JPH01136323A - Nonlinear dielectric element - Google Patents
Nonlinear dielectric elementInfo
- Publication number
- JPH01136323A JPH01136323A JP62294158A JP29415887A JPH01136323A JP H01136323 A JPH01136323 A JP H01136323A JP 62294158 A JP62294158 A JP 62294158A JP 29415887 A JP29415887 A JP 29415887A JP H01136323 A JPH01136323 A JP H01136323A
- Authority
- JP
- Japan
- Prior art keywords
- bao
- nonlinear dielectric
- dielectric element
- hfo2
- zro2
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims description 10
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 11
- 238000005245 sintering Methods 0.000 abstract description 6
- 229910052573 porcelain Inorganic materials 0.000 abstract description 5
- 239000003989 dielectric material Substances 0.000 abstract description 3
- 229910002113 barium titanate Inorganic materials 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 abstract 4
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 abstract 4
- 239000004615 ingredient Substances 0.000 abstract 1
- 239000002075 main ingredient Substances 0.000 abstract 1
- 230000003405 preventing effect Effects 0.000 abstract 1
- 239000000654 additive Substances 0.000 description 15
- 238000010586 diagram Methods 0.000 description 9
- 230000009466 transformation Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000009532 heart rate measurement Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910015806 BaTiO2 Inorganic materials 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910003087 TiOx Inorganic materials 0.000 description 1
- 229910003134 ZrOx Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野〕
この発明は、ＢａＴｉ Ｏｓ系多結晶体からなる、非直
線特性の優れた非直線性誘電体素子に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a nonlinear dielectric element having excellent nonlinear characteristics and made of a BaTiOs polycrystal.
Ｃ従来の技術〕
一般にＢａＴｉ Ｏｓ系セラミックを中心とするペロブ
スカイ）Ｊｌ（構造を有するＡ Ｂ Ｏｓ系強誘電体の
応用分野としては、その高誘電率や圧電特性を利用する
分野の他に、強誘電体の非直線性を利用した分野が知ら
れている。C. Prior Art] Application fields of ABOs-based ferroelectrics, which are generally based on BaTiOs-based ceramics (perovsky) Fields that utilize the nonlinearity of dielectrics are known.
近年新たな応用例として、このような強誘電体を、蛍光
灯、水銀放電灯、す） ＩＪウム放電灯などの放電灯無
接点始動装置の高圧パルス発生素子として用い４ること
が、特公昭４８−２８７２６号公報などにおいて開示さ
れている。In recent years, as a new example of application, the use of such ferroelectric materials as high-voltage pulse generating elements in non-contact starting devices for discharge lamps such as fluorescent lamps, mercury discharge lamps, and IJum discharge lamps has been proposed4. It is disclosed in Japanese Patent No. 48-28726 and the like.
ところで、かかる用途に使用される非直線性誘電体素子
としては、Ｄ−Ｅヒステリシス曲線の傾斜が急峻でその
温度特性が良好であること、誘電率が高い値でしかも温
度特性が良好であること、すなわち電圧Ｖと電荷Ｑの関
係が第８図に示すように角形特性であり、温度に対して
安定であることが要求される。By the way, nonlinear dielectric elements used for such applications must have a steep DE hysteresis curve and good temperature characteristics, and have a high dielectric constant and good temperature characteristics. That is, the relationship between the voltage V and the charge Q is required to be square as shown in FIG. 8, and to be stable with respect to temperature.
ＢａＴｉ Ｏａ単結晶は、かかるヒステリシス曲線が角
形特性を示すために非直線性誘電体素子としては有効で
あるが、温度変化に対して非直線特性が不安定であり、
またその製造法も研究段階で実用化に至っていない、し
たがって従来はＢａＴｌ Ｏｓ系多結晶体を用いた非直
線性誘電体素子の利用が考えられているが、このＢａＴ
ｉＯ３系多結晶体は、−触に第９図に示すように、Ｄ−
Ｅヒステリシス曲線がある程度の飽和特性を示すが、残
留分極のばらつきが大きく、また誘電率が温度に対して
不安定であり、更にはＤ−Ｆ、ヒステリシス曲線の傾斜
が緩慢であり、非直線性誘電体素子としては良好な特性
のものが実用化されるに至っていない。BaTi Oa single crystal is effective as a nonlinear dielectric element because its hysteresis curve exhibits square characteristics, but its nonlinear characteristics are unstable with respect to temperature changes.
Furthermore, the manufacturing method is still at the research stage and has not yet been put to practical use.Therefore, conventionally, the use of nonlinear dielectric elements using BaTlOs polycrystals has been considered;
The iO3-based polycrystal is D-
Although the E hysteresis curve shows some degree of saturation characteristics, the residual polarization varies greatly, the dielectric constant is unstable with respect to temperature, and the slope of the D-F hysteresis curve is slow, resulting in nonlinearity. A dielectric element with good characteristics has not yet been put into practical use.
この点を改善するため、特開昭５７−１２８０１９号公
報では、ＢａＯ−ＴｉＯｇ−３ｎＯｇを主成分としたＢ
ａＴｔＯ，系多結晶体からなる非直線性誘電体素子が提
案されている。この組成をもつ非直線性誘電体素子は、
従来のＢａＴｉＯ３系多結晶体からなる非直線性誘電体
素子に比べ、Ｄ−Ｅヒステリシス曲線の傾斜が急峻で、
誘電率が高くしかも誘電体損失の小さい優れた特徴を有
するものである。In order to improve this point, Japanese Patent Application Laid-Open No. 57-128019 proposes a B
A nonlinear dielectric element made of aTtO, a polycrystalline material, has been proposed. A nonlinear dielectric element with this composition is
Compared to conventional nonlinear dielectric elements made of BaTiO3 polycrystalline material, the slope of the D-E hysteresis curve is steeper,
It has excellent characteristics of high dielectric constant and low dielectric loss.
ところが、ＢＢａｏ−Ｔｉ０ｚ−５ｎｏを主成分とした
ＢａＴｉ Ｏｓ系多結晶体からなる非直線性誘電体素子
は上記のように、従来のものに比べかなり特性が改善さ
れたものであるけれども、パルス発生装置に用いた場合
のパルス発生電圧が低く、しかもその温度特性、特に高
温領域（５０〜６０℃）におけるパルス発生特性が悪い
という問題点を有しているものである。この高温領域は
、始動器内蔵の高圧ナトリウムランプ等の高輝度放電灯
が再始動する場合の始動器付近の温度であり、この温度
領域におけるパルス発生特性の低下は大きな欠点となる
ものである。However, although the nonlinear dielectric element made of BaTiOs-based polycrystalline material containing BBao-Ti0z-5no as the main component has considerably improved characteristics compared to the conventional one, it is difficult to generate pulses. When used in a device, the pulse generation voltage is low and the temperature characteristics, especially the pulse generation characteristics in the high temperature range (50 to 60° C.), are poor. This high-temperature region is the temperature near the starter when a high-intensity discharge lamp such as a high-pressure sodium lamp with a built-in starter is restarted, and a decrease in pulse generation characteristics in this temperature region is a major drawback.
本発明は、上記提案された非直線性誘電体素子における
上記問題点を改善するためになされたもので、パルス発
生電圧を高め、特に高温側のパルス発生特性の改善され
た非直線性誘電体素子を提供することを目的とする。The present invention has been made in order to improve the above-mentioned problems in the non-linear dielectric element proposed above. The purpose is to provide an element.
〔問題点を解決するための手段及び作用〕上記問題点を
解決するため、本発明者等は、種々実験を重ね検討した
結果、ＢａＴｉ Ｏ２の結晶構造が正方晶系及び立方晶
系においては良好な非線形特性を示さないが、菱面体晶
系と斜方晶系においては良好な非線形特性を示すことを
見出した。[Means and effects for solving the problems] In order to solve the above problems, the inventors of the present invention have conducted various experiments and studied, and have found that the crystal structure of BaTiO2 is good in the tetragonal system and the cubic system. However, we found that rhombohedral and orthorhombic systems show good nonlinear characteristics.
一般に純粋なりａＴｉＯｓにおける温度に対する結晶構
造の変化は、第１図に示すように、キュリー点ＴＣＤ以
上では立方晶系、キュリー点Ｔｃ、と第２変態点Ｔ。と
の間では正方晶系、第２変態点Ｔ’ｃｔと第３変態点Ｔ
’ｃ３との間では斜方晶系、第３変態点Ｔｃ３以下では
菱面体晶系となることが知られている（岡崎清著「セラ
ミック誘電体工学Ｊ １９６９年９月１５日学献社発行
、第２１頁参照）、シたがって良好な非線形特性を示す
菱面体晶系及び斜方晶系領域は、第２変態点’ｒｃｉ以
下の温度領域である。In general, the crystal structure of pure aTiOs changes with temperature as shown in FIG. 1. Above the Curie point TCD, the crystal structure changes to a cubic system, the Curie point Tc, and the second transformation point T. between the tetragonal system, the second transformation point T'ct and the third transformation point T
'c3, it becomes an orthorhombic system, and below the third transformation point Tc3, it becomes a rhombohedral system (Kiyoshi Okazaki, Ceramic Dielectric Engineering J, September 15, 1969, published by Gakkensha). , p. 21), therefore, the rhombohedral and orthorhombic regions exhibiting good nonlinear properties are in the temperature region below the second transformation point 'rci.
高温側の非線形特性、すなわちパルス発生特性を改善す
るためには、できるだけ第２変態点Ｔｃｚを高温側にシ
フトする必要がある。第２図に示すように、ＢａＴｉ
Ｏ３におけるＴｉをＳｎ、 Ｚｒ、 Ｈｆで置換するこ
とにより、第２変態点ＴＣ！は高温側にシフトする（Ｂ
ｅｒｎａｒｄ Ｊａｆｆｅ他２名著” Ｐｉｅｚｏｅｌ
ｅｃｔｒｉｃＣｅｒａｍｉｃｓ″ Ａｃａｄｉｍｉｃ
Ｐｒｅｓｓ １９７１年発行、第９４頁参照〉、そして
この第２図から明らかなように、ＳｎよりもＺｒ、 ）
ＩｆでＴｉを置換することにより、第２変態点ＴＣｔは
より高温側ヘシフトし、したがって高温側のパルス発生
特性のより良好な改善効果が得られることがわかる。In order to improve the nonlinear characteristics on the high temperature side, that is, the pulse generation characteristics, it is necessary to shift the second transformation point Tcz to the high temperature side as much as possible. As shown in Figure 2, BaTi
By replacing Ti in O3 with Sn, Zr, and Hf, the second transformation point TC! shifts to the high temperature side (B
"Piezoel" by Ernard Jaffe and 2 others
etricCeramics'' Academic
Press, published in 1971, page 94>, and as is clear from this Figure 2, Zr is more active than Sn.
It can be seen that by replacing Ti with If, the second transformation point TCt is shifted to a higher temperature side, and therefore a better effect of improving the pulse generation characteristics on the high temperature side can be obtained.
そこで本発明においては、ＢａＯＴｉ０ｚ Ｚｒ０ｔ
−ＨｆＯ！の組み合わせで、ＢａＴｉ Ｏｓ系多結晶体
を形成し、非線形誘電体素子を構成するものである。Therefore, in the present invention, BaOTi0z Zr0t
-HfO! A BaTiOs-based polycrystal is formed by the combination of the above, and a nonlinear dielectric element is constructed.
そして特に、Ｔｉ０ｉを８５．２５〜９６．７５ｓｏ１
％、Ｚｒ０ｚを３〜９．７５ａｏ１％、Ｈｆ０１を０．
２５〜５ ＋ａｏ１％、ＢａＯと（ＴｉＯｔ＋Ｚｒ０ｇ
＋ＨｆＯ＊）とのｍｏｌ比を０．９８〜１．０２の範囲
とした基本組成の多結晶体からなり、ＭｎｔＣｒの酸化
物の１種又は１種以上を０．００４〜０．０４重量％含
有させて非直線性誘電体を構成するものである。これに
より、非直線性が改善されて相対的なパルス発生電圧が
高められ、特にその高温側のパルス発生特性が改善され
ると共に、磁器焼結に際して還元防止作用並びにその焼
結性が向上し、緻密で均質な優れた多結晶体からなる非
直線性誘電体素子が得られる。And in particular, Ti0i is 85.25-96.75so1
%, Zr0z 3-9.75ao1%, Hf01 0.
25~5 +ao1%, BaO and (TiOt+Zr0g
It consists of a polycrystalline body with a basic composition in which the molar ratio with +HfO*) is in the range of 0.98 to 1.02, and contains 0.004 to 0.04% by weight of one or more MntCr oxides. This constitutes a nonlinear dielectric. This improves nonlinearity and increases the relative pulse generation voltage, particularly improves the pulse generation characteristics on the high temperature side, and also improves the reduction prevention effect and sinterability during porcelain sintering. A nonlinear dielectric element made of dense, homogeneous, and excellent polycrystalline material can be obtained.
（実施例〕 以下実施例について説明する。(Example〕 Examples will be described below.
Ｏ第１実施例
原料粉末Ｔｉｅｓ ｔ Ｚｒ０ｇ 、 ｌＩｆｏｇを第
１表に示す組成比とし、原料粉末ＢａＯと（ＴｉＯ雪＋
Ｚｒ０ｔ＋Ｈｆ０ｔ）のｍｏｌ比を０．９８〜１．０２
の範囲とし、更に、ＭｎＯ＊を０．０１重量％＋ Ｃｒ
＊ ０３を０．０１５重量％添加してポリエチレンポッ
ト、メノーボールを用いて湿式混合した０次いで脱水乾
燥後、１１５０℃を保持して２時間仮焼成し、その後再
びポリエチレンポット、メノーボールを用いて粉砕を行
った０次いで、水分を蒸発させた後これに適当量のバイ
ンダーを加え、１０トンプレスで１８．５φ、 ０．７
５ｍの円板に加圧成型した０次いで、１３００〜１４０
０℃で２時間焼成して磁器素子を形成し、これに銀電極
を焼き付けて非直線性誘電体素子を作成した。なお第１
表において試料ｍ１． ２． ８．１１は、対比するた
め作成した本発明の範囲外の素子である。O First Example Raw material powders Ties t Zr0g and lIfog were made into composition ratios shown in Table 1, and raw material powders BaO and (TiO snow +
The molar ratio of Zr0t+Hf0t) is 0.98 to 1.02.
Furthermore, MnO* is in the range of 0.01% by weight + Cr
* 0.015% by weight of 03 was added and mixed wet using a polyethylene pot and an agate ball. After dehydration and drying, the mixture was pre-calcined at 1150°C for 2 hours, and then pulverized again using a polyethylene pot and an agate ball. Then, after evaporating the water, add an appropriate amount of binder to it and press it with a 10 ton press to make it 18.5φ and 0.7
Pressure molded into a 5m disc, then 1300~140
A ceramic element was formed by firing at 0° C. for 2 hours, and a silver electrode was baked onto this to create a nonlinear dielectric element. Note that the first
In the table, sample m1. 2. 8.11 is an element outside the scope of the present invention that was created for comparison.
このようにして得られた非直線性誘電体素子を、第３図
に示すパルス発生回路及びパルス測定回路を用いて、周
囲の温度を変えてパルス発生電圧を測定した結果、第４
図に示すような結果が得られた。なおパルス発生回路は
、第３図に示すように、上記構成の各非直線性誘電体素
子１と１２５Ｗ水銀灯用安定器２の直列回路を、２００
Ｖ、 ５０Ｈｚの交流電源３に接続して構成し、発生パ
ルス電圧を非直線性誘電体素子１の端子間に接続したオ
シロスコープ４により測定した。Using the pulse generation circuit and pulse measurement circuit shown in FIG. 3, the pulse generation voltage of the thus obtained nonlinear dielectric element was measured while changing the surrounding temperature.
The results shown in the figure were obtained. As shown in FIG. 3, the pulse generation circuit includes a series circuit of each nonlinear dielectric element 1 having the above configuration and a ballast 2 for a 125W mercury lamp.
V, 50 Hz, and the generated pulse voltage was measured with an oscilloscope 4 connected between the terminals of the nonlinear dielectric element 1.
第１表
上記第１表及び第４図かられかるように、本発明に係る
非直線性誘電体素子のパルス発生電圧は、−３０〜＋６
０℃に亘ッテ、６００−１１００Ｖという高い値を示し
ており、特に高圧ナトリウムランプ等の高輝度放電灯の
再始動温度である５０〜６０℃の高温領域において、６
００〜９００ Ｖと高い値を示している。Table 1 As can be seen from the above Table 1 and FIG. 4, the pulse generation voltage of the nonlinear dielectric element according to the present invention is -30 to +6
It shows a high value of 600-1100V over 0℃, especially in the high temperature range of 50-60℃, which is the restart temperature of high-intensity discharge lamps such as high-pressure sodium lamps.
It shows a high value of 00 to 900 V.
以上のデータから本発明はＢａ０−Ｔｉｅ、−ＺｒＯ。Based on the above data, the present invention is based on Ba0-Tie, -ZrO.
−ＨｆＯ＊の基本組成において、ＴｉＯｘを８５．２５
〜９６．７５ｍｏｌ％、Ｚｒ０ｚを３〜９．７５ｍｏｌ
％、 ［Ｏｔを０．２５〜５ ｍｏｌ％、ＢａＯと（
Ｔｉ Ｏｔ ＋ Ｚｒ Ｏｚ ＋ Ｈｆ Ｏ富）とのｍ
ｏｌ比を０．９８〜１．０２の範囲に限定するものであ
る。なお、第２表に示すように、ＢａＯと（ＴｉＯ１＋
Ｚｒ Ｏｚ ＋ ｌ（ｆ Ｏｔ）とのｓｏｌ比を０．９
８未満にすると結晶が尼大化し、且つ粒界が広くなって
非直線性が悪くなり、またそのｍｏｌ比が１．０２を越
えると結晶が小さくなりすぎて同様に非直線性が悪くな
ることが確かめられた。-In the basic composition of HfO*, TiOx is 85.25
~96.75 mol%, 3 to 9.75 mol of Zr0z
%, [0.25-5 mol% of Ot, BaO and (
m with Ti Ot + Zr Oz + Hf O wealth)
The ol ratio is limited to a range of 0.98 to 1.02. Furthermore, as shown in Table 2, BaO and (TiO1+
The sol ratio with Zr Oz + l (f Ot) is 0.9
If the molar ratio is less than 8, the crystals will become larger and the grain boundaries will become wider, resulting in poor nonlinearity, and if the molar ratio exceeds 1.02, the crystals will become too small, resulting in similarly poor nonlinearity. was confirmed.
第 ２ 表・
Ｏ第２実施例
上記第１実施例において最も高いパルス電圧を発生した
ｌ１ｋＬ６の試料と同一の基本組成（Ｔｉｏｌ ：９
２ｍｏｌ％＋ Ｚｒ０ｍ ： ５ｍｏｌ％＊
Ｈｆ０ｔ ： ３ｍｏｌ％） で、ＢａＯと（Ｔ
ｉ Ｏ＠ 十Ｚｒ Ｏｚ ＋ Ｉｆ Ｏｇ）との−ｏｌ
比を１とした組成物に、添加物としてＭｎ０ｇ＋ Ｃｒ
ａｂｓの１種又は２種を第３表に示すように添加して、
第１実施例と同様な工程で非直線性誘電体素子を作成し
た。そして、かくして得られた素子のパルス発生電圧を
第３図の測定回路を用いて測定したところ、第３表及び
第５図に示すような結果が得られた。Table 2 - Second Example The same basic composition as the l1kL6 sample that generated the highest pulse voltage in the first example (Tiol: 9).
2 mol% + Zr0m: 5 mol%*
Hf0t: 3 mol%), BaO and (T
-ol with i O@ 10Zr Oz + If Og)
In the composition with a ratio of 1, Mn0g + Cr was added as an additive.
Adding one or two types of abs as shown in Table 3,
A nonlinear dielectric element was created using the same steps as in the first example. When the pulse generation voltage of the device thus obtained was measured using the measuring circuit shown in FIG. 3, the results shown in Table 3 and FIG. 5 were obtained.
第３表
なお、第３表において試料１１１．１４．１５は本発明
の範囲外のものであり、比較のため例示した。Table 3 Note that samples 111.14.15 in Table 3 are outside the scope of the present invention and are exemplified for comparison.
また第５図において、ａはＭｎ０１の単独添加、ｂはＣ
ｒ１Ｏｓの単独添加、Ｃは双方を添加した場合の特性曲
線をそれぞれ示している。In addition, in Fig. 5, a indicates the addition of Mn01 alone, and b indicates the addition of C.
Characteristic curves are shown when r1Os is added alone, and when both are added.
第３表及び第５図かられかるように、添加物の添加量に
よって発生パルス電圧の値は大幅に変化するが、主成分
に対して０．００４〜０．０４重量％の範囲で、満足す
べきパルス発生電圧が発生しており、特に単独添加より
も両者をある割合（２： ３）で添加するのが最も良好
な特性を示している。そして上記範囲以外では試料１ｋ
ｌ、 １４．１５で示すようにパルス発生電圧が低下し
満足すべき特性が得られない、これは、これらの添加物
が粒界内に析出して絶縁抵抗を上げ、結果としてヒステ
リシス特性を角形にして非直線特性を改善しているもの
であるが、これらの添加物の添加量が多（なるとそれら
の添加物が結晶粒内に拡散し非直線特性を悪化させるか
らである。As can be seen from Table 3 and Figure 5, the value of the generated pulse voltage varies greatly depending on the amount of additive added, but it is satisfactory within the range of 0.004 to 0.04% by weight based on the main component. In particular, adding both in a certain ratio (2:3) shows the best characteristics than adding either one. And outside the above range, sample 1k
As shown in 14.15, the pulse generation voltage decreases and satisfactory characteristics cannot be obtained.This is because these additives precipitate within the grain boundaries and increase the insulation resistance, resulting in the hysteresis characteristics becoming square. However, if the amount of these additives added is large, the additives will diffuse into the crystal grains and deteriorate the nonlinear characteristics.
なお、このＭｎ０ｔ 、Ｃｒａｂｓの添加によって焼結
に際し、磁器の還元防止あるいは緻密焼結を促進するも
のである。またこれらの添加物を添加する時、本実施例
ではＭｎはＭｎ０ｇ 、 ＣｒはＣｒｇ Ｏ３として添
加したちの゛を示したが、これに限定されるものではな
く、他の化合物として添加しても同様の効果が得られる
ものである。The addition of Mn0t and Crabs prevents reduction of the porcelain or promotes dense sintering during sintering. In addition, when adding these additives, in this example, Mn was added as Mn0g and Cr was added as CrgO3, but the additives are not limited to this and may be added as other compounds. Similar effects can be obtained.
０第３実施例
通常の誘電体組成においては、上記各実施例で示したよ
うな添加物の他に、Ｓｔｏｗ ＋ Ａ１１０３等を焼結
促進剤として０．３〜１．０重量％添加することが多い
、これらの添加物は原料中に不純物として含有されてい
たり、また製造する際に工程中で混入される場合もあり
、これらは通常不純物として扱われるが、いずれにして
も通常の誘電体としては１．０重量％程度までは許容さ
れている。そこで本発明においてもこの不純物が、本件
非直線性誘電体素子のパルス発生特性にどのような影響
を与えるかについて、次のような実験を行った。すなわ
ち第１実施例において最も高いパルス電圧を発生した−
６の試料と同一の基本組成（ＴｉＯｇ ：９２ｍｏｌ
％、 Ｚｒ０１ ： ５ｍｏｌ％＋ ＨｆＯｘ
： ３ｍｏｌ％） で、ＢａＯと（Ｔｉ Ｏｚ
＋ Ｚｒ Ｏｚ ＋ Ｉｆ Ｏｚ）とのｍｏｌ比を１
とした組成物に添加物Ｍｎ０１を０．０１重量％とＣｒ
２Ｏ２を０．０１５重量％添加したものに、更に不純物
としてＮｂ＊（）ｓ＋ ＡｌｔＯｓ＋ Ｂ１Ｏｓ＋ Ｍ
ｇＯ，Ｓｔｏｗを添加量を変えて添加して作成し、パル
ス電圧を測定したところ、第６図に示すような結果が得
られた。0 Third Example In a normal dielectric composition, in addition to the additives shown in the above examples, 0.3 to 1.0% by weight of Stow + A1103 or the like is added as a sintering accelerator. These additives are often contained in raw materials as impurities, or may be mixed in during the manufacturing process, and are usually treated as impurities, but in any case, they cannot be used with normal dielectrics. However, up to about 1.0% by weight is permitted. Therefore, in the present invention, the following experiment was conducted to examine how these impurities affect the pulse generation characteristics of the present nonlinear dielectric element. That is, the highest pulse voltage was generated in the first embodiment.
Same basic composition as sample No. 6 (TiOg: 92 mol
%, Zr01: 5mol%+HfOx
: 3mol%), BaO and (TiOz
+ Zr Oz + If Oz), the molar ratio is 1
Additives Mn01 and Cr
Nb*()s+ AltOs+ B1Os+ M was added as an impurity to 0.015% by weight of 2O2.
When different amounts of gO and Stow were added and the pulse voltage was measured, the results shown in FIG. 6 were obtained.
この第６図かられかるように、不純物添加量とパルス発
生電圧との間には明瞭な相関が認められ、特に不純物添
加量が０．２重量％を越えるとパルス電圧は急激に低下
している。As can be seen from Fig. 6, there is a clear correlation between the amount of impurities added and the pulse generation voltage, and especially when the amount of impurities added exceeds 0.2% by weight, the pulse voltage decreases rapidly. There is.
この理由は、添加される不純物はＢａＯ−Ｔｉ１ｔ−Ｚ
ｒＯオーＨｆ０ｔ系固溶固溶体結晶界に析出し、固溶体
結晶に歪みを与え、素子の非直線性に悪影響を及ぼして
いるものと考えられ、したがってその粒界ができるだけ
発達しないように不純物の添加量を上記のように０．２
重量％以下に限定する必要がある。The reason for this is that the added impurity is BaO-Ti1t-Z
It is thought that it precipitates at the rO-Hf0t system solid solution crystal boundaries, distorts the solid solution crystal, and has an adverse effect on the nonlinearity of the device. 0.2 as above
It is necessary to limit the content to % by weight or less.
Ｏ第４実施例
この実施例は、第１実施例において最も高いパルス電圧
を発生した磁６の試料と同一の基本組成（Ｔｉ Ｏｚ
： ９２＋ｔｏ１％、 ＺｒＯｘ ： ５
ｍｏｌ％、 ＨｆＯｘ ？３ｍｏｌ％）で、Ｂａ
Ｏと（ＴｉＯ＊＋Ｚｒ０ｚ＋ＨＮ）ｔ）とのｍｏｌ比を
１とした組成物に添加物？ＩｎＯｘを０．０１重量％と
ＣｒｚＯｌを０．１５重量％添加したものに、更にＣａ
ｂ、ｐｂｏｌ ＳｒＯを１種又は２種以上を添加して非
直線性誘電体素子を形成するものである。そして上記Ｃ
ａ Ｏ、Ｐｂ Ｏ、Ｓｒ Ｏをそれぞれ添加量を変えて
添加して非直線性誘電体素子を作成し、パルス電圧を測
定したところ、第７図に示すような結果が得られた。な
おＣａｂ、ＰｂＯ，ＳｒＯの添加量は、ＢａＯに対する
ｍｏｌ％で表している。O Fourth Example This example has the same basic composition (TiOz
: 92+to1%, ZrOx: 5
mol%, HfOx? 3 mol%), Ba
An additive to a composition in which the molar ratio of O and (TiO*+Zr0z+HN)t) is 1? Ca was added to 0.01% by weight of InOx and 0.15% by weight of CrzOl.
b, pbol One or more types of SrO are added to form a nonlinear dielectric element. And the above C
When a nonlinear dielectric element was prepared by adding a O, Pb O, and Sr O in varying amounts, and the pulse voltage was measured, the results shown in FIG. 7 were obtained. Note that the amounts of Cab, PbO, and SrO added are expressed in mol% relative to BaO.
この第７図かられかるように、これらの添加量をＢａＯ
に対して０．１〜１．（１＋ｏ１％とした場合、パルス
発生電圧が大幅に向上していることがわかる。As can be seen from this Figure 7, the amounts of these additions are BaO
0.1 to 1. (It can be seen that when it is set to 1+o1%, the pulse generation voltage is significantly improved.
これは上記ＣａＯ等を添加することにより、キュリー点
（Ｔｃｐ）における比誘電率が高（なり、非直線特性が
改善されて、ヒステリシス特性の飽和電圧が低くなるた
めパルス発生電圧が高くなっているものと考えられる。This is because by adding the above-mentioned CaO, etc., the relative dielectric constant at the Curie point (Tcp) becomes high, the nonlinear characteristics are improved, and the saturation voltage of the hysteresis characteristic is lowered, so the pulse generation voltage is increased. considered to be a thing.
なお第７図に示したデータは、不純物添加量を零とした
場合のデータを示しているが、第３実施例に示したよう
にＮｂｇＯｓ等の不純物を０．２重量％以下添加したも
のに上記ＣａＯ等を添加した場合もほぼ同様な結果が得
られた。Note that the data shown in FIG. 7 shows data when the amount of impurities added is zero, but as shown in the third example, when impurities such as NbgOs are added in an amount of 0.2% by weight or less, Almost similar results were obtained when the above-mentioned CaO and the like were added.
以上実施例に基づいて説明したように、本発明によれば
、ＢａＴｉ Ｏ，系多結晶体において、ＢａＯ−ＴｉＣ
ｈ ＺｒＱｌ ＨｆＯ□を主成分としてそれらの混
合比を特定値にした基本組成物で非直線性誘電体素子を
構成したので、高温領域における非直線性を改善し、パ
ルス発生特性を向上させることができる。As described above based on the embodiments, according to the present invention, in the BaTiO, polycrystalline body, BaO-TiC
Since the nonlinear dielectric element was constructed with a basic composition containing h ZrQl HfO□ as its main component and a specific mixing ratio thereof, it was possible to improve nonlinearity in the high temperature region and improve pulse generation characteristics. can.
第１図は、ＢａＴｉＯｓ磁器の温度に対する比誘電率ｍ
ｓと結晶構造の変化を示す図、第２図は、ＢａＴｉ Ｏ
ｓ磁器における置換元素による変態点の変動を示す図、
第３図は、パルス発生回路とパルス測定回路を示す図、
第４図は、組成比を変えた各試料の周囲温度に対する発
生パルス電圧の変動を示す図、第５図は、添加物の添加
量に対するパルス電圧の変動を示す図、第６図は、不純
物の添加量に対するパルス電圧の変動を示す図、第７図
は、他の添加物の添加量に対するパルス発生電圧の変動
を示す図、第８図は、ＢａＴｉ Ｏ３単結晶体のＤ−Ｅ
ヒステリシス曲線図、第９図は、従来のＢａＴｉＯｓ多
結晶体のＤ−Ｅヒステリシス曲線図である。Figure 1 shows the relative permittivity m of BaTiOs porcelain versus temperature.
Figure 2 shows changes in crystal structure and BaTiO
s A diagram showing the variation of the transformation point depending on the substitution element in porcelain,
FIG. 3 is a diagram showing a pulse generation circuit and a pulse measurement circuit;
Figure 4 is a diagram showing the fluctuation of the generated pulse voltage with respect to the ambient temperature of each sample with different composition ratio, Figure 5 is a diagram showing the fluctuation of the pulse voltage with respect to the amount of additive added, and Figure 6 is a diagram showing the fluctuation of the pulse voltage with respect to the amount of additive added. FIG. 7 is a diagram showing fluctuations in pulse voltage with respect to the amount of other additives added. FIG. 8 is a diagram showing variations in pulse generation voltage with respect to the amount of other additives added.
Hysteresis Curve Diagram FIG. 9 is a DE hysteresis curve diagram of a conventional BaTiOs polycrystal.
Claims (3)
主成分とし、ＴｉＯ＿２，を８５．２５〜９６．７５ｍ
ｏｌ％、ＺｒＯ＿２を３〜９．７５ｍｏｌ％，ＨｆＯ＿
２を０．２５〜５ｍｏｌ％，ＢａＯと（ＴｉＯ＿２＋Ｚ
ｒＯ＿２＋ＨｆＯ＿２）とのｍｏｌ比を０．９８〜１．
０２の範囲とした基本組成の多結晶体からなり、Ｍｎ，
Ｃｒの酸化物の１種又は１種以上を０．００４〜０．０
４重量％含有させたことを特徴とする非直線性誘電体素
子。(1) BaO-TiO_2-ZrO_2-HfO_2 as the main component, TiO_2, 85.25-96.75m
ol%, ZrO_2 3 to 9.75 mol%, HfO_
0.25 to 5 mol% of 2, BaO and (TiO_2+Z
rO_2+HfO_2) at a molar ratio of 0.98 to 1.
It consists of a polycrystalline body with a basic composition in the range of 02, Mn,
0.004 to 0.0 of one or more Cr oxides
A non-linear dielectric element characterized by containing 4% by weight.
％以下としたことを特徴とする特許請求の範囲第１項記
載の非直線性誘電体素子。(2) The nonlinear dielectric element according to claim 1, characterized in that the content of elements serving as impurities is 0.2% by weight or less as an oxide.
ＢａＯに対して０．１〜１．０ｍｏｌ％を添加したこと
を特徴とする特許請求の範囲第１項又は第２項記載の非
直線性誘電体素子。(3) Claim 1 or 2, characterized in that 0.1 to 1.0 mol% of one or more oxides of Ca, Pb, and Sr is added to BaO. The nonlinear dielectric element described above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62294158A JPH01136323A (en) | 1987-11-24 | 1987-11-24 | Nonlinear dielectric element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62294158A JPH01136323A (en) | 1987-11-24 | 1987-11-24 | Nonlinear dielectric element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01136323A true JPH01136323A (en) | 1989-05-29 |
| JPH0440853B2 JPH0440853B2 (en) | 1992-07-06 |
Family
ID=17804062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62294158A Granted JPH01136323A (en) | 1987-11-24 | 1987-11-24 | Nonlinear dielectric element |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01136323A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000191371A (en) * | 1998-12-25 | 2000-07-11 | Murata Mfg Co Ltd | Nonlinear dielectric porcelain, capacitor for pulse generation, high pressure vapor discharge lamp circuit and high pressure vapor discharge lamp |
| US6356037B1 (en) | 1998-04-08 | 2002-03-12 | Murata Manufacturing Co., Ltd. | Dielectric ceramic and a capacitor using the same |
| CN103408298A (en) * | 2013-08-05 | 2013-11-27 | 无锡鑫圣慧龙纳米陶瓷技术有限公司 | Microwave dielectric ceramic material applicable to low temperature sintering and preparation method of microwave dielectric ceramic material |
-
1987
- 1987-11-24 JP JP62294158A patent/JPH01136323A/en active Granted
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6356037B1 (en) | 1998-04-08 | 2002-03-12 | Murata Manufacturing Co., Ltd. | Dielectric ceramic and a capacitor using the same |
| JP2000191371A (en) * | 1998-12-25 | 2000-07-11 | Murata Mfg Co Ltd | Nonlinear dielectric porcelain, capacitor for pulse generation, high pressure vapor discharge lamp circuit and high pressure vapor discharge lamp |
| EP1013625A3 (en) * | 1998-12-25 | 2000-09-27 | Murata Manufacturing Co., Ltd. | Nonlinear dielectric ceramic, pulse generating capacitor, high-pressure vapor discharge lamp circuit, and high-pressure vapor discharge lamp |
| CN103408298A (en) * | 2013-08-05 | 2013-11-27 | 无锡鑫圣慧龙纳米陶瓷技术有限公司 | Microwave dielectric ceramic material applicable to low temperature sintering and preparation method of microwave dielectric ceramic material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0440853B2 (en) | 1992-07-06 |
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