive raw material is 0.1 to 3.0 in terms of Bi2O3.
0 yen o 1%, Co 20. Convert to 0.
05-3.0io1%, antimony t! -8b2O converted to Te 0.1~5.0@ol? , ”Introduction to SiO2C
:Convert 14 to 0.05~5, Qmo1$, Cr to chromium
0.02 to 3.0 mol% in terms of 2O3, 0.1 to 5゜0iol in terms of nickel 3NiO, 0.55 to 0.70 mob in terms of manganese as MnO2; blended and sintered. The temperature is set at 1100 to 1300°C, or a zinc borosilicate compound (B2O30"
X, S l 021 (1%, Z n O 60%)
0.02-0.5wt,% and AI2O0.001
Since we adopted the method of adding ~0.05mol$1,
By decreasing the limiting voltage ratio of the voltage nonlinear resistor, it is possible to increase the absorption of surges, and by increasing the nonlinearity index, it is possible to reduce leakage current, reduce power loss, and prevent thermal runaway. This has the effect of preventing short-circuit accidents due to
【図面の簡単な説明】
第１図乃至第１２図は本発明の非直線抵抗１本の特性を
示す図面であり、第１図はＭ ｎ Ｏｚの添加量に対す
る損失の変１ヒを示すグラフ、第２図は焼結温度に対す
る損失の変化を示すグラフ、第３図はＭｎＯ２の添加量
に対する非直線指数αの変（ヒを示すグラフ、第４図は
焼＠温度に対する非直線指数αの変化を示すグラフ、第
５図はＭ ｎ Ｏ□の添加量に対する制限電圧比の変１
ヒと示すグラフ、第６図は焼結温度に対する制限電圧比
の変化を示すグラフ、第７図は池の実施例におけるＭｎ
Ｏ２の添加量に対する損失の変化を示すグラフ、第８図
は焼結温度に対する損失の変化を示すグラフ、第９図は
ＭｎＯ２の添加１に対する非直線指数αの変化を示すグ
ラフ、第１０図は焼結温度に対する非直線指数αの変（
ヒと示すグラフ、
第１１図はへ・Ｉ ｎ Ｏ２の添
加量に対する制限電圧比の変１ヒ３示すグラフ、第
１２図は焼結温度に対する制限電圧比の変１ヒと示すグ
ラフである。
“′”″″Ｘ′″−，１，Ｌｄ−）
外２名
境鑓１度（′Ｃ）
第
図
焼結１度（０Ｃ）
第
図
慢結！（Ｃ）
第
図
Ｍｎ０ｚ （ｍｏ！ ６１ｏ））
第１１
因
第１２
図[Brief Description of the Drawings] Figures 1 to 12 are diagrams showing the characteristics of one nonlinear resistor of the present invention, and Figure 1 is a graph showing changes in loss with respect to the amount of M n Oz added. , Figure 2 is a graph showing changes in loss with respect to sintering temperature, Figure 3 is a graph showing changes in nonlinear index α with respect to the amount of MnO2 added, and Figure 4 is a graph showing changes in nonlinear index α with respect to sintering temperature. A graph showing changes in the limiting voltage ratio with respect to the amount of M n O□ added is shown in Figure 5.
6 is a graph showing changes in limiting voltage ratio with respect to sintering temperature, and FIG. 7 is a graph showing changes in limiting voltage ratio with respect to sintering temperature.
A graph showing the change in loss with respect to the amount of O2 added, FIG. 8 is a graph showing the change in loss with respect to the sintering temperature, FIG. 9 is a graph showing the change in the nonlinear index α with respect to addition 1 of MnO2, and FIG. Variation of nonlinear index α with respect to sintering temperature (
FIG. 11 is a graph showing the variation of the limiting voltage ratio with respect to the amount of H.I n O2 added, and FIG. 12 is a graph showing the variation of the limiting voltage ratio with respect to the sintering temperature. "'"""X'"-, 1, Ld-) Outside 2 names boundary 1 degree ('C) Fig. Sintering 1 degree (0C) Fig. Sintering! (C) Fig. Mn0z (mo! 61o )) 11th cause 12th figure
Claims (2)
スラリーを造粒、成型、焼結して成る電圧非直線抵抗体
の製造方法において、 前記添加原料としてビスマスをＢｉ＿２Ｏ＿３に換算し
て０．１〜３．０ｍｏｌ％，コバルトをＣｏ＿２Ｏ＿３
に換算して０．０５〜３．０ｍｏｌ％，アンチモンをＳ
ｂ＿２Ｏ＿３に換算して０．１〜５．０ｍｏｌ％，ケイ
素をＳｉＯ＿２に換算して０．０５〜５．０ｍｏｌ％，
クロムをＣｒ＿２Ｏ＿３に換算して０．０２〜３．０ｍ
ｏｌ％，ニッケルをＮｉＯに換算して０．１〜５．０ｍ
ｏｌ％，マンガンをＭｎＯ＿２に換算して０．５５〜０
．７０ｍｏｌ％配合し、かつ焼結温度を１１００〜１３
００℃とすることを特徴とする電圧非直線抵抗体の製造
方法。(1) In a method for manufacturing a voltage nonlinear resistor by granulating, molding, and sintering a mixed slurry containing ZnO as a main component and other additive raw materials, bismuth as the additive raw material is converted into Bi_2O_3. 0.1 to 3.0 mol%, Co_2O_3
0.05 to 3.0 mol% in terms of S
0.1 to 5.0 mol% in terms of b_2O_3, 0.05 to 5.0 mol% in terms of silicon to SiO_2,
0.02 to 3.0m when converting chromium to Cr_2O_3
ol%, 0.1 to 5.0 m when converting nickel to NiO
ol%, converting manganese to MnO_2 is 0.55 to 0
．． 70 mol% blended and sintering temperature 1100-13
A method for manufacturing a voltage nonlinear resistor, characterized in that the temperature is 00°C.
＿３０％，ＳｉＯ＿２１０％，ＺｎＯ６０％）０．０２
〜０．５ｗｔ％と、Ａｌ＿２Ｏ＿３０．００１〜０．０
５ｍｏｌ％とを加えたことを特徴とする請求項（１）に
記載の電圧非直線抵抗体の製造方法。(2) Zinc borosilicate compound (B_2O
_30%, SiO_210%, ZnO60%) 0.02
~0.5wt% and Al_2O_30.001~0.0
The method for manufacturing a voltage nonlinear resistor according to claim 1, wherein 5 mol% is added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63236792A JPH0283902A (en) | 1988-09-21 | 1988-09-21 | Voltage-dependent nonlinear resistor and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63236792A JPH0283902A (en) | 1988-09-21 | 1988-09-21 | Voltage-dependent nonlinear resistor and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0283902A true JPH0283902A (en) | 1990-03-26 |
Family
ID=17005862
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63236792A Pending JPH0283902A (en) | 1988-09-21 | 1988-09-21 | Voltage-dependent nonlinear resistor and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0283902A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101702358B (en) | 2009-12-03 | 2011-03-16 | 陕西科技大学 | High voltage varistor and preparation method thereof |
| WO2013088847A1 (en) * | 2011-12-14 | 2013-06-20 | 株式会社明電舎 | Method for producing non-linear resistor element |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5490597A (en) * | 1977-12-28 | 1979-07-18 | Meidensha Electric Mfg Co Ltd | Voltage non-linear resistor |
| JPS59903A (en) * | 1982-06-25 | 1984-01-06 | 株式会社東芝 | Voltage nonlinear resistor |
-
1988
- 1988-09-21 JP JP63236792A patent/JPH0283902A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5490597A (en) * | 1977-12-28 | 1979-07-18 | Meidensha Electric Mfg Co Ltd | Voltage non-linear resistor |
| JPS59903A (en) * | 1982-06-25 | 1984-01-06 | 株式会社東芝 | Voltage nonlinear resistor |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101702358B (en) | 2009-12-03 | 2011-03-16 | 陕西科技大学 | High voltage varistor and preparation method thereof |
| WO2013088847A1 (en) * | 2011-12-14 | 2013-06-20 | 株式会社明電舎 | Method for producing non-linear resistor element |
| JP2013125821A (en) * | 2011-12-14 | 2013-06-24 | Meidensha Corp | Method for manufacturing nonlinear resistor element |
| CN103999169A (en) * | 2011-12-14 | 2014-08-20 | 株式会社明电舍 | Method for producing non-linear resistor element |
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