JP3362644B2 - Thermistor element, method of manufacturing the same, and temperature sensor using thermistor element - Google Patents
Thermistor element, method of manufacturing the same, and temperature sensor using thermistor elementInfo
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- JP3362644B2 JP3362644B2 JP26847197A JP26847197A JP3362644B2 JP 3362644 B2 JP3362644 B2 JP 3362644B2 JP 26847197 A JP26847197 A JP 26847197A JP 26847197 A JP26847197 A JP 26847197A JP 3362644 B2 JP3362644 B2 JP 3362644B2
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- thermistor element
- temperature
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は、高温領域で使用さ
れ、負の温度係数を有するサーミスタ素子とその製造方
法及びそのサーミスタ素子を用いた温度センサに関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermistor element used in a high temperature range and having a negative temperature coefficient, a method for manufacturing the thermistor element, and a temperature sensor using the thermistor element.
【０００２】[0002]
【従来の技術】近年、環境問題や燃費向上等の要求によ
り、排気ガス対策用触媒が用いられているが、その触媒
性能を充分に発揮させるためには、触媒の温度を正確に
測定する必要がある。そのためには、サーミスタ素子の
サーミスタ定数Ｂが大きい方が望ましい。2. Description of the Related Art In recent years, catalysts for exhaust gas countermeasures have been used due to environmental problems and demands for improvement of fuel consumption. However, in order to exert the catalytic performance sufficiently, it is necessary to measure the temperature of the catalyst accurately. There is. For that purpose, it is desirable that the thermistor constant B of the thermistor element is large.
【０００３】従来、最高使用温度７００℃を超える高温
用サーミスタとしては、（Ａｌ，Ｃｒ，Ｆｅ）2Ｏ3系に
代表されるコランダム型のサーミスタ材料が用いられて
いた。Conventionally, as a high temperature thermistor whose maximum operating temperature exceeds 700 ° C., a corundum type thermistor material typified by (Al, Cr, Fe) 2 O 3 has been used.
【０００４】[0004]
【発明が解決しようとする課題】従来のサーミスタ材料
は６００−８００℃間のＢ定数が高々４０００Ｋ程度と
低く、６００−８００℃での温度測定には不利であると
いう問題点を有していた。The conventional thermistor material has a problem that the B constant between 600 ° C. and 800 ° C. is as low as about 4000 K, which is disadvantageous for temperature measurement at 600 ° C. to 800 ° C. .
【０００５】そこで本発明は、６００−８００℃でのＢ
定数が大きいサーミスタ素子とその製造方法及びそのサ
ーミスタ素子を用いた温度センサを提供することを目的
としている。Therefore, the present invention is based on B at 600-800 ° C.
An object of the present invention is to provide a thermistor element having a large constant, a manufacturing method thereof, and a temperature sensor using the thermistor element.
【０００６】[0006]
【課題を解決するための手段】この目的を達成するため
に、本発明のサーミスタ素子は、（Ｍｇ x ，Ｎｉ y ，Ｃｏ
z ）Ｏ（ただし、０．１０≦ｘ≦０．９０，０．１０≦
ｙ≦０．９０，０．１０≦ｚ≦０．９０，ｘ＋ｙ＋ｚ＝
１．０）である（Ｍｇ，Ｎｉ，Ｃｏ）Ｏ系組成物を主成
分とするものであり、６００−８００℃でのＢ定数が大
きいものとなる。In order to achieve this object, the thermistor element of the present invention comprises (Mg x , Ni y , Co
z ) O (provided that 0.10 ≦ x ≦ 0.90, 0.10 ≦
y ≦ 0.90, 0.10 ≦ z ≦ 0.90, x + y + z =
1.0) as the main component of the (Mg, Ni, Co) O-based composition, and has a large B constant at 600-800 ° C.
【０００７】[0007]
【発明の実施の形態】本発明の請求項１に記載の発明
は、（Ｍｇ x ，Ｎｉ y ，Ｃｏ z ）Ｏ（ただし、０．１０≦
ｘ≦０．９０，０．１０≦ｙ≦０．９０，０．１０≦ｚ
≦０．９０，ｘ＋ｙ＋ｚ＝１．０）である（Ｍｇ，Ｎ
ｉ，Ｃｏ）Ｏ系組成物を主成分とするサーミスタ素子で
あり、６００−８００℃でのＢ定数が大きいものである
とともに、適切な抵抗値を有するものである。 BEST MODE FOR CARRYING OUT THE INVENTION The invention according to claim 1 of the present invention is ( Mg x , Ni y , Co z ) O (where 0.10 ≦
x ≦ 0.90, 0.10 ≦ y ≦ 0.90, 0.10 ≦ z
≦ 0.90, x + y + z = 1.0) (Mg, N
(i, Co) O-based composition as a main component, and has a large B constant at 600 to 800 ° C.
In addition, it has an appropriate resistance value.
【０００８】[0008]
【０００９】[0009]
【００１０】請求項２に記載の発明は、ＮａＣｌ型の結
晶構造の（Ｍｇx，Ｎｉy，Ｃｏz）Ｏ（ただし、０．１
０≦ｘ≦０．９０，０．１０≦ｙ≦０．９０，０．１０
≦ｚ≦０．９０，ｘ＋ｙ＋ｚ＝１．０）を用いる請求項
１に記載のサーミスタ素子であり、適切な抵抗値を有す
るものである。According to a second aspect of the present invention, (Mg x , Ni y , Co z ) O (provided that the content is 0.1
0 ≦ x ≦ 0.90, 0.10 ≦ y ≦ 0.90, 0.10
≦ z ≦ 0.90, x + y + z = 1.0)
1 is a thermistor element having an appropriate resistance value.
【００１１】請求項３に記載の発明は、少なくともＭｇ
化合物と、Ｎｉ化合物と、Ｃｏ化合物とを混合して成形
体を形成する第１の工程と、次にこの成形体を焼成する
第２の工程とを備え、この第２の工程の焼成は、昇温過
程と、保持過程と、降温過程とを有し、降温過程はＣｏ
ＯがＣｏ3Ｏ4に変化しないような速度で降温するサーミ
スタ素子の製造方法であり、適切な抵抗値を有するサー
ミスタ素子を得ることができる。The invention according to claim 3 is at least Mg.
The method includes a first step of mixing a compound, a Ni compound, and a Co compound to form a molded body, and a second step of subsequently firing the molded body. It has a temperature raising process, a holding process, and a temperature lowering process, and the temperature lowering process is Co
This is a method of manufacturing a thermistor element in which the temperature is lowered at a rate such that O does not change to Co 3 O 4 , and a thermistor element having an appropriate resistance value can be obtained.
【００１２】請求項４に記載の発明は、ＣｏＯがＣｏ3
Ｏ4に変化しないように、２００℃／ｈ以上の速度で降
温する請求項３に記載のサーミスタ素子の製造方法であ
り、適切な抵抗値を有するサーミスタ素子を得ることが
できる。In the invention according to claim 4 , CoO is Co 3
The method of manufacturing a thermistor element according to claim 3 , wherein the temperature is lowered at a rate of 200 ° C./h or more so as not to change to O 4, and the thermistor element having an appropriate resistance value can be obtained.
【００１３】請求項５に記載の発明は、第２の工程の焼
成において、保持過程の酸素分圧よりも降温過程の酸素
分圧を低くする請求項３あるいは請求項４に記載のサー
ミスタ素子の製造方法であり、ＣｏＯがＣｏ3Ｏ4に変化
するのを防止できる。[0013] The invention according to claim 5, firing of the second step, the thermistor element according to claim 3 or claim 4 to reduce the oxygen partial pressure in the cooling process than the oxygen partial pressure holding step This is a manufacturing method and can prevent CoO from changing to Co 3 O 4 .
【００１４】請求項６に記載の発明は、第２の工程の焼
成において、保持過程の温度は、Ｃｏ化合物がＣｏＯに
変化する温度以上である請求項３〜請求項５のいずれか
一つに記載のサーミスタ素子の製造方法であり、ＮａＣ
ｌ型の結晶構造のサーミスタ素子を得ることができる。[0014] The invention according to claim 6, firing of the second step, the temperature of the holding process, in any one of claims 3 to 5 Co compound is a temperature above which changes CoO A method for manufacturing a thermistor element as described above, comprising NaC
It is possible to obtain a thermistor element having an l-type crystal structure.
【００１５】請求項７に記載の発明は、第１の工程後、
成形体を仮焼する請求項３〜請求項６のいずれか一つに
記載のサーミスタ素子の製造方法であり、焼結体密度の
低下を防止できる。According to the invention of claim 7 , after the first step,
The method for manufacturing a thermistor element according to any one of claims 3 to 6 , wherein the compact is calcined, and a decrease in the density of the sintered body can be prevented.
【００１６】請求項８に記載の発明は、仮焼の時の最高
温度を第２の工程の焼成における保持過程の温度よりも
高くする請求項７に記載のサーミスタ素子の製造方法で
あり、ＭｇＯ，ＮｉＯ，ＣｏＯ以外の化合物を出発原料
に用いた場合、仮焼によりそれぞれＭｇＯ，ＮｉＯ，Ｃ
ｏＯに変化するので、焼結体密度の低下を防止できる。The invention according to claim 8 is the method of manufacturing a thermistor element according to claim 7 , wherein the maximum temperature during calcination is set higher than the temperature during the holding process in the firing in the second step. , NiO and CoO are used as starting materials, they are calcined to form MgO, NiO and C, respectively.
Since it changes to oO, it is possible to prevent a decrease in the density of the sintered body.
【００１７】請求項９に記載の発明は、仮焼の時の酸素
分圧を第２の工程の焼成の時の酸素分圧よりも高くする
請求項７あるいは請求項８に記載のサーミスタ素子の製
造方法であり、ＣｏＯがＣｏ3Ｏ4に変化するのを防止で
きる。According to a ninth aspect of the present invention, in the thermistor element according to the seventh or eighth aspect , the oxygen partial pressure during calcination is set higher than the oxygen partial pressure during firing in the second step. This is a manufacturing method and can prevent CoO from changing to Co 3 O 4 .
【００１８】請求項１０に記載の発明は、Ｃｏ化合物を
ＣｏＯに変化させてから用いる請求項３〜請求項９のい
ずれか一つに記載のサーミスタ素子の製造方法であり、
体積変化を防止することができる。The tenth aspect of the present invention is the method for producing the thermistor element according to any one of the third to ninth aspects, in which the Co compound is changed to CoO before use.
Volume change can be prevented.
【００１９】請求項１１に記載の発明は、金属製の耐熱
キャップと、この耐熱キャップ内に収納したサーミスタ
素子と、このサーミスタ素子に電気的に接続するととも
に、前記耐熱キャップ外に引き出したリード線とを備
え、前記サーミスタ素子は（Ｍｇ x ，Ｎｉ y ，Ｃｏ z ）Ｏ
（ただし、０．１０≦ｘ≦０．９０，０．１０≦ｙ≦
０．９０，０．１０≦ｚ≦０．９０，ｘ＋ｙ＋ｚ＝１．
０）である（Ｍｇ，Ｎｉ，Ｃｏ）Ｏを主成分とするとと
もに、その表面を絶縁体でコーティングされたものであ
る温度センサであり、６００−８００℃での高精度な温
度測定が可能なものである。According to an eleventh aspect of the present invention, a metal heat-resistant cap, a thermistor element housed in the heat-resistant cap, a lead wire that is electrically connected to the thermistor element and is drawn out of the heat-resistant cap. And the thermistor element is (Mg x , Ni y , Co z ) O
(However, 0.10 ≦ x ≦ 0.90, 0.10 ≦ y ≦
0.90, 0.10 ≦ z ≦ 0.90, x + y + z = 1.
( 0) is a temperature sensor whose main component is (Mg, Ni, Co) O and whose surface is coated with an insulator, which enables highly accurate temperature measurement at 600 to 800 ° C. It is a thing.
【００２０】請求項１２に記載の発明は、絶縁体をＭｇ
Ｏを主成分とする請求項１１に記載の温度センサであ
り、信頼性が向上する。According to a twelfth aspect of the invention, the insulator is Mg
The temperature sensor according to claim 11 , wherein O is a main component, and reliability is improved.
【００２１】以下、本発明の一実施の形態を説明する。
（実施の形態１）図１は、本実施の形態における触媒温
度検知用の温度センサの断面図であり、サーミスタ素子
１を耐熱キャップ５内に密封し、白金パイプ２ａ，２ｂ
には二芯管３のリード線４ａ，４ｂを溶接し、サーミス
タ素子１からリード線４ａ，４ｂを引き出していた。An embodiment of the present invention will be described below. (Embodiment 1) FIG. 1 is a sectional view of a temperature sensor for detecting a catalyst temperature in the present embodiment, in which a thermistor element 1 is sealed in a heat resistant cap 5, and platinum pipes 2a, 2b are provided.
The lead wires 4a and 4b of the two-core tube 3 were welded to the lead wire 4a and 4b from the thermistor element 1.
【００２２】図２は図１の温度センサに用いるサーミス
タ素子１の斜視図であり、サーミスタ素子１に白金パイ
プ２ａ，２ｂを挿入して一体焼成したものである。FIG. 2 is a perspective view of the thermistor element 1 used in the temperature sensor of FIG. 1, in which platinum pipes 2a and 2b are inserted into the thermistor element 1 and integrally fired.
【００２３】図３は図２に示すサーミスタ素子を形成す
る材料のＸ線回折パターン図である。FIG. 3 is an X-ray diffraction pattern diagram of a material forming the thermistor element shown in FIG.
【００２４】まずＭｇＯ，ＮｉＯ，ＣｏＯを（Ｍｇx，
Ｎｉy，Ｃｏz）Ｏにおいてｘ，ｙ，ｚが（表１）及び
（表２）に示す組成になるように所定量秤量し、試料１
〜３６を作製した。First, MgO, NiO, and CoO are added to (Mg x ,
In Ni y , Co z ) O, a predetermined amount was weighed so that x, y, z had the compositions shown in (Table 1) and (Table 2), and sample 1
~ 36 were produced.
【００２５】[0025]
【表１】 [Table 1]
【００２６】[0026]
【表２】 [Table 2]
【００２７】次に試料１をボールミルにて１６時間混合
し、１２００℃で仮焼した後、再びボールミルで１８時
間粉砕し、乾燥後５重量％のＰＶＡ（ポリビニルアルコ
ール）水溶液を１０重量％添加して造粒を行い、最後に
図２に示す形状に成形し、白金パイプ２ａ，２ｂを挿入
した後、２００℃／ｈで昇温し、１６００℃で５時間保
持し、その後２００℃／ｈで降温して焼成し、サーミス
タ素子を得た。試料２〜３６についても同様に作製し
た。Next, Sample 1 was mixed in a ball mill for 16 hours, calcined at 1200 ° C., pulverized again in the ball mill for 18 hours, dried and added with 10% by weight of a 5% by weight PVA (polyvinyl alcohol) aqueous solution. Granulation is performed, and finally, the shape shown in FIG. 2 is formed, the platinum pipes 2a and 2b are inserted, the temperature is raised at 200 ° C./h, the temperature is maintained at 1600 ° C. for 5 hours, and then at 200 ° C./h. The temperature was lowered and firing was performed to obtain a thermistor element. Samples 2-36 were similarly prepared.
【００２８】このようにして得られたサーミスタ素子１
の表面をＭｇＯよりなる絶縁体で被覆した後、従来と同
様に図１に示す触媒温度検知用センサ中に組み込んだ。
なお耐熱キャップ５、二芯管３は耐熱材料であるＳＵＳ
３１０Ｓで形成されている。そして、６００℃、８００
℃における抵抗値を測定し、６００−８００℃間のＢ定
数を（数１）により算出し、（表１）、（表２）にＲ６
００、Ｒ８００、Ｂ定数で示した。The thermistor element 1 thus obtained
After being coated with an insulator made of MgO, it was incorporated into the catalyst temperature detecting sensor shown in FIG. 1 as in the conventional case.
The heat-resistant cap 5 and the two-core tube 3 are made of SUS which is a heat-resistant material.
It is formed of 310S. And 600 ℃, 800
The resistance value at ℃ was measured, the B constant between 600 and 800 ℃ was calculated by (Equation 1), and R6 was added to (Table 1) and (Table 2).
00, R800, and B constant.
【００２９】[0029]
【数１】 [Equation 1]
【００３０】本実施の形態に示すように、（Ｍｇ，Ｎ
ｉ，Ｃｏ）Ｏによる電気伝導を導入する事により、測定
に好都合な抵抗値及び、６００−８００℃でのＢ定数を
増大させることが可能になる。As shown in this embodiment, (Mg, N
By introducing electric conduction by i, Co) O, it becomes possible to increase the resistance value convenient for measurement and the B constant at 600 to 800 ° C.
【００３１】ここで本発明のポイントについて記載して
おく。
（１）Ｂ定数の大きなサーミスタ素子を得るために、
（Ｍｇ，Ｎｉ，Ｃｏ）Ｏは、ＮａＣｌ型単相の結晶構造
をとるようにする。Here, the points of the present invention will be described. (1) To obtain a thermistor element having a large B constant,
(Mg, Ni, Co) O has an NaCl-type single-phase crystal structure.
【００３２】（２）（Ｍｇ，Ｎｉ，Ｃｏ）Ｏ系組成とし
て、（Ｍｇx，Ｎｉy，Ｃｏz）Ｏ（ただし、０．１０≦
ｘ≦０．９０，０．１０≦ｙ≦０．９０，０．１０≦ｚ
≦０．９０，ｘ＋ｙ＋ｚ＝１．０）を用いることが、高
Ｂ定数及び温度センサとして適切な抵抗温度特性を得る
のに望ましい。(2) As a (Mg, Ni, Co) O-based composition, (Mg x , Ni y , Co z ) O (provided that 0.10≤
x ≦ 0.90, 0.10 ≦ y ≦ 0.90, 0.10 ≦ z
It is preferable to use ≦ 0.90, x + y + z = 1.0) to obtain a high B constant and a resistance temperature characteristic suitable as a temperature sensor.
【００３３】（３）焼成時にＣｏＯがＣｏ3Ｏ4に変化し
ないように、２００℃／ｈ以上の速度で降温する。これ
よりも降温速度が小さいとＣｏＯがＣｏ3Ｏ4に変化し
て、ＮａＣｌ型単相でなく、ＮａＣｌ型とスピネル型の
２相になり、Ｂ定数が低くなってしまうからである。(3) The temperature is lowered at a rate of 200 ° C./h or more so that CoO does not change to Co 3 O 4 during firing. This is because if the temperature lowering rate is lower than this, CoO changes to Co 3 O 4 and becomes not an NaCl type single phase but two phases of NaCl type and spinel type, and the B constant becomes low.
【００３４】（４）焼成時に、保持過程の酸素分圧より
も降温過程の酸素分圧を低くして、ＣｏＯがＣｏ3Ｏ4に
変化するのを防止する。ただし降温過程の酸素分圧は、
サーミスタ素子を構成する金属酸化物が還元されて金属
にならない程度にすることが必要である。本実施の形態
ではＮｉＯが還元されやすいので、気をつけなければな
らない。(4) During firing, the oxygen partial pressure in the temperature lowering process is made lower than the oxygen partial pressure in the holding process to prevent CoO from changing to Co 3 O 4 . However, the oxygen partial pressure during the cooling process is
It is necessary that the metal oxide forming the thermistor element is not reduced to metal. In this embodiment, NiO is easily reduced, so care must be taken.
【００３５】（５）本実施の形態では、焼成時の保持過
程の温度を１６００℃としたが、Ｃｏ化合物がＣｏＯに
変化する温度以上であればよく、大体１０００℃以上で
ある。(5) In the present embodiment, the temperature of the holding process during firing is set to 1600 ° C., but it may be set to a temperature higher than the temperature at which the Co compound changes to CoO, and is generally 1000 ° C. or higher.
【００３６】（６）原料を仮焼することにより、焼結体
密度の低下を防ぎ、サーミスタ素子の強度の低下を防止
することができる。ここでＭｇＯ，ＮｉＯ，ＣｏＯ以外
の化合物を出発原料として用いる場合、この仮焼の時の
最高温度を焼成の時の最高温度よりも高くして、それぞ
れＭｇＯ，ＮｉＯ，ＣｏＯにしておくことが好ましい。(6) By calcining the raw material, it is possible to prevent a decrease in the density of the sintered body and a decrease in the strength of the thermistor element. When a compound other than MgO, NiO, and CoO is used as a starting material, it is preferable that the maximum temperature at the time of calcination is set higher than the maximum temperature at the time of firing to make MgO, NiO, and CoO respectively. .
【００３７】また仮焼の時の酸素分圧を焼成の時の酸素
分圧よりも高くすることにより、仮焼の時にＣｏＯに変
化させたものが、焼成によりＣｏ3Ｏ4に変化するのを防
止する。Further, by making the oxygen partial pressure during calcination higher than the oxygen partial pressure during calcination, what is changed to CoO during calcination is changed to Co 3 O 4 during calcination. To prevent.
【００３８】（７）ＣｏＯ以外のＣｏ化合物はＣｏＯに
変化させてから用いることにより、焼結体密度の低下を
防ぐことができる。(7) By using Co compounds other than CoO after changing them to CoO, it is possible to prevent the density of the sintered body from lowering.
【００３９】（８）温度センサに組み込む際、サーミス
タ素子の表面を絶縁体でコーティングすることにより、
温度センサとして使用中耐熱キャップ内が還元雰囲気に
なったとしても、サーミスタ素子が還元されるのを防止
できる。(8) By coating the surface of the thermistor element with an insulator when incorporating it into the temperature sensor,
Even if the heat-resistant cap is in a reducing atmosphere during use as a temperature sensor, the thermistor element can be prevented from being reduced.
【００４０】また絶縁体としては、ＭｇＯのようにサー
ミスタ素子と熱膨張係数が同程度のものを主成分とする
ことにより、絶縁体が破壊するのを防止できる。If the main component of the insulator is a material having a thermal expansion coefficient similar to that of the thermistor element such as MgO, it is possible to prevent the insulator from being broken.
【００４１】[0041]
【発明の効果】以上本発明によると、６００−８００℃
でのＢ定数が大きく、適切な抵抗値を有するサーミスタ
素子を得ることができる。そしてこのサーミスタ素子を
用いた温度センサは、６００−８００℃での高精度な温
度測定が可能で、信頼性の高いものである。As described above, according to the present invention, 600-800 ° C
It is possible to obtain a thermistor element having a large B constant and a proper resistance value. The temperature sensor using this thermistor element is highly reliable because it can measure temperature with high accuracy at 600 to 800 ° C.
【図１】本発明の一実施の形態における温度センサの断
面図FIG. 1 is a sectional view of a temperature sensor according to an embodiment of the present invention.
【図２】図１に示す温度センサに用いたサーミスタ素子
の斜視図FIG. 2 is a perspective view of a thermistor element used in the temperature sensor shown in FIG.
【図３】図２に示すサーミスタ素子を形成する材料のＸ
線回折パターン図3 is X of a material forming the thermistor element shown in FIG.
Line diffraction pattern diagram
１ サーミスタ素子 ２ａ 白金パイプ ２ｂ 白金パイプ ４ａ リード線 ４ｂ リード線 ５ 耐熱キャップ 1 Thermistor element 2a platinum pipe 2b Platinum pipe 4a lead wire 4b lead wire 5 heat-resistant cap
Claims (12)
０．１０≦ｘ≦０．９０，０．１０≦ｙ≦０．９０，
０．１０≦ｚ≦０．９０，ｘ＋ｙ＋ｚ＝１．０）である
（Ｍｇ，Ｎｉ，Ｃｏ）Ｏ系組成物を主成分とするサーミ
スタ素子。1. (Mg x , Ni y , Co z ) O (provided that
0.10 ≦ x ≦ 0.90, 0.10 ≦ y ≦ 0.90,
A thermistor element whose main component is a (Mg, Ni, Co) O-based composition satisfying 0.10 ≦ z ≦ 0.90, x + y + z = 1.0) .
０．１０≦ｘ≦０．９０，０．１０≦ｙ≦０．９０，
０．１０≦ｚ≦０．９０，ｘ＋ｙ＋ｚ＝１．０）は、Ｎ
ａＣｌ型の結晶構造である請求項１に記載のサーミスタ
素子。2. (Mg x , Ni y , Co z ) O (provided that
0.10 ≦ x ≦ 0.90, 0.10 ≦ y ≦ 0.90,
0.10 ≦ z ≦ 0.90, x + y + z = 1.0) is N
The thermistor element according to claim 1 , which has an aCl type crystal structure.
と、Ｃｏ化合物とを混合して成形体を形成する第１の工
程と、次にこの成形体を焼成する第２の工程とを備え、
この第２の工程の焼成は、昇温過程と、保持過程と、降
温過程とを有し、この降温過程はＣｏＯがＣｏ3Ｏ4に変
化しないような速度で降温するサーミスタ素子の製造方
法。3. A first step of mixing at least a Mg compound, a Ni compound and a Co compound to form a molded body, and a second step of subsequently firing the molded body,
The firing in the second step includes a temperature raising process, a holding process, and a temperature lowering process, and in the temperature lowering process, the temperature is lowered at a rate such that CoO does not change to Co 3 O 4 .
度は、２００℃／ｈ以上とする請求項３に記載のサーミ
スタ素子の製造方法。4. The method for producing a thermistor element according to claim 3 , wherein the rate at which CoO does not change to Co 3 O 4 is 200 ° C./h or more.
酸素分圧よりも降温過程の酸素分圧を低くする請求項３
あるいは請求項４に記載のサーミスタ素子の製造方法。5. A method according to claim 3 in the baking of the second step, than the oxygen partial pressure in the holding process to lower the oxygen partial pressure in the cooling process
Alternatively, the method of manufacturing the thermistor element according to claim 4 .
温度は、Ｃｏ化合物がＣｏＯに変化する温度以上である
請求項３〜請求項５のいずれか一つに記載のサーミスタ
素子の製造方法。In firing wherein the second step, the temperature of the holding process, the manufacturing method of the thermistor element according to any one of claims 3 to 5 Co compound is a temperature above which changes CoO .
３〜請求項６のいずれか一つに記載のサーミスタ素子の
製造方法。7. The molded body is calcined after the first step.
3 to the manufacturing method of the thermistor element according to any one of claims 6.
成における保持過程の温度よりも高い請求項７に記載の
サーミスタ素子の製造方法。8. The method of manufacturing a thermistor element according to claim 7 , wherein the maximum temperature during the calcination is higher than the temperature during the holding process in the firing in the second step.
の時の酸素分圧よりも高くする請求項７あるいは請求項
８に記載のサーミスタ素子の製造方法。9. The method of claim 7 or claim higher than the oxygen partial pressure at the time of firing of the oxygen partial pressure of the second step when the calcination
8. The method for manufacturing the thermistor element according to item 8 .
用いる請求項３〜請求項９のいずれか一つに記載のサー
ミスタ素子の製造方法。10. A method for producing a thermistor element according to any one of claims 3 to 9 using a Co compound from varied to CoO.
ャップ内に収納したサーミスタ素子と、このサーミスタ
素子に電気的に接続するとともに、前記耐熱キャップ外
に引き出したリード線とを備え、前記サーミスタ素子は
（Ｍｇ x ，Ｎｉ y ，Ｃｏ z ）Ｏ（ただし、０．１０≦ｘ≦
０．９０，０．１０≦ｙ≦０．９０，０．１０≦ｚ≦
０．９０，ｘ＋ｙ＋ｚ＝１．０）である（Ｍｇ，Ｎｉ，
Ｃｏ）Ｏを主成分とするとともに、その表面を絶縁体で
コーティングされたものである温度センサ。11. A thermistor element, comprising: a metal heat-resistant cap; a thermistor element housed in the heat-resistant cap; and a lead wire that is electrically connected to the thermistor element and is pulled out of the heat-resistant cap. Is
(Mg x , Ni y , Co z ) O (where 0.10 ≦ x ≦
0.90, 0.10 ≦ y ≦ 0.90, 0.10 ≦ z ≦
0.90, x + y + z = 1.0) (Mg, Ni,
Co) A temperature sensor whose main component is O and whose surface is coated with an insulator.
項１１に記載の温度センサ。12. The temperature sensor according to claim 11 , wherein the insulator contains MgO as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26847197A JP3362644B2 (en) | 1997-10-01 | 1997-10-01 | Thermistor element, method of manufacturing the same, and temperature sensor using thermistor element |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26847197A JP3362644B2 (en) | 1997-10-01 | 1997-10-01 | Thermistor element, method of manufacturing the same, and temperature sensor using thermistor element |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11111508A JPH11111508A (en) | 1999-04-23 |
| JP3362644B2 true JP3362644B2 (en) | 2003-01-07 |
Family
ID=17458971
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|---|---|---|---|
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| CN108439982B (en) * | 2018-05-14 | 2021-06-15 | 济南大学 | Axial composite negative temperature coefficient thermal sensitive ceramic material and preparation method thereof |
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