JPH0521209A - Composition for thermistor - Google Patents
Composition for thermistorInfo
- Publication number
- JPH0521209A JPH0521209A JP3168436A JP16843691A JPH0521209A JP H0521209 A JPH0521209 A JP H0521209A JP 3168436 A JP3168436 A JP 3168436A JP 16843691 A JP16843691 A JP 16843691A JP H0521209 A JPH0521209 A JP H0521209A
- Authority
- JP
- Japan
- Prior art keywords
- thermistor
- oxides
- oxide
- composition
- niobium
- 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
Landscapes
- Thermistors And Varistors (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、温度測定用サーミス
タ、温度補償用サーミスタ、ラッシュ電流防止用サーミ
スタ等に用いるサーミスタ用組成物に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermistor composition used for temperature measuring thermistors, temperature compensating thermistors, rush current preventing thermistors and the like.
【０００２】[0002]
【従来の技術】従来、この種のサーミスタ用組成物とし
て、マンガン、コバルト、ニッケル、鉄、銅等の遷移金
属の酸化物のうち２種以上を選択し、所定の配合比で混
合した原料を９００〜１４００℃で焼成して得られた複
合酸化物セラミックスが知られている。また、この種の
サーミスタ組成物においては、比抵抗の低いサーミスタ
用組成物が要望されており、特に、マンガン（Ｍｎ）に
対して原子価制御を目的に銅（Ｃｕ）を添加することに
より低抵抗化したＭｎ−Ｃｕ系酸化物を主成分とするも
の、例えばＭｎ−Ｃｏ−Ｃｕ系酸化物、Ｍｎ−Ｎｉ−Ｃ
ｕ系酸化物、Ｍｎ−Ｃｏ−Ｎｉ−Ｃｕ系酸化物が多く使
用されている。2. Description of the Related Art Conventionally, as a composition for a thermistor of this kind, two or more kinds of oxides of transition metals such as manganese, cobalt, nickel, iron and copper are selected and mixed at a predetermined mixing ratio. A composite oxide ceramic obtained by firing at 900 to 1400 ° C. is known. Further, in this type of thermistor composition, a thermistor composition having a low specific resistance is desired, and in particular, by adding copper (Cu) to manganese (Mn) for the purpose of controlling valence, Those whose main component is a resistance-enhanced Mn-Cu-based oxide, for example, Mn-Co-Cu-based oxide, Mn-Ni-C
U-based oxides and Mn-Co-Ni-Cu-based oxides are often used.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記の
ような酸化銅を含む複合酸化物セラミックスは、（複合
酸化物中の酸化銅の添加量が多くなると）抵抗値の経時
変化、即ち抵抗変化率が大きくなるという問題点を有す
る。この原因を解明するために様々な研究がなされ、そ
の原因として、複合酸化物セラミックス素子内の金属元
素が雰囲気中の温度または酸素分圧に依存しながら不安
定に価数を変えることが挙げられている。この中で特に
Ｃｕは還元されやすく、サーミスタの経時変化に最も影
響を与えていると推定されている。本発明は、かかる問
題点を解消したサーミスタ用組成物を提供することを目
的とする。However, the complex oxide ceramics containing copper oxide as described above has a change in resistance value over time (ie, an increase in the amount of copper oxide added to the complex oxide), that is, the rate of change in resistance. Has a problem that it becomes large. Various studies have been conducted to elucidate the cause of this, and one of the causes is that the valence of the metal element in the complex oxide ceramics element is unstable and changes depending on the temperature or oxygen partial pressure in the atmosphere. ing. Of these, Cu is particularly easily reduced, and it is presumed that Cu has the greatest influence on the change over time of the thermistor. An object of the present invention is to provide a composition for a thermistor that solves such a problem.
【０００４】[0004]
【課題を解決するための手段】本発明のサーミスタ用組
成物は、マンガン、ニッケルおよび銅のそれぞれの元素
の酸化物からなる主成分に、ニオブ、タンタル及びタン
グステンのそれぞれの元素の酸化物のうちの少なくとも
１種をその元素に換算して、前記主成分の元素に対して
０．０５〜５０モル％添加したことを特徴とする。上記
ニオブ、タンタル及びタングステンのそれぞれの元素の
酸化物のうちの少なくとも１種の添加割合を前記範囲内
としたのは、該範囲を外れると温度１２５℃における抵
抗変化率が小さくならないからである。The composition for a thermistor of the present invention comprises, as a main component consisting of oxides of elements of manganese, nickel and copper, among oxides of elements of niobium, tantalum and tungsten. At least one of the above is converted to the element, and 0.05 to 50 mol% is added to the element of the main component. The addition ratio of at least one of the oxides of the respective elements of niobium, tantalum, and tungsten is set within the above range because the rate of change in resistance at a temperature of 125 ° C. does not become small outside this range.
【０００５】[0005]
【作用】ニオブ、タンタル及びタングステンのそれぞれ
の元素の酸化物のうちの少なくとも１種を添加すること
により、Ｍｎ−Ｎｉ−Ｃｕ系複合酸化物中の特にＣｕの
還元を抑制し、経時変化が少ないサーミスタを作成す
る。By adding at least one of the oxides of the elements of niobium, tantalum and tungsten, the reduction of Cu in the Mn-Ni-Cu composite oxide is suppressed and the change with time is small. Create a thermistor.
【０００６】[0006]
【実施例】次に、本発明の具体的な実施例を比較例と共
に説明する。先ず原料として、純度９９．９％以上の酸
化マンガン（Ｍｎ3Ｏ4）、酸化ニッケル（ＮｉＯ）及び
酸化銅（ＣｕＯ）、五酸化ニオブ（Ｎｂ2Ｏ5）、五酸化
タンタル（Ｔａ2Ｏ5）、三酸化タングステン（ＷＯ3）
をそれぞれ用意した。試料の作成にあたって、各原料を
表１に示す組成比（組成比：各酸化物中の元素のモル数
とした）となるように秤量した。次に、これらをウレタ
ンボールを玉石としたボールミルによって１５時間湿式
混合した。この混合物を磁製ルツボ中で温度９００℃で
２時間仮焼した後、再度、前記ボールミルにより湿式粉
砕し、粉砕後の粉末にバインダーとしてポリビニルアル
コールを加えて混合造粒し、これを乾式成型プレスを用
いて直径６mm、厚さ１mmの円板状に成型した。得られた
成形体をアルミナセッター上で、温度９５０〜１０５０
℃で２時間の焼成を施し、サーミスタ磁器を作成した。
作成されたサーミスタ磁器の表裏面にＡｇ−Ｐｄ電極材
料ペーストを塗布した後、温度８５０℃で焼き付けて電
極を形成し、該電極上に共晶半田にてリード線付けを行
なった。EXAMPLES Next, specific examples of the present invention will be described together with comparative examples. First, as raw materials, manganese oxide (Mn 3 O 4 ) having a purity of 99.9% or more, nickel oxide (NiO) and copper oxide (CuO), niobium pentoxide (Nb 2 O 5 ), tantalum pentoxide (Ta 2 O 5) are used. ), Tungsten trioxide (WO 3 )
Prepared respectively. In preparing the sample, each raw material was weighed so as to have the composition ratio shown in Table 1 (composition ratio: mol number of element in each oxide). Next, these were wet-mixed for 15 hours by a ball mill using urethane balls as cobblestones. This mixture was calcined in a porcelain crucible at a temperature of 900 ° C. for 2 hours, then again wet-milled by the ball mill, polyvinyl alcohol was added to the pulverized powder as a binder to carry out granulation, and this was dry-molded and pressed. Was used to form a disc having a diameter of 6 mm and a thickness of 1 mm. The obtained molded body was placed on an alumina setter at a temperature of 950 to 1050.
The thermistor porcelain was prepared by firing at 2 ° C. for 2 hours.
After the Ag-Pd electrode material paste was applied to the front and back surfaces of the prepared thermistor porcelain, it was baked at a temperature of 850 ° C. to form an electrode, and a lead wire was attached on the electrode with eutectic solder.
【０００７】こうして作成された表裏面に電極を備えた
各サーミスタ素子の夫々について、温度２５℃における
抵抗値（Ｒ25）と、温度８５℃における抵抗値（Ｒ85）
を測定し、測定値から比抵抗、サーミスタ定数Ｂ、抵抗
変化率（経時特性）を求めたところ、表１に示すような
結果が得られた。尚、比抵抗は温度２５℃における抵抗
値（Ｒ25）と焼結体の形状（直径、厚み）により求め
た。また、サーミスタ定数Ｂは温度２５℃における抵抗
値（Ｒ25）と、温度８５℃における抵抗値（Ｒ85）から
次式により求めた。 また、抵抗変化率（経時特性）は、温度２５℃で抵抗
値（Ｒ25Ａ）を測定した試料を温度１２５℃に維持した
恒温槽中に１０００時間放置した後、該試料の抵抗値
（Ｒ25Ｂ）を温度２５℃で再度測定し、放置前後の抵抗
値の変化率を次式により求めた。 With respect to each of the thermistor elements having electrodes on the front and back surfaces thus created, the resistance value at a temperature of 25 ° C. (R 25 ) and the resistance value at a temperature of 85 ° C. (R 85 )
Was measured, and the specific resistance, thermistor constant B, and resistance change rate (time-dependent characteristics) were determined from the measured values, and the results shown in Table 1 were obtained. The specific resistance was determined from the resistance value (R 25 ) at a temperature of 25 ° C. and the shape (diameter, thickness) of the sintered body. Further, the thermistor constant B was obtained from the resistance value at a temperature of 25 ° C. (R 25 ) and the resistance value at a temperature of 85 ° C. (R 85 ) by the following formula. The rate of change in resistance (temporal characteristics) was measured by measuring the resistance value (R 25 A) at a temperature of 25 ° C. for 1000 hours in a constant temperature bath maintained at a temperature of 125 ° C., and then measuring the resistance value (R 25 B) was measured again at a temperature of 25 ° C., and the rate of change in resistance value before and after standing was determined by the following formula.
【０００８】[0008]
【表１−１】 [Table 1-1]
【０００９】[0009]
【表１−２】 [Table 1-2]
【００１０】尚、表中で※印を付したものは本発明の範
囲外のものであり、その他は本発明の範囲内のものであ
る。表１（表１−１および表１−２）より明らかなよう
に、マンガン、ニッケル、および銅の各酸化物から成る
主成分に添加するニオブ、タンタルおよびタングステン
の各酸化物のうち少なくとも１種の組成割合が本発明の
範囲内として実施例は、比抵抗が１００Ω・cm以下であ
り、かつ抵抗変化率が５％以下と低いのに対してマンガ
ン、ニッケルおよび銅の各酸化物から成る主成分に添加
するニオブ、タンタルおよびタングステンの各酸化物の
うち少なくとも１種の組成割合が本発明の範囲外の比較
例（表中の※）は比抵抗が１００Ω・cm以上と高く、か
つ抵抗変化率が５％以上と大きく、或いは比抵抗が１０
０Ω・cm以下と低いのにもかかわらず抵抗変化率が５％
以上と大きかった。尚、マンガン、ニッケルおよび銅の
各酸化物から成る主成分に添加するニオブ、タンタルお
よびタングステンの各酸化物のうち少なくとも１種の組
成割合が本発明の範囲内とした実施例のサーミスタ定数
はサーミスタ用組成物としての実用性に適した値であっ
た。Those marked with * in the table are outside the scope of the present invention, and others are within the scope of the present invention. As is clear from Table 1 (Table 1-1 and Table 1-2), at least one of niobium, tantalum, and tungsten oxides added to the main component composed of manganese, nickel, and copper oxides. In the examples, the composition ratio of which is within the range of the present invention, the specific resistance is 100 Ω · cm or less, and the rate of resistance change is as low as 5% or less, while the main components are manganese, nickel and copper oxides. Comparative examples (* in the table) in which the composition ratio of at least one of the oxides of niobium, tantalum, and tungsten added to the components are outside the scope of the present invention have a high specific resistance of 100 Ω · cm or more and a resistance change. The ratio is as large as 5% or more, or the specific resistance is 10
Resistance change rate is 5% despite being as low as 0 Ω · cm or less
It was big as above. Incidentally, the thermistor constants of the examples in which the composition ratio of at least one of the oxides of niobium, tantalum and tungsten added to the main component composed of oxides of manganese, nickel and copper are within the scope of the present invention are thermistor constants. The value was suitable for practical use as a composition for use.
【００１１】前記実施例ではマンガンの酸化物として酸
化マンガン（Ｍｎ3Ｏ4）、ニッケルの酸化物として酸化
ニッケル（ＮｉＯ）、銅の酸化物として酸化銅（Ｃｕ
Ｏ）を用い、またニオブの酸化物として五酸化ニオブ
（Ｎｂ2Ｏ5）、タンタルの酸化物として五酸化タンタル
（Ｔａ2Ｏ5）、タングステンの酸化物として三酸化タン
グステン（ＷＯ3）を用いたが、本発明はこれに限定さ
れるものではなく、マンガンの酸化物の場合を１例にす
れば二酸化マンガン（ＭｎＯ2）を用いるようにしても
よい。In the above embodiment, manganese oxide (Mn 3 O 4 ) is used as manganese oxide, nickel oxide (NiO) is used as nickel oxide, and copper oxide (Cu) is used as copper oxide.
O), niobium pentoxide (Nb 2 O 5 ) as niobium oxide, tantalum pentoxide (Ta 2 O 5 ) as tantalum oxide, and tungsten trioxide (WO 3 ) as tungsten oxide. However, the present invention is not limited to this, and manganese dioxide (MnO 2 ) may be used if the case of an oxide of manganese is taken as an example.
【００１２】[0012]
【発明の効果】このように本発明によれば、比抵抗が１
００Ω・cmより低く、かつ１２５℃における抵抗変化率
が５％以下と低く、経時特性に優れたサーミスタ組成物
を提供することができるという効果を有する。As described above, according to the present invention, the specific resistance is 1 or less.
It has an effect that it is possible to provide a thermistor composition which has a resistance change rate at 125 ° C. of less than 5 Ω · cm and is as low as 5% or less, and which is excellent in aging characteristics.
Claims (1)
の元素の酸化物からなる主成分に、ニオブ、タンタル及
びタングステンのそれぞれの元素の酸化物のうちの少な
くとも１種をその元素に換算して、前記主成分の元素に
対して０．０５〜５０モル％添加したことを特徴とする
サーミスタ用組成物。Claim: What is claimed is: 1. A main component consisting of oxides of manganese, nickel and copper, and at least one of oxides of niobium, tantalum and tungsten. The composition for a thermistor, which is added in an amount of 0.05 to 50 mol% based on the element of the main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3168436A JP2572312B2 (en) | 1991-07-09 | 1991-07-09 | Composition for thermistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3168436A JP2572312B2 (en) | 1991-07-09 | 1991-07-09 | Composition for thermistor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0521209A true JPH0521209A (en) | 1993-01-29 |
| JP2572312B2 JP2572312B2 (en) | 1997-01-16 |
Family
ID=15868084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3168436A Expired - Lifetime JP2572312B2 (en) | 1991-07-09 | 1991-07-09 | Composition for thermistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2572312B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6861622B2 (en) | 2002-07-25 | 2005-03-01 | Murata Manufacturing Co., Ltd. | Negative temperature coefficient thermistor and method for manufacturing the same |
| US9058913B2 (en) | 2010-06-24 | 2015-06-16 | Epcos Ag | Cobalt-free NTC ceramic and method for producing a cobalt-free NTC ceramic |
| CN114751724A (en) * | 2022-05-31 | 2022-07-15 | 汕头市瑞升电子有限公司 | NTC thermistor medium material and preparation method thereof |
-
1991
- 1991-07-09 JP JP3168436A patent/JP2572312B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6861622B2 (en) | 2002-07-25 | 2005-03-01 | Murata Manufacturing Co., Ltd. | Negative temperature coefficient thermistor and method for manufacturing the same |
| US9058913B2 (en) | 2010-06-24 | 2015-06-16 | Epcos Ag | Cobalt-free NTC ceramic and method for producing a cobalt-free NTC ceramic |
| CN114751724A (en) * | 2022-05-31 | 2022-07-15 | 汕头市瑞升电子有限公司 | NTC thermistor medium material and preparation method thereof |
| CN114751724B (en) * | 2022-05-31 | 2023-04-14 | 汕头市瑞升电子有限公司 | NTC thermosensitive resistor medium material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2572312B2 (en) | 1997-01-16 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19960709 |