JP2010225903A - Composition for thermistor, thermistor element, and method of manufacturing the same - Google Patents
Composition for thermistor, thermistor element, and method of manufacturing the same Download PDFInfo
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この発明は、遷移金属酸化物等の粉末を焼成して成るセラミックスであり、比較的高温での温度検知を行うサーミスタ用組成物とサーミスタ素子及びその製造方法に関する。 The present invention relates to a thermistor composition, a thermistor element, and a method of manufacturing the thermistor, which are ceramics obtained by firing powders of transition metal oxides and the like and detect temperature at a relatively high temperature.
従来、特に高温における安定性の高い負の温度係数を持つサーミスタ用組成物及びその組成物から製造したサーミスタ素子として、特許文献１，２に開示されているようなものがあった。これらのサーミスタ素子は、おもに自動車の排ガス温度センサとして用いられ、室温から１０００℃程度の高温に至るまでの温度検知を行うものである。 Conventionally, as a thermistor composition having a negative temperature coefficient having high stability particularly at a high temperature and a thermistor element manufactured from the composition, there are those disclosed in Patent Documents 1 and 2. These thermistor elements are mainly used as exhaust gas temperature sensors for automobiles, and perform temperature detection from room temperature to a high temperature of about 1000 ° C.
その他、高温までの測定が可能なセンサとしては、白金測温抵抗体、熱電対等が用いられている。 In addition, as a sensor capable of measuring up to a high temperature, a platinum resistance temperature detector, a thermocouple, or the like is used.
しかし、上記特許文献１，２に開示されたサーミスタ素子の組成は組成元素の種類が多く、製造が難しい上、焼成温度が１４００〜１６００℃の高温にする必要があり、焼成コスト及びセンサ素子としてのコストが高くなるものであった。 However, the composition of the thermistor element disclosed in Patent Documents 1 and 2 has many kinds of composition elements, and is difficult to manufacture. Further, it is necessary to set the firing temperature to a high temperature of 1400 to 1600 ° C. The cost of was high.
更に上記各温度センサは、温度検知に対する出力感度が低く、精度が悪いので使いづらい上、温度検出回路側での増幅回路が別途必要であり、装置全体としては高価になるものであった。 Further, each of the above temperature sensors has a low output sensitivity to temperature detection and is inaccurate, so that it is difficult to use and requires an additional amplifier circuit on the temperature detection circuit side, which makes the entire apparatus expensive.
ＮＴＣサーミスタにおいては、高温レンジのものは従来、温度係数（Ｂ定数）の高いものであり、低温・高温側の検知精度が鈍る。それにより測定レンジが限定される可能性があった。また、ＮＴＣサーミスタにおいては、長期熱的安定度を確保する為に、製造プロセス中の最終工程等でエージング、或いはアニーリングを実施して、予め抵抗値をドリフトさせて安定化させるという工程を有し、この抵抗値ドリフトを換算して目標の抵抗値に収束させるという複雑な工程があり、このためコストもかかるものであった。 In the NTC thermistor, those in the high temperature range are conventionally high in the temperature coefficient (B constant), and the detection accuracy on the low temperature / high temperature side is dull. This could limit the measurement range. In addition, NTC thermistors have a process of drifting and stabilizing the resistance value in advance by performing aging or annealing in the final process during the manufacturing process in order to ensure long-term thermal stability. There is a complicated process of converting the resistance value drift to converge to the target resistance value, which is also expensive.
また、使用される温度が高温の場合については、サーミスタ素子を製造するにあたり、使用温度範囲よりも極めて高温領域にて焼成する必要があり、製造経費等の低減が困難となっていた。 In the case where the temperature used is high, it is necessary to fire in a temperature range extremely higher than the operating temperature range when manufacturing the thermistor element, and it is difficult to reduce the manufacturing cost.
また、その他の白金測温抵抗体においてはＰｔ貴金属の材料高騰により、購入価格が高く変動が著しいといった問題がある。Ｋ熱電対の場合では繰返しの使用に弱く、センサ出力の劣化が大きいといった欠点があった。またＲ熱電対は機械的強度にも優れないという欠点がある。 In addition, other platinum resistance thermometers have a problem that the purchase price is high and the fluctuation is remarkable due to the rise in the material of Pt noble metal. In the case of the K thermocouple, there is a drawback that it is weak to repeated use and the deterioration of the sensor output is large. Further, the R thermocouple has a drawback that it is not excellent in mechanical strength.
この発明は、前記従来の技術に鑑みて成されたもので、簡単な構成で、排ガスセンサ等の過酷な温度条件においても、低温度から高温にわたり正確な温度検知が可能で、且つ安定性が高いサーミスタ用組成物とサーミスタ素子及びその製造方法を提供することを目的とする。 The present invention has been made in view of the above-described conventional technology. With a simple configuration, even under severe temperature conditions such as an exhaust gas sensor, accurate temperature detection is possible from a low temperature to a high temperature, and the stability is high. An object of the present invention is to provide a high thermistor composition, a thermistor element, and a method for producing the same.
この発明は、典型金属元素及び遷移金属元素の酸化物で構成されたサーミスタ用組成物であって、配合組成は下記の通りであり、
（Ｍ１ｘＭ２１−ｘ）・（Ｍ３ｙＭ４１−ｙ）Ｏ３
ｘ＝0.6〜0.9且つ、ｘ中のＳｍ、Ｄｙの配合量はＹに対して0.1〜0.2
ｙ＝0.2〜0.6且つ、ｙ中のＡｌ量はＭｎに対して0〜0.5
前記Ｍ１は元素周期律表でＢｅ、Ｒａを除く２Ａ族から選ばれた１種以上の典型金属元素及び、３Ａ族の遷移金属元素Ｙを示し、前記Ｍ２は６Ａ、７Ａ、３Ｂ族元素から選択される少なくとも１種以上の元素であり、前記Ｍ３はＣｒであり、前記Ｍ４はＭｎ及び／又はＡｌであり、結合材としてＭｇ２ＳｉＯ４の混合物または、Ｃａ及び／又はＡｌの酸化物或いは、これらの混合酸化物を２種類以上含むサーミスタ用組成物である。
The present invention is a thermistor composition comprising a typical metal element and an oxide of a transition metal element, the compounding composition is as follows,
(M1 x M2 1-x ) · (M3 y M4 1-y ) O 3
x = 0.6 to 0.9 and the blending amount of Sm and Dy in x is 0.1 to 0.2 with respect to Y.
y = 0.2 to 0.6, and the amount of Al in y is 0 to 0.5 with respect to Mn.
In the periodic table, M1 represents one or more typical metal elements selected from Group 2A excluding Be and Ra, and Group 3A transition metal element Y, and M2 is selected from Group 6A, 7A, and 3B elements. At least one element selected from the group consisting of M3 and Cr, and M4 and Mn and / or Al. As a binder, a mixture of Mg 2 SiO 4 or an oxide of Ca and / or Al, or A thermistor composition containing two or more of these mixed oxides.
また、前記Ｍ１、Ｍ２は、
Ｍ１：Ｙ、Ｓｍ、及び／又はＤｙ
Ｍ２：Ｃａ、Ｓｒ、及び／又はＢａ
である。さらに、混合するＭｇ２ＳｉＯ４の添加範囲は、0.05〜5.0％である。
The M1 and M2 are
M1: Y, Sm, and / or Dy
M2: Ca, Sr, and / or Ba
It is. Furthermore, the addition range of mixing Mg 2 SiO 4 is 0.05 to 5.0%.
さらに、前記組成物は焼成により得られ、さらに0.8〜1.3μｍ粒径に粉砕されたものである。 Further, the composition is obtained by firing and further pulverized to a particle size of 0.8 to 1.3 μm.
またこの発明は、典型金属元素及び遷移金属元素の酸化物で構成されたサーミスタ用組成物であって、配合組成は下記の通りであり、
（Ｍ１ｘＭ２１−ｘ）・（Ｍ３ｙＭ４１−ｙ）Ｏ３
ｘ＝0.6〜0.9且つ、ｘ中のＳｍ、Ｄｙの配合量はＹに対して0.1〜0.2
ｙ＝0.2〜0.6且つ、ｙ中のＡｌ量はＭｎに対して0〜0.5
前記Ｍ１は元素周期律表でＢｅ、Ｒａを除く２Ａ族から選ばれた１種以上の典型金属元素及び、３Ａ族の遷移金属元素Ｙを示し、前記Ｍ２は６Ａ、７Ａ、３Ｂ族元素から選択される少なくとも１種以上の元素であり、前記Ｍ３はＣｒであり、前記Ｍ４はＭｎ及び／又はＡｌであり、且つ、前記組成の（Ｍ１ｘＭ２１−ｘ）・（Ｍ３ｙＭ４１−ｙ）Ｏ３のペロプスカイト構造に、Ｍｇ２ＳｉＯ４の混合物、又はＣａ及び／又はＡｌの酸化物、或いは混合酸化物を２種類以上含む混合焼結体からなるサーミスタ素子である。
Further, the present invention is a thermistor composition composed of oxides of typical metal elements and transition metal elements, the composition of which is as follows:
(M1 x M2 1-x ) · (M3 y M4 1-y ) O 3
x = 0.6 to 0.9 and the blending amount of Sm and Dy in x is 0.1 to 0.2 with respect to Y.
y = 0.2 to 0.6, and the amount of Al in y is 0 to 0.5 with respect to Mn.
In the periodic table, M1 represents one or more typical metal elements selected from Group 2A excluding Be and Ra, and Group 3A transition metal element Y, and M2 is selected from Group 6A, 7A, and 3B elements. And M3 is Cr, M4 is Mn and / or Al, and (M1 x M2 1-x ) · (M3 y M4 1-y ) A thermistor element composed of a mixed sintered body containing a mixture of Mg 2 SiO 4 , Ca and / or Al oxide, or two or more kinds of mixed oxides in an O 3 perovskite structure.
また、前記Ｍ１、Ｍ２は
Ｍ１：Ｙ、Ｓｍ、及び／又はＤｙ
Ｍ２：Ｃａ、Ｓｒ、及び／又はＢａ
である。
The M1 and M2 are M1: Y, Sm, and / or Dy.
M2: Ca, Sr, and / or Ba
It is.
さらに、前記（Ｍ１ｘＭ２１−ｘ）・（Ｍ３ｙＭ４１−ｙ）Ｏ３＋（Ｍｇ２ＳｉＯ４）に、（ＣａＡｌ２Ｏ３）又は３Ａ族のＹを用いて前記混合組成を希釈して成り、この希釈範囲は、（ＣａＡｌ２Ｏ３）で5〜40％、３Ａ族のＹで5〜9％である。 Further, the mixed composition is diluted with (CaAl 2 O 3 ) or 3A group Y in (M1 x M2 1-x ) · (M3 y M4 1-y ) O 3 + (Mg 2 SiO 4 ). This dilution range is 5 to 40% for (CaAl 2 O 3 ) and 5 to 9% for 3A group Y.
また、前記（Ｍ１ｘＭ２１−ｘ）・（Ｍ３ｙＭ４１−ｙ）Ｏ３に添加するＭｇ２ＳｉＯ４は、フォルステライト型の結晶構造を示し、ＣａＡｌ２Ｏ３はスピネル型の結晶構造の形で含まれており、素子として最終的に混晶型である。 Further, Mg 2 SiO 4 added to the (M1 x M2 1-x ) · (M3 y M4 1-y ) O 3 shows a forsterite type crystal structure, and CaAl 2 O 3 shows a spinel type crystal structure. As a device, it is finally a mixed crystal type.
またこの発明は、前記サーミスタ素子を製造する製造方法において、前記サーミスタ組成物の仮焼成温度は1350〜1450℃の範囲で行うサーミスタ素子の製造方法である。 Moreover, this invention is the manufacturing method of the said thermistor element, The provision temperature of the said thermistor composition is a manufacturing method of the thermistor element performed in 1350-1450 degreeC.
さらに、水酸化マグネシウムを用いて、結合材としてのＭｇ２ＳｉＯ４のＭｇを添加するものである。また、前記仮焼成により得られたサーミスタ組成物を、0.8〜1.3μｍ粒径のサイズとなるように、粉砕して、所定形状に焼成するものである。 Furthermore, Mg of Mg 2 SiO 4 as a binder is added using magnesium hydroxide. Further, the thermistor composition obtained by the preliminary firing is pulverized so as to have a particle size of 0.8 to 1.3 μm and fired into a predetermined shape.
また、前記組成物に、Ｍｇ２ＳｉＯ４を添加し、1200〜1300℃で焼成してサーミスタ素子を形成するものである。 In addition, Mg 2 SiO 4 is added to the composition and fired at 1200 to 1300 ° C. to form a thermistor element.
この発明は、簡単な構成で、排ガスセンサ等の過酷な温度条件においても、低温度から高温にわたり正確な温度検知が可能で、且つ安定性が高いサーミスタ用組成物とサーミスタ素子及びその製造方法を提供することができる。 The present invention provides a thermistor composition, a thermistor element, and a method of manufacturing the thermistor that have a simple configuration and that can accurately detect a temperature from a low temperature to a high temperature even under severe temperature conditions such as an exhaust gas sensor. Can be provided.
また、焼成温度が比較的低く、焼成が容易であり、温度特性も良好で、熱履歴後の抵抗値と初期抵抗値との変化も極めて小さいものである。 Also, the firing temperature is relatively low, firing is easy, the temperature characteristics are good, and the change between the resistance value after the heat history and the initial resistance value is extremely small.
以下この発明の実施の形態について説明する。この実施形態のサーミスタ用組成物は、典型金属元素及び遷移金属元素の酸化物で構成されたサーミスタ用組成物であって、配合組成は下記の通りである。 Embodiments of the present invention will be described below. The thermistor composition of this embodiment is a thermistor composition composed of oxides of typical metal elements and transition metal elements, and the blending composition is as follows.
（Ｍ１ｘＭ２１−ｘ）・（Ｍ３ｙＭ４１−ｙ）Ｏ３
ｘ＝0.6〜0.9且つ、ｘ中のＳｍ、Ｄｙの配合量はＹに対して0.1〜0.2
ｙ＝0.2〜0.6且つ、ｙ中のＡｌ量はＭｎに対して0〜0.5
前記Ｍ１は、元素周期律表でＢｅ、Ｒａを除く２Ａ族から選ばれた１種以上の典型金属元素及び、３Ａ族の遷移金属元素Ｙを示し、前記Ｍ２は６Ａ、７Ａ、３Ｂ族元素から選択される少なくとも１種以上の元素である。例えば、Ｍ１はＹ、Ｓｍ、及び／又はＤｙであり、Ｍ２は、Ｃａ、Ｓｒ、及び／又はＢａである。また、前記Ｍ３はＣｒであり、前記Ｍ４はＭｎ及び／又はＡｌである。
(M1 x M2 1-x ) · (M3 y M4 1-y ) O 3
x = 0.6 to 0.9 and the blending amount of Sm and Dy in x is 0.1 to 0.2 with respect to Y.
y = 0.2 to 0.6, and the amount of Al in y is 0 to 0.5 with respect to Mn.
The M1 represents one or more typical metal elements selected from the 2A group excluding Be and Ra in the periodic table, and the transition metal element Y of the 3A group, and the M2 includes 6A, 7A, and 3B group elements. At least one element selected. For example, M1 is Y, Sm, and / or Dy, and M2 is Ca, Sr, and / or Ba. The M3 is Cr, and the M4 is Mn and / or Al.
さらに、結合材として、Ｍｇ２ＳｉＯ４の混合物または、Ｃａ及び／又はＡｌの酸化物、或いはこれらの混合酸化物を２種類以上含む。混合するＭｇ２ＳｉＯ４の添加範囲は、例えば、0.05〜5.0％である。焼成により得られた組成物は、例えば、0.8〜1.3μｍ粒径に粉砕する。 Further, the binder includes a mixture of Mg 2 SiO 4 , an oxide of Ca and / or Al, or a mixed oxide of these two or more. The addition range of Mg 2 SiO 4 to be mixed is, for example, 0.05 to 5.0%. The composition obtained by firing is pulverized to a particle size of 0.8 to 1.3 μm, for example.
この実施形態のサーミスタ素子は、上記組成物を粉砕したものを、成型して焼成した混合焼結体からなるものである。 The thermistor element of this embodiment consists of a mixed sintered body obtained by molding and firing the pulverized composition.
さらに、この実施形態のサーミスタ素子は、前記（Ｍ１ｘＭ２１ｘ）・（Ｍ３ｙＭ４１ｙ）Ｏ３＋（Ｍｇ２ＳｉＯ４）に、（ＣａＡｌ２Ｏ３）又は３Ａ族のＹを用いて前記混合組成を希釈して成り、この希釈範囲は、（ＣａＡｌ２Ｏ３）で5〜40％、３Ａ族のＹで5〜9％である。 Further, in the thermistor element of this embodiment, the (M1 x M2 1x ) · (M3 y M4 1y ) O 3 + (Mg 2 SiO 4 ) is replaced with (CaAl 2 O 3 ) or 3A group Y. The mixture composition is diluted, and this dilution range is 5 to 40% for (CaAl 2 O 3 ) and 5 to 9% for 3A group Y.
前記（Ｍ１ｘＭ２１−ｘ）・（Ｍ３ｙＭ４１−ｙ）Ｏ３に添加するＭｇ２ＳｉＯ４は、フォルステライト型の結晶構造を示し、ＣａＡｌ２Ｏ３はスピネル型の結晶構造の形で含まれており、サーミスタ素子としては最終的に混晶型となる。 Mg 2 SiO 4 added to the (M1 x M2 1-x ) · (M3 y M4 1-y ) O 3 shows a forsterite type crystal structure, and CaAl 2 O 3 has a spinel type crystal structure. The thermistor element finally becomes a mixed crystal type.
この実施形態のサーミスタ組成物の製造方法について、図１を基に説明する。サーミスタ組成物の組成割合は、下記の実施例の表１の組成欄に示すものであり、その割合になるように各成分を秤量する。まず、希釈元の原料として
純度が９９．９％以上で、平均粒径が１μｍのＹ２Ｏ３と、
純度が９９．０％以上で、平均粒径が１μｍのＣａＣＯ３と、
純度が９９．０％以上で、平均粒径が１μｍのＣｒ２Ｏ３と、
純度が９９．０％以上で、平均粒径が１μｍのＭｎＯ２を、
（Ｙ１−ｘ・Ｃａｘ）（Ｃｒ１−ｙ・Ｍｎｙ）Ｏ３と表したとき、ｘ，ｙを表１の組成欄に示す割合に秤量、混合を行い、その後１４００℃にて２時間の仮焼成を行う。仮焼成を行った粉末は、湿式にて粉砕を行う。これにより、粒径１μｍの原料粉末を得る。
The manufacturing method of the thermistor composition of this embodiment is demonstrated based on FIG. The composition ratio of the thermistor composition is shown in the composition column of Table 1 of the following Examples, and each component is weighed so as to be the ratio. First, Y 2 O 3 having a purity of 99.9% or more and an average particle size of 1 μm as a raw material for dilution,
CaCO 3 having a purity of 99.0% or more and an average particle diameter of 1 μm;
Cr2O 3 having a purity of 99.0% or more and an average particle diameter of 1 μm;
MnO 2 having a purity of 99.0% or more and an average particle diameter of 1 μm,
When expressed as (Y 1−x · Ca x ) (Cr 1−y · Mn y ) O 3 , x and y are weighed and mixed in the proportions shown in the composition column of Table 1 and then 2 at 1400 ° C. Temporary calcination is performed. The pre-baked powder is pulverized wet. Thereby, a raw material powder having a particle diameter of 1 μm is obtained.
さらに、第１の希釈成分として、純度が９９．９％以上で、平均粒径が１μｍのＹ２Ｏ３を利用する。第２の希釈成分として、ＣａＡｌ２Ｏ４は、純度が９９．９９％以上で、平均粒径が０．３μｍのものを用い、さらに、純度が９９．０％以上で、平均粒径が１μｍのＣａＣＯ３を焼成後、ＣａＡｌ２Ｏ４の化学式の比率となるように秤量し、混合処理して、その後１４００℃にて２時間の仮焼成を行う。仮焼成を行った粉末は、湿式により粉砕を行い、例えば0.8〜1.3μｍ粒径、平均粒径１μｍの合成粉末を得る。 Further, Y 2 O 3 having a purity of 99.9% or more and an average particle diameter of 1 μm is used as the first dilution component. As the second dilution component, CaAl 2 O 4 having a purity of 99.99% or more and an average particle size of 0.3 μm is used. Further, the purity is 99.0% or more and the average particle size is 1 μm. After the CaCO 3 is fired, it is weighed so as to have a ratio of the chemical formula of CaAl 2 O 4 , mixed, and then temporarily fired at 1400 ° C. for 2 hours. The pre-baked powder is pulverized by a wet process to obtain, for example, a synthetic powder having a particle diameter of 0.8 to 1.3 μm and an average particle diameter of 1 μm.
次に、結合材としてＭｇ２ＳｉＯ４を混ぜる。Ｍｇ２ＳｉＯ４は、純度が９９．０％以上で、平均粒径が１μｍのＭｇ（ＯＨ）２と、純度が９９．９９％以上で、平均粒径が１μｍのＳｉＯ２を、焼成後にＭｇＳｉＯ４の化学式となるように秤量、十分に混合を行う。これにより、結合材粉末を得る。 Next, Mg 2 SiO 4 is mixed as a binder. Mg 2 SiO 4 is composed of Mg (OH) 2 having a purity of 99.0% or more and an average particle diameter of 1 μm, and SiO 2 having a purity of 99.99% or more and an average particle diameter of 1 μm after firing. Weigh and mix well so that the chemical formula 4 is obtained. Thereby, a binder powder is obtained.
結合材としてＭｇ２ＳｉＯ４を用いることで、高温まで安定なＭｇＳｉＯ４結合材を低温にて合成することが可能となる。 By using Mg 2 SiO 4 as the binder, it is possible to synthesize a MgSiO 4 binder that is stable up to a high temperature at a low temperature.
これらの、希釈元の原料粉末、第１の希釈成分、第２の希釈成分、結合材を混合し有機ビヒクル(例えばＰＶＢ)を２０〜３０％の濃度になるように、アルコール中に分散させてスラリー化する。このスラリーを、リード線となる白金線を任意の間隔を設けて２本平行に配列させ、ディスペンス等で塗布して２本の白金線を間隔を設けた形で包み込むようにしてビード形状のサーミスタ素子に成型する。或いは、任意の間隔に配置した金型に、スラリーを充填して一定の圧力でプレスする事によりサーミスタ素子を形成する。 These raw material powder, the first diluted component, the second diluted component, and the binder are mixed and the organic vehicle (for example, PVB) is dispersed in alcohol so as to have a concentration of 20 to 30%. Slurry. This slurry is a bead-shaped thermistor in which two platinum wires as lead wires are arranged in parallel at an arbitrary interval and coated with a dispense or the like so as to wrap the two platinum wires in a spaced manner. Mold into the element. Alternatively, a thermistor element is formed by filling a metal mold arranged at an arbitrary interval with slurry and pressing it at a constant pressure.
この後、Ｍｇ２ＳｉＯ４を添加し、1200〜1300℃、例えば1250℃で大気中で焼成し、サーミスタ素子を形成する
この実施形態のサーミスタ素子においては、1000℃以上の高温領域においても、1000時間以上特性の劣化が無く安定性が高い。さらに、室温〜1000℃の熱履歴等を与えた場合でも、熱履歴後の抵抗値と初期抵抗値との変化（ΔR）が極めて小さく、安定な素子を得ることができる。
Thereafter, Mg 2 SiO 4 is added and fired in the atmosphere at 1200 to 1300 ° C., for example, 1250 ° C. to form the thermistor element. In the thermistor element of this embodiment, even in a high temperature region of 1000 ° C. or higher, High stability without deterioration of characteristics over time. Furthermore, even when a thermal history of room temperature to 1000 ° C. is given, a change (ΔR) between the resistance value and the initial resistance value after the thermal history is extremely small, and a stable element can be obtained.
作られるサーミスタ素子の特性は、抵抗値と抵抗温度係数（抵抗値の温度依存性：2点の温度間の温度係数／Ｂ定数）、抵抗値は5ｋΩ〜100ｋΩ範囲、Ｂ定数（例25℃/85℃）は1800Ｋ〜2800Ｋであり、-40℃の時の抵抗値は300ｋΩ〜1ＭΩ、そして仮に1000℃の時の抵抗値が30Ω〜100Ωの範囲である。これは温度センサを構成する温度検出回路にて十分実用的な抵抗値範囲に対応する事が出来る。 The characteristics of the thermistor element are as follows: resistance value and resistance temperature coefficient (temperature dependence of resistance value: temperature coefficient between two temperatures / B constant), resistance value ranging from 5 kΩ to 100 kΩ, B constant (eg 25 ° C / 85 ° C.) is 1800K to 2800K, the resistance value at -40 ° C. is 300 kΩ to 1 MΩ, and the resistance value at 1000 ° C. is 30Ω to 100Ω. This can correspond to a sufficiently practical resistance value range in the temperature detection circuit constituting the temperature sensor.
さらに、この発明のサーミスタ素子において、素子完成時にアニーリングを実施した場合、ΔR≦3.0％となり、完成品としての抵抗値を整合し易いものである。 Further, in the thermistor element of the present invention, when annealing is performed when the element is completed, ΔR ≦ 3.0%, and the resistance value as a completed product can be easily matched.
（Ｍ1ｘＭ２1-ｘ）・（Ｍ３ｙＭ４1-ｙ）Ｏ3に、材料自体の結晶層が低温から高温まで相変態しない状態で安定に存在するＭｇ２ＳｉＯ４を添加する事により、安定性の他、低温焼成無機助剤としての効果も発揮する。具体的には、サーミスタ素子焼成時に、低温にてＭｇ２ＳｉＯ４が合成され、材料が結合される事となり、サーミスタ素子を低温にて焼結可能となる。 By adding Mg 2 SiO 4, which exists stably in a state where the crystal layer of the material itself does not undergo phase transformation from low temperature to high temperature, to (M1 x M2 1-x ) · (M3 y M4 1-y ) O 3 , In addition to stability, it also exhibits an effect as a low temperature firing inorganic auxiliary. Specifically, when the thermistor element is fired, Mg 2 SiO 4 is synthesized and the materials are bonded at a low temperature, and the thermistor element can be sintered at a low temperature.
この発明のサーミスタ用組成物とサーミスタ素子及びその製造方法は、上記実施形態に限定されるものではなく、上記条件の範囲で適宜組成元素やその割合を変更し得るものである。 The composition for the thermistor, the thermistor element, and the manufacturing method thereof according to the present invention are not limited to the above-described embodiment, and the composition elements and the ratio thereof can be appropriately changed within the range of the above conditions.
以下、この発明のサーミスタ用組成物によるチップサーミスタの実施例について、試験結果を示す。まず、この発明の一実施例のサーミスタ用組成物の製造方法は前記の通りであり、各実施例のサーミスタ組成物の組成割合は、表１の組成欄に示す割合に秤量した。素子サイズは、１．５ｍｍφの円盤状に形成され、その中に０．０６ｍｍの白金線を０．５ｍｍ間隔で配置したものである。また、抵抗値のばらつきを示すΔＲの測定は、１０００℃の高温にさらした後、２５℃、８５℃、３００℃に校正されたオイル槽に浸漬して測定した。 Hereinafter, test results are shown for examples of chip thermistors using the thermistor composition of the present invention. First, the manufacturing method of the composition for the thermistors of one Example of this invention is as above-mentioned, The composition ratio of the thermistor composition of each Example was weighed in the ratio shown in the composition column of Table 1. The element size is formed in a disk shape of 1.5 mmφ, in which 0.06 mm platinum wires are arranged at intervals of 0.5 mm. Further, ΔR indicating the variation in resistance value was measured by immersing in an oil tank calibrated at 25 ° C., 85 ° C., and 300 ° C. after exposure to a high temperature of 1000 ° C.
まず、サーミスタの製造に際して、希釈元の原料として
純度が９９．９％以上で、平均粒径が１μｍのＹ２Ｏ３と、
純度が９９．０％以上で、平均粒径が１μｍのＣａＣＯ３と、
純度が９９．０％以上で、平均粒径が１μｍのＣｒ２Ｏ３と、
純度が９９．０％以上で、平均粒径が１μｍのＭｎＯ２を、表１の組成欄に示す割合に秤量、混合を行い、その後１４００℃にて２時間の仮焼成を行った。仮焼成を行った粉末は、湿式にて粉砕を行い、粒径１μｍの合成原料粉末を得た。
First, when manufacturing the thermistor, Y2O3 having a purity of 99.9% or more and an average particle size of 1 μm as a raw material for dilution,
CaCO3 having a purity of 99.0% or more and an average particle diameter of 1 μm;
Cr2O3 having a purity of 99.0% or more and an average particle diameter of 1 μm;
MnO 2 having a purity of 99.0% or more and an average particle size of 1 μm was weighed and mixed in the proportions shown in the composition column of Table 1, and then calcined at 1400 ° C. for 2 hours. The pre-baked powder was pulverized wet to obtain a synthetic raw material powder having a particle size of 1 μm.
次に、第１の希釈成分として、純度が９９．９％以上で、平均粒径が１μｍのＹ２Ｏ３を利用い、第２の希釈成分として、ＣａＡｌ２Ｏ４は、純度が９９．９９％以上で、平均粒径が０．３μｍのものを用いた。さらに、純度が９９．０％以上で、平均粒径が１μｍのＣａＣＯ３を焼成後、ＣａＡｌ２Ｏ４の化学式の比率となるように秤量し、混合を行い、その後１４００℃にて２時間の仮焼成を行った。仮焼成を行った粉末は、湿式により粉砕を行い、例えば0.8〜1.3μｍ粒径、平均粒径１μｍの合成粉末を得た。 Next, Y 2 O 3 having a purity of 99.9% or more and an average particle diameter of 1 μm is used as the first dilution component, and CaAl 2 O 4 has a purity of 99. 9% as the second dilution component. 99% or more and an average particle diameter of 0.3 μm were used. Further, after calcining CaCO 3 having a purity of 99.0% or more and an average particle diameter of 1 μm, it was weighed so as to have a ratio of the chemical formula of CaAl 2 O 4 , mixed, and then heated at 1400 ° C. for 2 hours. Pre-baking was performed. The pre-baked powder was pulverized by a wet process to obtain, for example, a synthetic powder having a particle diameter of 0.8 to 1.3 μm and an average particle diameter of 1 μm.
この後、結合材としてＭｇ２ＳｉＯ４を混ぜた。Ｍｇ２ＳｉＯ４は、純度が９９．０％以上で、平均粒径が１μｍのＭｇ（ＯＨ）２と、純度が９９．９９％以上で、平均粒径が１μｍのＳｉＯ２を、焼成後にＭｇＳｉＯ４の化学式となるように秤量し、十分に混合を行い、結合材粉末を得た。 Thereafter, Mg 2 SiO 4 was mixed as a binder. Mg 2 SiO 4 is composed of Mg (OH) 2 having a purity of 99.0% or more and an average particle diameter of 1 μm, and SiO 2 having a purity of 99.99% or more and an average particle diameter of 1 μm after firing. 4 was weighed so as to have the chemical formula 4 and sufficiently mixed to obtain a binder powder.
次に、第２の希釈成分として、ＣａＡｌ２Ｏ４は、純度が９９．９９％以上で、平均粒径が０．３μｍのＡｌ２Ｏ３と、純度が９９．０％以上で、平均粒径が１μｍのＣａＣＯ３を、焼成後にＣａＡｌ２Ｏ４の化学式となるように秤量し混合して、その後１４００℃にて２時間の仮焼成を行った。仮焼成を行った粉末を湿式粉砕し、粒径１μｍの合成粉末を得た。 Next, as the second dilution component, CaAl 2 O 4 has a purity of 99.99% or more and Al 2 O 3 having an average particle size of 0.3 μm, and a purity of 99.0% or more and the average particle size. CaCO 3 having a diameter of 1 μm was weighed and mixed so as to have a chemical formula of CaAl 2 O 4 after firing, and then pre-fired at 1400 ° C. for 2 hours. The pre-fired powder was wet pulverized to obtain a synthetic powder having a particle size of 1 μm.
次に、結合材としてＭｇ２ＳｉＯ４は、純度が９９．０％以上で、平均粒径が１μｍのＭｇ（ＯＨ）２と、純度が９９．９９％以上で、平均粒径が１μｍのＳｉＯ２を、焼成後にＭｇ２ＳｉＯ４の化学式となるように秤量、十分に混合を行い、結合材粉末を得た。 Next, Mg 2 SiO 4 as a binder is Mg (OH) 2 having a purity of 99.0% or more and an average particle size of 1 μm, and SiO having a purity of 99.99% or more and an average particle size of 1 μm. 2 was weighed and sufficiently mixed so as to have the chemical formula of Mg 2 SiO 4 after firing to obtain a binder powder.
この後、以上の希釈元の原料、第１の希釈成分、第２の希釈成分、結合材を混合しＰＶＢを２５％の濃度になるように、アルコールに分散しスラリー化した。 Thereafter, the raw material of the dilution source, the first diluted component, the second diluted component, and the binder were mixed and dispersed in alcohol so as to have a concentration of PVB of 25% to form a slurry.
このスラリーをリード線となる白金線を所定間隔で２本平行に配列させた所にディスペンス等で塗布して、２本の白金線を間隔空けた形で包み込むようにしてビード形状のサーミスタ素子形状に形成した。そして、この成型品を、1250℃の大気中で焼成しサーミスタ素子を得た。 A bead-shaped thermistor element shape is formed by applying this slurry to a place where two platinum wires as lead wires are arranged in parallel at a predetermined interval with a dispense, etc., and wrapping the two platinum wires in a spaced manner. Formed. The molded product was fired in the atmosphere at 1250 ° C. to obtain a thermistor element.
以上の工程により形成したサーミスタ素子の各実施例の成分ごとの性能を表１に示す。また、比較例も４例示す。さらに、焼成温度を変えた実施例を３例と比較例を２例、表２に示す。
以上のように、この発明のサーミスタ用組成物とサーミスタ素子によれば、低温焼成により、高性能で信頼性の高く、室温から１０００℃以上の高温での測定も可能なサーミスタ素子を得ることができる。さらに、その製造も容易なものである。
As described above, according to the thermistor composition and the thermistor element of the present invention, it is possible to obtain a thermistor element that is high-performance and highly reliable and can be measured at room temperature to 1000 ° C. or higher by low-temperature firing. it can. Furthermore, its manufacture is also easy.
Claims (12)
（Ｍ１ｘＭ２１−ｘ）・（Ｍ３ｙＭ４１−ｙ）Ｏ３
ｘ＝0.6〜0.9且つ、ｘ中のＳｍ、Ｄｙの配合量はＹに対して0.1〜0.2
ｙ＝0.2〜0.6且つ、ｙ中のＡｌ量はＭｎに対して0〜0.5
前記Ｍ１は元素周期律表でＢｅ、Ｒａを除く２Ａ族から選ばれた１種以上の典型金属元素及び、３Ａ族の遷移金属元素Ｙを示し、
前記Ｍ２は６Ａ、７Ａ、３Ｂ族元素から選択される少なくとも１種以上の元素であり、
前記Ｍ３はＣｒであり、
前記Ｍ４はＭｎ及び／又はＡｌであり、
結合材としてＭｇ２ＳｉＯ４の混合物または、Ｃａ及び／又はＡｌの酸化物或いは、これらの混合酸化物を２種類以上含むことを特徴とするサーミスタ用組成物。 It is a composition for a thermistor composed of oxides of typical metal elements and transition metal elements, and the composition is as follows:
(M1 x M2 1-x ) · (M3 y M4 1-y ) O 3
x = 0.6 to 0.9 and the blending amount of Sm and Dy in x is 0.1 to 0.2 with respect to Y.
y = 0.2 to 0.6, and the amount of Al in y is 0 to 0.5 with respect to Mn.
M1 represents one or more typical metal elements selected from Group 2A excluding Be and Ra in the Periodic Table of Elements and Group 3A transition metal element Y;
M2 is at least one element selected from group 6A, 7A, and 3B elements;
M3 is Cr;
M4 is Mn and / or Al,
A thermistor composition comprising a mixture of Mg 2 SiO 4 , an oxide of Ca and / or Al, or two or more of these mixed oxides as a binder.
Ｍ１：Ｙ、Ｓｍ、及び／又はＤｙ
Ｍ２：Ｃａ、Ｓｒ、及び／又はＢａ
であることを特徴とする請求項１記載のサーミスタ用組成物。 M1 and M2 are
M1: Y, Sm, and / or Dy
M2: Ca, Sr, and / or Ba
The thermistor composition according to claim 1, wherein
（Ｍ１ｘＭ２１−ｘ）・（Ｍ３ｙＭ４１−ｙ）Ｏ３
ｘ＝0.6〜0.9且つ、ｘ中のＳｍ、Ｄｙの配合量はＹに対して0.1〜0.2
ｙ＝0.2〜0.6且つ、ｙ中のＡｌ量はＭｎに対して0〜0.5
前記Ｍ１は元素周期律表でＢｅ、Ｒａを除く２Ａ族から選ばれた１種以上の典型金属元素及び、３Ａ族の遷移金属元素Ｙを示し、
前記Ｍ２は６Ａ、７Ａ、３Ｂ族元素から選択される少なくとも１種以上の元素であり、
前記Ｍ３はＣｒであり、
前記Ｍ４はＭｎ及び／又はＡｌであり、
且つ、前記組成の（Ｍ１ｘＭ２１−ｘ）・（Ｍ３ｙＭ４１−ｙ）Ｏ３のペロプスカイト構造に、Ｍｇ２ＳｉＯ４の混合物、又はＣａ及び／又はＡｌの酸化物、或いは混合酸化物を２種類以上含む混合焼結体からなることを特徴とするサーミスタ素子。 It is a composition for a thermistor composed of oxides of typical metal elements and transition metal elements, and the composition is as follows:
(M1 x M2 1-x ) · (M3 y M4 1-y ) O 3
x = 0.6 to 0.9 and the blending amount of Sm and Dy in x is 0.1 to 0.2 with respect to Y.
y = 0.2 to 0.6, and the amount of Al in y is 0 to 0.5 with respect to Mn.
M1 represents one or more typical metal elements selected from Group 2A excluding Be and Ra in the Periodic Table of Elements and Group 3A transition metal element Y;
M2 is at least one element selected from group 6A, 7A, and 3B elements;
M3 is Cr;
M4 is Mn and / or Al,
In addition, a perovskite structure of (M1 x M2 1-x ) · (M3 y M4 1-y ) O 3 having the above composition, a mixture of Mg 2 SiO 4 , oxides of Ca and / or Al, or mixed oxidation A thermistor element comprising a mixed sintered body containing two or more kinds of objects.
Ｍ１：Ｙ、Ｓｍ、及び／又はＤｙ
Ｍ２：Ｃａ、Ｓｒ、及び／又はＢａ
であることを特徴とする請求項５記載のサーミスタ素子。 M1 and M2 are M1: Y, Sm, and / or Dy.
M2: Ca, Sr, and / or Ba
The thermistor element according to claim 5, wherein:
The method for producing a thermistor element according to claim 9, wherein Mg 2 SiO 4 is added and thermistor element is formed by firing at 1200 to 1300 ° C.
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| WO2018235432A1 (en) * | 2017-06-20 | 2018-12-27 | 株式会社芝浦電子 | Thermistor sintered body and thermistor element |
| CN111386581A (en) * | 2018-10-31 | 2020-07-07 | 株式会社芝浦电子 | Thermistor sintered compact and temperature sensor element |
| CN112088411A (en) * | 2018-10-30 | 2020-12-15 | 株式会社芝浦电子 | Thermistor sintered compact and temperature sensor element |
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| WO2018235432A1 (en) * | 2017-06-20 | 2018-12-27 | 株式会社芝浦電子 | Thermistor sintered body and thermistor element |
| JPWO2018235432A1 (en) * | 2017-06-20 | 2019-06-27 | 株式会社芝浦電子 | Thermistor sintered body and thermistor element |
| CN110024053A (en) * | 2017-06-20 | 2019-07-16 | 株式会社芝浦电子 | Thermistor sintering body and thermistor element |
| US10643768B2 (en) | 2017-06-20 | 2020-05-05 | Shibaura Electronics Co., Ltd. | Thermistor sintered body and thermistor element |
| CN110024053B (en) * | 2017-06-20 | 2021-03-09 | 株式会社芝浦电子 | Thermistor sintered compact and thermistor element |
| CN112088411A (en) * | 2018-10-30 | 2020-12-15 | 株式会社芝浦电子 | Thermistor sintered compact and temperature sensor element |
| CN111386581A (en) * | 2018-10-31 | 2020-07-07 | 株式会社芝浦电子 | Thermistor sintered compact and temperature sensor element |
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