JPS62252904A - Porcelain compound for voltage nonlinear resistance unit andmanufacture of the same - Google Patents
Porcelain compound for voltage nonlinear resistance unit andmanufacture of the sameInfo
- Publication number
- JPS62252904A JPS62252904A JP61097139A JP9713986A JPS62252904A JP S62252904 A JPS62252904 A JP S62252904A JP 61097139 A JP61097139 A JP 61097139A JP 9713986 A JP9713986 A JP 9713986A JP S62252904 A JPS62252904 A JP S62252904A
- Authority
- JP
- Japan
- Prior art keywords
- parts
- mol parts
- range
- temperature
- 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.)
- Pending
Links
- 229910052573 porcelain Inorganic materials 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 title 1
- 239000000203 mixture Substances 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 239000004065 semiconductor Substances 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims 2
- 230000001590 oxidative effect Effects 0.000 claims 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 5
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 238000010405 reoxidation reaction Methods 0.000 description 4
- 229910019714 Nb2O3 Inorganic materials 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910002637 Pr6O11 Inorganic materials 0.000 description 2
- 229910004481 Ta2O3 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 235000010216 calcium carbonate Nutrition 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(III) oxide Inorganic materials O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000000644 propagated effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
産業上の利用分野
本発明は５ｒ（ｊ ｚ）ＣａｘＴｉ０５を主成分とする
、コンデンサとバリスタの両機能を有する電圧非直線性
抵抗体磁器組成物及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a voltage nonlinear resistor ceramic composition having both the functions of a capacitor and a varistor, and a method for manufacturing the same, which is mainly composed of 5r(j z)CaxTi05.
従来の技術
電子機器において、機器の内外部より伝播する異常電圧
やノイズ等によるトランジスタや集積回路等の破壊誤動
作を防止するため、各種のコンデンサやバリスタ等が使
用されているが、部品ではこれらノイズやサージパルス
等の吸収 ｉｌ／Ｉτ去が不完全である。近年登場した
容量性バリスタは、コンデンサとバリスタの両機能を有
するもので、ノイズやサージパルス等の吸収、除去、又
はバイパスとしての機能を単品で行うことができる。Conventional technology In electronic devices, various capacitors and varistors are used to prevent malfunctions of transistors and integrated circuits due to abnormal voltages and noise propagated from inside and outside the device. The absorption of il/Iτ from pulses and surge pulses is incomplete. Capacitive varistors, which have appeared in recent years, have both the functions of a capacitor and a varistor, and are capable of absorbing and removing noise and surge pulses, or acting as a bypass.
発明が解決しようとする問題点
しかし、従来のＳｒ Ｔｉ ０５材に半導体化元素（Ｎ
ｄ２Ｏ３ 、 Ｔａ２Ｏ３ 、 ＣｅＯ２等）ならびに
粒界に析出する元素Ｂｉ、Ｃｕ、Ｍｎ等）を添加して作
製したものは、サージ耐量が１０〜６０人と小さいだめ
、信頼性が乏しく、利用範囲も限定されたものであった
。また、電子機器の高性能、多機能化に伴い、小型大容
量でなおかつサージ耐量の大きな、信頼性の高い容量性
バリスタが要求されている。Problems to be Solved by the Invention However, the semiconductor element (N) is added to the conventional SrTi05 material.
Products made by adding elements such as d2O3, Ta2O3, CeO2) and elements precipitated at grain boundaries (Bi, Cu, Mn, etc.) have a small surge resistance of 10 to 60 people, have poor reliability, and have a limited range of use. It was something that was done. Further, as electronic equipment becomes more sophisticated and multifunctional, there is a demand for highly reliable capacitive varistors that are small in size, have large capacity, and have high surge resistance.
問題点を解決するだめの手段
本発明にかかわる磁器組成物は、Ｓｒ（＋−ｘ）””Ｔ
ｉＯ３（但しＸは０．０１４Ｘ ｌ−（Ｊ ５の範囲）
成分が１００モル部、Ｎｂ２Ｏ３、Ｔａ２Ｏ３ 、 Ｗ
Ｏ３、ＧｅＯ２。Means for Solving the Problems The porcelain composition according to the present invention has Sr(+-x)""T
iO3 (X is 0.014X l- (range of J5)
Ingredients: 100 mole parts, Nb2O3, Ta2O3, W
O3, GeO2.
”２Ｏ３ 、Ｎｄ２ ｏ３ ｒ Ｙ２Ｏ３ ＊ ”２Ｏ
３ ｒ Ｄ３’２ ｏ５ ＋ ”２Ｏ３及びＰｒ６０，
１ の内、少くとも１種の金属酸物成分が、０、ｏＯ
°６〜３．００モル部、Ｃｒ２Ｏ３成分が０．０１〜２
８００モル部、さらに、ＳｉＯ２．ＣｕＯ及びＭｎ ０
２の内、少くとも１種の酸化物成分が０．０１〜２．０
０モル部からなるものである。"2O3, Nd2 o3 r Y2O3 *"2O
3 r D3'2 o5 + "2O3 and Pr60,
1, at least one metal oxide component is 0, oO
°6 to 3.00 mole parts, Cr2O3 component is 0.01 to 2
800 mole parts, and further SiO2. CuO and Mn0
2, at least one oxide component is 0.01 to 2.0
It consists of 0 mole part.
作用
本発明は以上の手段よりなるため、５ｒ（１−ｘ）Ｃａ
ｘＴｉ０５成分の内Ｃ＆がバリスタ電圧の非直線係数を
大きくするとともにサージ耐量を向上させＮｂ２ｏ５な
どは、５ｒ（ｊ ｚ）ＣａｘＴｉ０５を原子価制御の原
理により半導体化させるのに必要な成分であり、Ｃｒ２
Ｏ３は、結晶粒界での濃度が高く、バリスタ特性に寄与
し、さらにＳｉＯ２ 、 （ｕｏ及びＭｎＯ□はバリス
タ電圧の非直線係数を改善する。Effect Since the present invention consists of the above means, 5r(1-x)Ca
Of the xTi05 components, C& increases the nonlinear coefficient of the varistor voltage and improves the surge resistance.
O3 has a high concentration at grain boundaries and contributes to the varistor properties, and SiO2, (uo and MnO□) improve the nonlinear coefficient of the varistor voltage.
実施例 以下実施例をあげて、本発明につき詳細に説明する。Example The present invention will be described in detail below with reference to Examples.
実施例１
Ｓｒ（、ｚ）ＣａｘＴｉ０５のＸが第１表の主成分の欄
のＸの値になるように、市販の工業用原料５ｒＣＯ５粉
末（純度９９係以上）、ＣａＣＯ３粉末（純度９９チ以
上）、及びＴｉＯ２粉末（純度９９％９％以上それぞれ
秤量配合し、ボールミルで２０時間（、ｉ＋’５合した
。これを乾燥した後、この粉末を１１５０℃の温度で２
時間仮焼した。その後ボールミルで湿式粉砕した。この
ようにして得られた５ｒ（１−２）ＣａｚＴ１０５粉末
１００モル部に対して、市販の試薬特級（純度９９．９
％以上） Ｎｂ２Ｏ３、Ｔａ２Ｏ，、、ＷＯ３。Example 1 Commercially available industrial raw materials 5rCO5 powder (purity of 99% or higher) and CaCO3 powder (purity of 99% or higher) were used so that the value of ), and TiO2 powder (purity of 99% or higher, 9% or higher) were weighed and blended in a ball mill for 20 hours (i+'5). After drying, this powder was heated at a temperature of 1150°C for 20 hours.
Calcined for an hour. Thereafter, it was wet-pulverized using a ball mill. To 100 mol parts of the 5r(1-2)CazT105 powder thus obtained, commercially available reagent special grade (purity 99.9
% or more) Nb2O3, Ta2O,..., WO3.
ＣｅＯ２＋ Ｌ２Ｌ２ ”５ ＋ Ｎｄ２Ｏ３ ｒ Ｙ
２Ｏ３− ”２ ｏ５ ＊ Ｄ３’２Ｏ３ ｒＧｄ２ｏ
３及びＰｒ６Ｏ１１の内９、少くとも１種の金属酸化物
と、試薬特級（純度９９．９％以上）Ｃｒ２Ｏ３を第１
表に示すように秤量配合し、ボールミルで２０時時間式
混合した。乾燥後、５重量％のポリビニルアルコール水
溶液をバインダーとして１０重量係添加混合し、３２メ
ツシユバスに造粒した。CeO2+ L2L2 ”5 + Nd2O3 r Y
2O3- "2 o5 * D3'2O3 rGd2o
3 and 9 of Pr6O11, at least one metal oxide, and reagent special grade (purity 99.9% or more) Cr2O3 as the first
The ingredients were weighed and blended as shown in the table, and mixed in a ball mill for 20 hours. After drying, 10% by weight of a 5% by weight aqueous polyvinyl alcohol solution was added and mixed as a binder, and the mixture was granulated into a 32 mesh bath.
この造粒粉末を１０１００ｏ／ｃｍの圧力で円板形に成
形した。This granulated powder was molded into a disk shape under a pressure of 10,100 o/cm.
これらの成形体を空気中において１０００℃の温度で加
熱処理した後、Ｎ２ （９５容積％）＋Ｈ２（６容積チ
）の還元性雰囲気中で１４００℃の温度で４時間焼成し
、直径約６’ ｍｍ、厚さ約０．’７ ｍｍの半導体磁
器を得た。次に、これを空気中で１１５０℃の温度で４
時間熱処理した。次にこの磁器の両面にオーミックＡｇ
ペーストを塗布し、６５０℃の温度で焼付けて容量性バ
リスタを得た。These molded bodies were heat-treated at a temperature of 1000°C in air, and then fired at a temperature of 1400°C for 4 hours in a reducing atmosphere of N2 (95% by volume) + H2 (6 volumes) to give a diameter of approximately 6'. mm, thickness approximately 0. '7 mm semiconductor porcelain was obtained. Next, this was heated in air at a temperature of 1150℃ for 4 hours.
Heat treated for hours. Next, ohmic Ag is applied to both sides of this porcelain.
The paste was applied and baked at a temperature of 650°C to obtain a capacitive varistor.
次に容量性バリスタの特性評価を行うために、静電容量
（以下Ｃと略す）、誘電圧接（以下ｔａｎδと略す）、
バリスタ電圧ｖ＋ ＋非直線係数α、及びサージ耐量
を測定し、第２表に示す結果を得た。Next, in order to evaluate the characteristics of the capacitive varistor, the capacitance (hereinafter abbreviated as C), dielectric voltage contact (hereinafter abbreviated as tanδ),
The varistor voltage v+ + nonlinear coefficient α and surge resistance were measured, and the results shown in Table 2 were obtained.
Ｃおよびｔａｎδはブリッジ回路を用い２０℃。C and tan δ using a bridge circuit at 20°C.
１ＫＨｚで測定した。Measured at 1KHz.
また、バリスタ電圧ｖ１はバリスタに１ｍ人の電流を流
した時の電圧を測定し、非直線係数αはバリスタに１ｍ
ｍムラ０ｍ人の各電流を流した時のそれぞれの電圧ｖ＋
ｚｖＴｏを測定し、次式よシ求めた。In addition, the varistor voltage v1 is measured as the voltage when a current of 1 m is passed through the varistor, and the nonlinear coefficient α is the voltage when a current of 1 m is applied to the varistor.
Each voltage v+ when each current is passed through m unevenness 0m person
zvTo was measured and calculated using the following formula.
α＝１／βＯｇ（Ｌ＋ｏ／ ｖ４ ）
また、サージ耐量は、バリスタに８×２０μｓの電流波
形のサージを加え、その後バリスタ電圧ｖ１ を測定し
初期値に対して１０％変化した時の最大電流値を測定し
た。α=1/βOg(L+o/v4) In addition, the surge withstand capacity is the maximum current value when a surge with a current waveform of 8 x 20 μs is applied to the varistor, and then the varistor voltage v1 is measured and changes by 10% from the initial value. was measured.
また、寿命試験は、次に示す条件で湿空負荷寿命試験を
１０００時間行い、コンデンサ特性とバリスタ特性を前
述の方法で測定した。In addition, for the life test, a humid air load life test was conducted for 1000 hours under the following conditions, and the capacitor characteristics and varistor characteristics were measured using the method described above.
湿空負荷寿命試験条件
６５±２℃、９０〜９５チＲｈ、の恒温恒湿槽にてり、
Ｃ２０Ｖ連続印加を行った。Humid air load life test conditions: 65±2℃, 90-95cmRh, in a constant temperature and humidity chamber.
C20V was continuously applied.
（以 下 余 白）
第 １ 表
試料番号１はＳｒ（、ｚ）ＣａｘＴｉ０３のＸが０．０
１未満でバリスタ特性の改善に効果がなく、試料番号１
６はＸが０．５を超え、Ｃａｐが３４ｎＦと低くｔａｎ
δ も３．２俤と高く、本発明の範囲外とした。(Margin below) Table 1 Sample number 1 has Sr(,z)CaxTi03 with X of 0.0.
If it is less than 1, there is no effect on improving the varistor characteristics, and sample number 1
6 has a low tan with X exceeding 0.5 and a cap of 34nF.
δ was also as high as 3.2 k, which was outside the scope of the present invention.
また試料番号８は、Ｎｂ２Ｏ５の成分量が０．００５モ
ル部未満でｔａｎδが８．１チと高く、試料番号１５は
Ｎｂ２Ｏ５の成分量が３．００モル部を超え、ｔａｎδ
が５チと高くサージ耐量も了ＯＡと低く本発明の範囲外
とした。また試料番号２，５はＣｒ２Ｏ５の成分量が０
．０１モル部未満でサージ耐量４０．００人と低く、試
料番号９はＣｒ２Ｏ５の成分量が２００モル部を超え、
ｔａｎδが３．２％と高く、サージ耐量も８０Ａと低く
本発明の範囲外とした。In addition, sample number 8 has a component amount of Nb2O5 of less than 0.005 mol parts and has a high tan δ of 8.1, while sample number 15 has a component amount of Nb2O5 exceeding 3.00 mol parts and has a high tan δ of 8.1.
The surge resistance was as high as 5 cm, and the surge resistance was low as OA, which was outside the scope of the present invention. In addition, sample numbers 2 and 5 have a content of Cr2O5 of 0.
．． Sample No. 9 has a Cr2O5 component amount of over 200 mole parts, and the surge resistance is low at 40.00 mole parts.
The tan δ was high at 3.2%, and the surge resistance was low at 80 A, so it was outside the scope of the present invention.
実施例２
実施例１で示した主成分、半導体化元素、Ｃｒ２Ｏ５か
らなる組成に第３表に示すように、市販の試薬特級（純
度９９．９％以上） ＳｉＯ２ 、 ＣｕＯ、及びＭｎ
Ｏ２の内、少くとも１種の酸化物を添加し、容量性バリ
スタを実施例１と同一方法で作成、測定した。Example 2 In addition to the composition shown in Example 1 consisting of the main components, semiconducting elements, and Cr2O5, commercially available special grade reagents (purity of 99.9% or more) SiO2, CuO, and Mn were added as shown in Table 3.
A capacitive varistor was prepared and measured in the same manner as in Example 1 except that at least one oxide of O2 was added.
その結果を第４表に示す。The results are shown in Table 4.
試料番号７は、ＳｉＯ２ 、 ＣｕＯ、及びＭｎＯ２の
添加の効果を調べるための比較試料である。試料番号５
３．６３．７３は、それぞれＳｉＯ２ 、 Ｃｕ Ｏ、
ＭｎＯ２の成分量が、２．００モル部を超え、ｔａｎδ
が３チ以上あり、サージ耐量も５０Å以下と低く、本発
明の範囲外とした。Sample number 7 is a comparative sample for examining the effects of adding SiO2, CuO, and MnO2. Sample number 5
3.63.73 are SiO2, CuO, and
The component amount of MnO2 exceeds 2.00 mol parts, tan δ
3 or more, and the surge resistance was low at 50 Å or less, and was therefore outside the scope of the present invention.
実施例３
実施例１における試料番号７，４，１０．２９、実施例
２における試料番号６！５．９０の組成を用いて、実施
例１と同一方法で成形体を作成した。Example 3 Molded bodies were created in the same manner as in Example 1 using the compositions of sample numbers 7, 4, and 10.29 in Example 1 and sample numbers 6!5.90 in Example 2.
これら成形体を空気中において、１０００℃の温度で加
熱処理した後、Ｍ２（ｓ ｓ容積係）＋Ｈ２（６容積係
）の還元性雰囲気中で第６表に示す温度で４時間焼成し
、直径約ｅｍｍ、厚さ約０．７ ｍｍの半導体磁器を得
た。次にこれを空気中で第５表に示す再酸化温度で４時
間、熱処理した。次にこの磁器の両面にオーミックＡｇ
ペーストを！で布し、５５０℃の温度で焼付けて容量性
バリスタを心また〇測定は、実施例１と同一方法で行な
い、その結果を第ぢ表に併せて示す。These molded bodies were heat-treated in air at a temperature of 1000°C, and then fired for 4 hours at the temperatures shown in Table 6 in a reducing atmosphere of M2 (s s volume ratio) + H2 (6 volume ratio). A semiconductor porcelain with a thickness of about 0.7 mm and a thickness of about 0.7 mm was obtained. Next, this was heat treated in air at the reoxidation temperature shown in Table 5 for 4 hours. Next, ohmic Ag is applied to both sides of this porcelain.
Paste! The measurements were carried out in the same manner as in Example 1, and the results are also shown in Table 1.
試料番号１０１は雰囲気焼成温度が１３００℃未満で焼
結不足となり半導体化が充分性なわれず、コンデンサ特
性、バリスタ特性共に悪く、また試料番号１０５は雰囲
気焼成温度が１６００℃を超え、１００μｍ以上の粗大
粒子ができ、サージ耐量が５０Ａ以下であるので本発明
の範囲外とした。Sample No. 101 has an atmosphere firing temperature of less than 1300°C, which results in insufficient sintering, resulting in insufficient semiconductor formation and poor capacitor and varistor characteristics. Sample No. 105 has an atmosphere firing temperature of over 1600°C, resulting in insufficient sintering and poor varistor characteristics. Since coarse particles are formed and the surge resistance is 50A or less, it is excluded from the scope of the present invention.
また試料番号１０６は再酸化温度が８００℃未満で、結
晶粒界の絶縁化が不充分で、ｔａｎδが３係以上、サー
ジ耐量が５０Å以下になるので本発明の範囲外とした。Sample No. 106 had a reoxidation temperature of less than 800° C., insufficient insulation of grain boundaries, tan δ of 3 or more, and surge resistance of 50 Å or less, so it was excluded from the scope of the present invention.
また、試料番号１１１は再酸化温度が１３００℃を超え
、結晶粒子内部まで再酸化が進行し、サージ耐量が５０
Å以下になるので本発明の範囲外とした。In addition, sample number 111 has a reoxidation temperature exceeding 1300°C, and reoxidation progresses to the inside of the crystal grains, resulting in a surge resistance of 50°C.
Since it is less than Å, it is outside the scope of the present invention.
尚、本発明での実施例では、金属酸化物を使用したが、
最終的に金属酸化物が得られれば本発明の目的が達成さ
れるので、金属元素 Ｈ；、Ｈ、ｒｌ塩、水酸化物、硝
酸塩９シユウ酸塩を用いてもさしつかえない。In addition, in the examples of the present invention, metal oxides were used, but
Since the object of the present invention is achieved if a metal oxide is finally obtained, it is acceptable to use metal elements H;, H, rl salts, hydroxides, nitrates, and oxalates.
発明の効果
本発明の電圧非直線性抵抗体は以上のように、Ｓ ｒ
（１ｚ ） （： ａ Ｘ Ｔ １０５ （但しＸは０
．０１４）（≦０．０５の範囲）の成分が１００モル部
、Ｎｂ２Ｏ５＋ Ｔ’２Ｏ３ 。Effects of the Invention As described above, the voltage nonlinear resistor of the present invention has S r
(1z) (: a X T 105 (X is 0
．． 014) (range of ≦0.05) is 100 mole parts, Nb2O5+ T'2O3.
ＷＯ３、ＣｅＯ２，Ｌａ２Ｏ３、Ｎｂ２Ｏ３、Ｙ２Ｏ３
、Ｙ２Ｏ３、Ｓｍ２Ｏ３、Ｄｙ２Ｏ３゜Ｇｄ２Ｏ３及び
Ｐｒ６Ｏ１１の内、少くとも１種の金属酸化物成分がＯ
１○０６〜：１ＪＯＯモル部、ｃｒ２ｏ、成分が０．０
１〜２．０Ｑモル部、ＳｉＯ２ 、 ＣｕＯ及びＭｎＯ
２の内、少くとも１種の酸化物成分が０．０１〜２．０
０モル部からなるだめサージ耐圧が高くまだバリスタ電
圧の非直線性係数が大きくなる。WO3, CeO2, La2O3, Nb2O3, Y2O3
, Y2O3, Sm2O3, Dy2O3°Gd2O3 and Pr6O11, at least one metal oxide component is O
1○06~: 1 JOO mole part, cr2o, component is 0.0
1-2.0Q mole parts, SiO2, CuO and MnO
2, at least one oxide component is 0.01 to 2.0
Due to the 0 molar part, the surge withstand voltage is high and the nonlinearity coefficient of the varistor voltage is large.
Claims (4)
但しｘは０．０１≦ｘ≦０．５の範囲）が１００モル部
と、Ｎｂ＿２Ｏ＿５、Ｔａ＿２Ｏ＿５、ＷＯ＿３、Ｇｅ
Ｏ＿２、Ｌａ＿２Ｏ＿３、Ｎｄ＿２Ｏ＿３、Ｙ＿２Ｏ＿
３、Ｓｍ＿２Ｏ＿３、Ｄｙ＿２Ｏ＿３、Ｇｄ＿２Ｏ＿３
及びＰｒ＿６Ｏ＿１＿１の内少くとも１種の金属酸化物
０．００５〜３．００モル部と、Ｃｒ＿２Ｏ＿３が０．
０１〜２．００モル部とを含む電圧非直線性抵抗体磁器
組成物。(1) Sr_(_1_−_x_)Ca_xTiO_3(
However, x is in the range of 0.01≦x≦0.5) is 100 mol parts, and Nb_2O_5, Ta_2O_5, WO_3, Ge
O_2, La_2O_3, Nd_2O_3, Y_2O_
3, Sm_2O_3, Dy_2O_3, Gd_2O_3
and 0.005 to 3.00 mol parts of at least one metal oxide among Pr_6O_1_1, and 0.005 to 3.00 mol parts of Cr_2O_3.
01 to 2.00 mole parts of a voltage nonlinear resistor ceramic composition.
但しｘは０．０１≦ｘ≦０．５の範囲）が１００モル部
と、Ｎｂ＿２Ｏ＿５、Ｔａ＿２Ｏ＿５、ＷＯ＿３、Ｃｅ
Ｏ＿２、Ｌａ＿２Ｏ＿３、Ｎｄ＿２Ｏ＿３、Ｙ＿２Ｏ＿
３、Ｓｍ＿２Ｏ＿３、Ｄｙ＿２Ｏ＿３、Ｇｄ＿２Ｏ＿３
及びＰｒ＿６Ｏ＿１＿１の内、少くとも１種の金属酸化
物０．００５〜３．００モル部と、Ｃｒ＿２Ｏ＿３が０
．０１〜２．００モル部とを含む組成物を成形体としこ
れを還元性雰囲気中において、１３００〜１５００℃の
範囲内の温度で焼結させ、得られた半導体磁器をさらに
酸化性雰囲気中において８００〜１３００℃の範囲内の
温度で加熱することを特徴とする電圧非直線性抵抗体磁
器組成物の製造方法。(2) Sr_(_1_−_x_)Ca_xTiO_3(
However, x is in the range of 0.01≦x≦0.5) is 100 mol parts, Nb_2O_5, Ta_2O_5, WO_3, Ce
O_2, La_2O_3, Nd_2O_3, Y_2O_
3, Sm_2O_3, Dy_2O_3, Gd_2O_3
and 0.005 to 3.00 mol parts of at least one metal oxide among Pr_6O_1_1 and 0.005 to 3.00 mol parts of Cr_2O_3.
．． A composition containing 01 to 2.00 mole parts is made into a molded body, and this is sintered in a reducing atmosphere at a temperature within the range of 1300 to 1500°C, and the obtained semiconductor porcelain is further sintered in an oxidizing atmosphere. A method for producing a voltage nonlinear resistor ceramic composition, which comprises heating at a temperature within the range of 800 to 1300°C.
但しｘは０．０１≦ｘ≦０．５の範囲）が１００モル部
と、Ｎｂ＿２Ｏ＿５、Ｔａ＿２Ｏ＿５、ＷＯ＿３、Ｃｅ
Ｏ＿２、Ｌａ＿２Ｏ＿３、Ｎｄ＿２Ｏ＿３、Ｙ＿２Ｏ＿
３、Ｓｍ＿２Ｏ＿３、Ｄｙ＿２Ｏ＿３、Ｇｄ＿２Ｏ＿３
及びＰｒ＿６Ｏ＿１＿１の内、少くとも１種の金属酸化
物０．００５〜３．００モル部と、Ｃｒ＿２Ｏ＿３が０
．０１〜２．００モル部と、ＳｉＯ＿２、ＣｕＯ及びＭ
ｎＯ＿２の内少くとも１種の酸化物０．０１〜２．００
モル部を含む電圧非直線性抵抗体磁器組成物。(3) Sr_(_1_−_x_)Ca_xTiO_3(
However, x is in the range of 0.01≦x≦0.5) is 100 mol parts, Nb_2O_5, Ta_2O_5, WO_3, Ce
O_2, La_2O_3, Nd_2O_3, Y_2O_
3, Sm_2O_3, Dy_2O_3, Gd_2O_3
and 0.005 to 3.00 mol parts of at least one metal oxide among Pr_6O_1_1 and 0.005 to 3.00 mol parts of Cr_2O_3.
．． 01 to 2.00 mole parts, SiO_2, CuO and M
At least one oxide of nO_2 0.01 to 2.00
A voltage nonlinear resistor ceramic composition comprising molar parts.
但しｘは０．０１≦ｘ≦０．５の範囲）が１００モル部
と、Ｎｂ＿２Ｏ＿５、Ｔａ＿２Ｏ＿５、ＷＯ＿３、Ｃｅ
Ｏ＿２、Ｌａ＿２Ｏ＿３、Ｎｄ＿２Ｏ＿３、Ｙ＿２Ｏ＿
３、Ｓｍ＿２Ｏ＿３、Ｄｙ＿２Ｏ＿３、Ｇｄ＿２Ｏ＿３
及びＰｒ＿６Ｏ＿１＿１の内、少くとも１種の金属酸化
物０．００５〜３．００モル部と、Ｃｒ＿２Ｏ＿３が０
．０１〜２．００モル部と、ＳｉＯ＿２、ＣｕＯ及びＭ
ｎＯ＿２の内、少くとも１種の酸化物０．０１〜２．０
０モル部とから成る組成物を成形体とし、これを還元性
雰囲気中で１３００〜１５００℃の範囲内の温度で焼結
させ、得られた半導体磁器を、さらに酸化性雰囲気中に
おいて８００〜１３００℃の範囲内の温度で加熱して再
酸化することを特徴とする電圧非直線性抵抗体磁器組成
物の製造方法。(4) Sr_(_1_−_x_)Ca_xTiO_3(
However, x is in the range of 0.01≦x≦0.5) is 100 mol parts, Nb_2O_5, Ta_2O_5, WO_3, Ce
O_2, La_2O_3, Nd_2O_3, Y_2O_
3, Sm_2O_3, Dy_2O_3, Gd_2O_3
and 0.005 to 3.00 mol parts of at least one metal oxide among Pr_6O_1_1 and 0.005 to 3.00 mol parts of Cr_2O_3.
．． 01 to 2.00 mole parts, SiO_2, CuO and M
At least one oxide of nO_2 0.01 to 2.0
A composition consisting of 0 molar part is made into a molded body, which is sintered at a temperature within the range of 1300 to 1500°C in a reducing atmosphere, and the obtained semiconductor porcelain is further sintered at a temperature of 800 to 1300°C in an oxidizing atmosphere. 1. A method for producing a voltage nonlinear resistor ceramic composition, which comprises heating and reoxidizing at a temperature within the range of °C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61097139A JPS62252904A (en) | 1986-04-25 | 1986-04-25 | Porcelain compound for voltage nonlinear resistance unit andmanufacture of the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61097139A JPS62252904A (en) | 1986-04-25 | 1986-04-25 | Porcelain compound for voltage nonlinear resistance unit andmanufacture of the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62252904A true JPS62252904A (en) | 1987-11-04 |
Family
ID=14184232
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61097139A Pending JPS62252904A (en) | 1986-04-25 | 1986-04-25 | Porcelain compound for voltage nonlinear resistance unit andmanufacture of the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62252904A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6444003A (en) * | 1987-08-12 | 1989-02-16 | Hokuriku Elect Ind | Voltage-dependent nonlinear resistance ceramic composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57187906A (en) * | 1981-05-14 | 1982-11-18 | Taiyo Yuden Kk | Semiconductor porcelain composition with nonlinear voltage/current characteristic and method of producing same |
-
1986
- 1986-04-25 JP JP61097139A patent/JPS62252904A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57187906A (en) * | 1981-05-14 | 1982-11-18 | Taiyo Yuden Kk | Semiconductor porcelain composition with nonlinear voltage/current characteristic and method of producing same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6444003A (en) * | 1987-08-12 | 1989-02-16 | Hokuriku Elect Ind | Voltage-dependent nonlinear resistance ceramic composition |
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