JPH038082B2 - - Google Patents
Info
- Publication number
- JPH038082B2 JPH038082B2 JP56203914A JP20391481A JPH038082B2 JP H038082 B2 JPH038082 B2 JP H038082B2 JP 56203914 A JP56203914 A JP 56203914A JP 20391481 A JP20391481 A JP 20391481A JP H038082 B2 JPH038082 B2 JP H038082B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- manganese
- cobalt
- atomic
- thermistor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- Magnetic Ceramics (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
Description
【発明の詳細な説明】
本発明は、汎用サーミスタの主な材料成分系で
あるマンガン、コバルト、銅３成分系のうちで、
銅の含有率が比較的低いサーミスタを銅の含有率
を容易に変化させ、特性範囲の広いサーミスタを
供給することを特徴とした負の温度係数を有する
サーミスタ用酸化物半導体の製造方法に関するも
のである。DETAILED DESCRIPTION OF THE INVENTION The present invention focuses on manganese, cobalt, and copper, which are the main material components of general-purpose thermistors.
This invention relates to a method for manufacturing an oxide semiconductor for a thermistor having a negative temperature coefficient, which is characterized by easily changing the copper content of a thermistor with a relatively low copper content and supplying a thermistor with a wide range of characteristics. be.
従来、負の抵抗温度係数を有する市販の汎用サ
ーミスタの製造方法は、他のセラミツクスの製造
工程と同様に目的組成の酸化物を配合し、これを
湿気混合、仮焼、湿式粉砕、造粒、成形、焼成と
いう工程を経るのが一般的である。 Conventionally, the manufacturing method for commercially available general-purpose thermistors with a negative temperature coefficient of resistance involves blending an oxide with the desired composition, as in other ceramic manufacturing processes, and then mixing it with moisture, calcination, wet pulverization, granulation, and so on. It is common to go through the steps of molding and firing.
また、酸化マンガン、酸化コバルト、酸化銅の
３成分からなるサーミスタ用酸化物半導体組成
は、上述したように既に広く知られ用いられてい
る（〔株〕日立製作所、中央研究所創立二十周年
記念文集、P30〜46、昭和37年）。 In addition, the oxide semiconductor composition for thermistors, which consists of the three components of manganese oxide, cobalt oxide, and copper oxide, is already widely known and used as mentioned above (Hitachi, Ltd., 20th Anniversary of the Central Research Laboratory) Anthology, pages 30-46, 1962).
本発明は、このマンガン、コバルト、銅３成分
系のうち、比較的銅含有率が少ない組成範囲の製
造方法に係り、マンガン−コバルトの２成分系の
仮焼物を、銅−有機酸錯塩溶液中で湿式粉砕する
ことにより銅を添加して目的サーミスタを得るこ
とを特徴とする。 The present invention relates to a method for manufacturing a composition range with a relatively low copper content among this three-component system of manganese, cobalt, and copper, in which a calcined product of a two-component system of manganese-cobalt is placed in a copper-organic acid complex salt solution. It is characterized by adding copper by wet grinding to obtain the desired thermistor.
以下、実施例を挙げて本発明を詳細に説明す
る。市販の原料MnCO3、CO3O4をそれぞれ金属
元素50原子％に配合し、これをボールミルで20時
間混合し、このスラリーを乾燥後800℃で仮焼す
る。この仮焼物を銅−エチレンジアミン四酢酸
（以下EDTAと略称する）溶液を用いてボールミ
ルで湿式粉砕する。その後、スラリーを過、乾
燥後、造粒、成形工程を経て、1250℃で２時間空
気中で焼成した。ここで、銅−EDTA溶液の濃
度、PHあるいは粉砕時間を変えることにより、銅
含有率を容易に調整できる。例えば、10M銅−
EDTA溶液を用いて16時間粉砕したものの最終
組成比は、Mn：Co：Cu＝44.7＝44.5＝9.8原子
％、5M銅−EDTA溶液を用いたものは、Mn：
Co：Cu＝47.2：48.0：4.8原子％であつた。従来
のように配合時に組成が決定されている場合に
は、多様な特性範囲をカバーするのは機能的でな
い。すなわち、一特性一組成比と限定される。と
ころが本発明の製造方法を用いれば、基本とする
Mn−Coの仮焼物を多量に準備しておけば、素子
特性の要望に対して容易に広範囲の特性に対処で
きる点で産業上の効果が大きい。これは特性に与
える影響度が銅が最も大きいことにもよる。 Hereinafter, the present invention will be explained in detail with reference to Examples. Commercially available raw materials MnCO 3 and CO 3 O 4 are each mixed at 50 atomic % of metal elements, mixed in a ball mill for 20 hours, and the slurry is dried and calcined at 800°C. This calcined product is wet-pulverized in a ball mill using a copper-ethylenediaminetetraacetic acid (hereinafter abbreviated as EDTA) solution. Thereafter, the slurry was filtered, dried, granulated, molded, and fired in air at 1250°C for 2 hours. Here, the copper content can be easily adjusted by changing the concentration, pH, or grinding time of the copper-EDTA solution. For example, 10M copper
The final composition ratio of the product milled for 16 hours using an EDTA solution is Mn:Co:Cu = 44.7 = 44.5 = 9.8 at%, and the final composition ratio of the product using a 5M copper-EDTA solution is Mn:
Co:Cu=47.2:48.0:4.8 atomic%. If the composition is determined at the time of formulation as in the past, it is not functional to cover a wide range of properties. In other words, it is limited to one property and one composition ratio. However, if the manufacturing method of the present invention is used, the basic
Preparing a large amount of calcined Mn-Co has a great industrial effect in that it can easily meet a wide range of device characteristics requirements. This is also because copper has the greatest influence on properties.
また、請求の範囲の中で限定したサーミスタの
組成の限定理由は、既に市販されている汎用サー
ミスタの特性値（比抵抗10Ω・cm〜1MΩ・cm、
Ｂ定数1000〓〜6000〓）および溶解度からくるも
のである。さらに、銅−有機酸錯塩溶液に限定す
るのは、また金属と有機酸錯塩に限定するのは、
金属と有機酸との錯形成能力が大きく容易に置換
反応をおこすこと、溶液PHが無機塩のように強酸
性でなく仮焼物を溶解せず中性での溶度が大きい
こと、さらに焼成段階で有機酸はNO2およびCO2
として分解する利点をもつことによる。 In addition, the reason for limiting the composition of the thermistor in the scope of claims is the characteristic values of general-purpose thermistors already on the market (specific resistance 10Ω・cm ~ 1MΩ・cm,
This is due to the B constant (1000~6000) and solubility. Furthermore, it is limited to copper-organic acid complex salt solution, and it is limited to metal and organic acid complex salt solution.
The ability to form complexes between metals and organic acids is large enough to easily cause substitution reactions, the pH of the solution is not strongly acidic like inorganic salts, does not dissolve the calcined product, and has high solubility at neutral temperatures, and the firing stage The organic acids are NO 2 and CO 2
This is because it has the advantage of being decomposed as
以上のように本発明は構成されているものであ
り、非常に簡単な方法でもつて容易に広範囲の特
性に応用できるサーミスタ用酸化物半導体を得る
ことができ、その産業性は大なるものである。 The present invention is constructed as described above, and it is possible to obtain an oxide semiconductor for a thermistor that can be easily applied to a wide range of characteristics by a very simple method, and its industrial efficiency is great. .
Claims (1)
るスラリーを乾燥後、所定の温度で仮焼した後、
この仮焼物を銅−有機酸錯塩溶液中で湿式粉砕
し、さらに乾燥、造粒、成形、焼成させて銅を添
加し、金属元素としてマンガン94.8〜５原子％、
コバルト５〜94.8原子％、銅0.01〜10原子％の３
種を合計100原子％含有することを特徴とするサ
ーミスタ用酸化物半導体の製造方法。1 After drying a slurry consisting of a mixture of two components of manganese and cobalt, and calcining it at a predetermined temperature,
This calcined product is wet-pulverized in a copper-organic acid complex solution, further dried, granulated, molded, and fired to add copper, manganese as a metal element, 94.8 to 5 at.%,
Cobalt 5-94.8 atomic%, copper 0.01-10 atomic% 3
A method for producing an oxide semiconductor for a thermistor, characterized by containing a total of 100 atomic percent of seeds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56203914A JPS58105502A (en) | 1981-12-17 | 1981-12-17 | Manufacturing method of oxide semiconductor for thermistor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56203914A JPS58105502A (en) | 1981-12-17 | 1981-12-17 | Manufacturing method of oxide semiconductor for thermistor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58105502A JPS58105502A (en) | 1983-06-23 |
| JPH038082B2 true JPH038082B2 (en) | 1991-02-05 |
Family
ID=16481780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56203914A Granted JPS58105502A (en) | 1981-12-17 | 1981-12-17 | Manufacturing method of oxide semiconductor for thermistor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58105502A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2658581B2 (en) * | 1990-12-28 | 1997-09-30 | 三菱マテリアル株式会社 | Oxide semiconductor composition |
-
1981
- 1981-12-17 JP JP56203914A patent/JPS58105502A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58105502A (en) | 1983-06-23 |
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