JP2016196392A - Sintered electroconductive oxide, and thermistor element and temperature sensor employing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem in which there is a possibility that high thermostability requested in recent years cannot be satisfied by the conventional art.SOLUTION: A sintered electroconductive oxide has a perovskite oxide crystal structure represented by M1M2MnAlCrO, where M1 represents at least one element selected from group 3 elements; and M2 represents at least one element selected from Mg, Ca, Sr and Ba. The element M1 predominantly includes at least one element selected from Nd, Pr and Sm, and a, b, c, d, e and f satisfy the following relationships: 0.600≤a<1.000, 0<b≤0.400, 0≤c<0.150, 0.400≤d<0.950, 0.050<e≤0.600, 0.50<e/(c+e)≤1.00, and 2.80≤f≤3.30.SELECTED DRAWING: Figure 4

Description

  The present invention relates to a conductive oxide sintered body and a device such as a thermistor element and a temperature sensor using the same.

  Conventionally, a thermistor element using a conductive oxide sintered body whose resistance value changes with temperature is known. As a use of the thermistor element, there is a temperature measurement of exhaust gas from an internal combustion engine such as an automobile engine. In this application, as the accuracy of exhaust gas purification systems increases in recent years, there is an increasing demand for heat resistance in the high temperature range around 900 ° C. for the thermistor elements. On the other hand, in order to detect a failure (disconnection) of a temperature sensor in a vehicle-mounted failure diagnosis system (OBD system) or the like, it is desired that the temperature can be detected even at a low temperature such as when the engine is started or when a key is turned on. In this case, particularly in cold regions, the starting temperature may be below freezing point, so a thermistor element capable of measuring temperature even at −40 ° C. is desired.

Patent Document 1 disclosed by the applicant of the present application, the composition _{formula: M1 a M2 b M3 c Al} d Cr e O f ( where, M1 is Y, Nd, Yb one or more, M2 is Mg, Ca, Sr A thermistor element using a conductive oxide sintered body having a perovskite crystal structure represented by one or more of the above and M3 is one or more of Mn and Fe) is disclosed. In this thermistor element, since the conductive oxide sintered body exhibits stable characteristics over a wide temperature range of −40 ° C. to 900 ° C., it is possible to appropriately measure the temperature in this temperature range.

Japanese Patent No. 5053563

  However, the inventor of the present application has found that the conductive oxide sintered body disclosed in Patent Document 1 has the following further problems. That is, in general, in a conductive oxide sintered body having a perovskite crystal structure, a B site element contributes to conductivity. In the perovskite crystal structure of Patent Document 1, the B site atoms are M3 (Mn, Fe), Al, and Cr, and the valence of Al is fixed at +3. It is mainly the element M3 (Mn, Fe) or Cr. In addition, since the coefficient c of the element M3 in Patent Document 1 is 0.150 to 0.600 and the coefficient e of Cr is 0.005 to 0.050, the element M3 (Mn, Fe) mainly contributes to conductivity. ). However, since Mn and Fe are elements that are relatively easily changed in valence, the temperature characteristics of the conductive oxide sintered body change at a high temperature exceeding 900 ° C., which satisfies recent high heat resistance requirements. There is a fear that it cannot be done.

  The present invention has been made to solve the above-described problems, and can be realized as the following forms.

(1) According to one aspect of the present invention, a conductive oxide sintered body having a perovskite oxide crystal structure is provided. In this conductive oxide sintered body, when one or more elements selected from Group 3 elements is M1, and one or more elements selected from Mg, Ca, Sr, Ba are M2, the composition formula: M1 a conductive oxide sintered body having _{a M2 b Mn c Al d Cr} e O f perovskite oxide crystal structure represented by. The element M1 mainly includes one or more elements selected from Nd, Pr, and Sm, and the a, b, c, d, e, and f are:
0.600 ≦ a <1.000
0 <b ≦ 0.400
0 ≦ c <0.150
0.400 ≦ d <0.950
0.050 <e ≦ 0.600
0.50 <e / (c + e) ≦ 1.00
2.80 ≦ f ≦ 3.30
It is characterized by satisfying.
This conductive oxide sintered body contains Mn, Al, Cr as the B site element of the perovskite crystal structure, and the Cr content ratio e / (c + e) is 0 with respect to the total amount of Mn and Cr excluding Al. The range is .50 to 1.00, and Cr mainly contributes to conductivity. Compared to Mn and Fe, Cr is an element having a stable valence, and therefore, changes in electrical characteristics with respect to thermal history can be reduced. Therefore, it is possible to provide a conductive oxide sintered body having higher heat resistance than conventional. Moreover, the heat resistance of the conductive oxide sintered body can be improved by mainly including at least one element selected from Nd, Pr, and Sm as the element M1.

(2) In the conductive oxide sintered body, the c and e may satisfy 0.65 ≦ e / (c + e) ≦ 1.00.
According to this configuration, it is possible to provide a conductive oxide sintered body having higher heat resistance.

(3) In the conductive oxide sintered body, a, b, c, d, e, f are
0.700 ≦ a <1.000
0 <b ≦ 0.300
0 ≦ c <0.140
0.500 <d <0.950
0.050 <e ≦ 0.500
0.65 <e / (c + e) ≦ 1.00
2.80 ≦ f ≦ 3.30
It is good also as satisfy | filling.
According to this configuration, it is possible to provide a conductive oxide sintered body having higher heat resistance.

(4) In the conductive oxide sintered body, the element M1 is one or more elements selected from Nd, Pr, and Sm, and the element M2 is one or more elements selected from Ca and Sr. It is good also as what is.
According to this configuration, it is possible to provide a conductive oxide sintered body having higher heat resistance.

  The present invention can be realized in various forms, for example, using a conductive oxide sintered body, various devices such as a thermistor element, a temperature sensor using the thermistor element, and conductive oxidation. It can be realized in the form of a method for manufacturing a sintered body or a thermistor element.

The fragmentary sectional view which shows an example of the temperature sensor as one Embodiment of this invention. The perspective view which shows the thermistor element as one Embodiment of this invention. The flowchart which shows an example of the manufacturing method of a thermistor element. The figure which shows the composition and characteristic value of various samples. The figure which shows the X-ray-diffraction result of the electroconductive oxide sintered compact of sample S6.

  FIG. 1 is a partially broken sectional view showing an example of a temperature sensor 200 as an embodiment of the present invention. The temperature sensor 200 of the present embodiment includes a thermistor element 202 as a temperature sensitive element, a sheath member 206 that attaches the thermistor element 202 to the tip, a metal tube 212 that houses the sheath member 206 and the thermistor element 202, and a metal tube. An attachment member 240 welded to one end of 212, a cylindrical member 260 welded to one end of the attachment member 240, and a nut member 250 that is rotatably fitted to the tubular member 260 are provided. The inside of the metal tube 212 is filled with ceramic cement (not shown) to prevent the thermistor element 202 and the sheath member 206 from swinging. The temperature sensor 200 is used by being mounted on an exhaust pipe of an internal combustion engine, for example. The thermistor element 202 provided on the front end side of the temperature sensor 200 is disposed in the exhaust pipe through which the exhaust gas flows, and detects the temperature of the exhaust gas.

  FIG. 2 is a perspective view showing the appearance of the thermistor element 202. The thermistor element 202 includes a plate-like thermistor section 203 having a hexagonal planar shape and two element electrode lines 204. The thermistor portion 203 is formed of a conductive oxide sintered body having a perovskite crystal structure. The preferred composition of this conductive oxide sintered body will be described in detail below.

<Preferred composition of conductive oxide sintered body>
The conductive oxide sintered body having a perovskite crystal structure preferably has a composition represented by the following formula (1).
_{(M1 a M2 b) (Mn} c Al d Cr e) O f ... (1)
Here, M1 is one or more elements selected from Group 3 elements, M2 is one or more elements selected from Mg, Ca, Sr, and Ba, and a to f are coefficients.

In this specification, the “Group 3 element” means an element group composed of scandium ( ₂₁ Sc), yttrium ( ₃₉ Y), lanthanoid ( ₅₇ La to ₇₁ Lu), and actinoid ( ₈₉ Ac to ₁₀₃ Lr). means.

The perovskite crystal structure is generally represented by the composition formula ABO ₃ . In the above formula (1), the elements M1 and M2 are A site elements, and the other elements Mn, Al, and Cr are B site elements. When the crystal having the composition of the above formula (1) has a typical perovskite crystal structure, it is preferable that a + b = 1, c + d + e = 1, and f is 3 ± x (x is about 0.3). It is preferable to take a value in the range of However, these relationships may vary somewhat as long as the temperature characteristics are not affected.

  As the element M1, one or more elements selected from Group 3 elements can be used. However, the element M1 is mainly composed of one or more elements selected from Nd, Pr, and Sm, that is, one or more elements selected from Nd, Pr, and Sm in the element M1 are 50 by mole fraction. % Or more is preferable. If one or more elements selected from Nd, Pr, and Sm are mainly used as the element M1, stable characteristics can be obtained over a wide temperature range, and heat resistance can be improved. . The reason why the characteristics are stabilized when the element M1 contains at least one element selected from Nd, Pd, and Sm is that the ionic radius of Nd or Pd, Sm is relatively large among the group 3 elements, and the element M2 ( In particular, it is presumed that the perovskite crystal structure is stable because the difference between the ionic radii of Ca and Sr) is small.

The coefficients a to f in the above formula (1) preferably satisfy the following conditions, respectively.
0.600 ≦ a <1.000 (2a)
0 <b ≦ 0.400 (2b)
0 ≦ c <0.150 (2c)
0.400 ≦ d <0.950 (2d)
0.050 <e ≦ 0.600 (2e)
0.50 <e / (c + e) ≦ 1.00 (2f)
2.80 ≦ f ≦ 3.30 (2g)

  The conductive oxide sintered body having a composition satisfying the above formulas (1) and (2a) to (2g) contains Mn, Al, and Cr as B site elements of the perovskite crystal structure. The Cr content ratio e / (c + e) with respect to the total amount is in the range of 0.50 to 1.00. Therefore, in this conductive oxide sintered body, not Mn but Cr mainly contributes to the conductivity. Compared to Mn and Fe, Cr is an element having a stable valence, and therefore, changes in electrical characteristics with respect to thermal history can be reduced. Therefore, it is possible to provide a conductive oxide sintered body having higher heat resistance than conventional. Hereinafter, the content ratio e / (c + e) is also referred to as “Cr content ratio e / (c + e)”.

  From the viewpoint of heat resistance, it is more preferable to satisfy 0.65 ≦ e / (c + e) ≦ 1.00 instead of the above formula (2f). By doing so, the Cr content is further increased, so that the heat resistance can be further increased.

Further, as the coefficients a to f, it is more preferable to satisfy the following instead of the above (2a) to (2g).
0.700 ≦ a <1.000 (3a)
0 <b ≦ 0.300 (3b)
0 ≦ c <0.140 (3c)
0.500 <d <0.950 (3d)
0.050 <e ≦ 0.500 (3e)
0.65 <e / (c + e) ≦ 1.00 (3f)
2.80 ≦ f ≦ 3.30 (3 g)
With this composition, a conductive oxide sintered body having higher heat resistance can be provided. This point will be described later according to the experimental results.

FIG. 3 is a flowchart showing a method for manufacturing a thermistor element according to an embodiment of the present invention. In step T110, first, raw material powder (Y ₂ O ₃ , Nd (OH) ₃ , Pr ₆ O ₁₁ , Sm ₂ O containing element M1) is used as a raw material powder for a conductive oxide sintered body having a perovskite crystal structure. ₃ , Yb ₂ O ₃ etc.), raw material powder containing element M2 (MgCO ₃ , CaCO ₃ , SrCO ₃ , BaCO ₃ ), and raw material powder containing other elements Mn, Al, Cr (MnO ₂ , Al ₂ O ₃ , Cr ₂ O _3, etc.) are weighed, and all the raw material powders are weighed and dried by adjusting the raw material powder mixture. . In step T120, the raw material powder mixture is calcined at 1400 ° C. for 2 hours in an air atmosphere to obtain a calcined powder. In step T130, the calcined powder is pulverized and granulated. Specifically, for example, wet mixing and pulverization are first performed using a resin pot and high-purity alumina cobblestone using ethanol as a dispersion medium. Next, the resultant slurry is dried in a hot water bath to obtain a synthetic powder. Thereafter, 20 parts by weight of a binder mainly composed of polyvinyl butyral is added to 100 parts by weight of the synthetic powder and mixed and dried. Further, the mixture is granulated through a sieve having an opening of 250 μm to obtain a granulated powder. In addition, as a binder which can be used, it is not specifically limited to the above-mentioned polyvinyl butyral, For example, other types of binders, such as polyvinyl alcohol and an acrylic binder, can also be utilized. The blending amount of the binder is usually 5 to 20 parts by weight and preferably 10 to 20 parts by weight with respect to 100 parts by weight of the synthetic powder. Moreover, when mixing with a binder, it is preferable that the average particle diameter of synthetic powder shall be 2.0 micrometers or less. As a result, uniform mixing can be achieved. The average particle diameter of the synthetic powder is a sphere equivalent diameter measured using a laser diffraction / scattering method.

In step T140, the granulated powder obtained in step T130 is used for press molding (press pressure: 4500 kg / cm ³ ) by a die molding method, and as shown in FIG. A hexagonal plate-like molded body in which one end side of the pair of element electrode wires 204 is embedded is obtained. In Step T150, the thermistor element 202 is manufactured by firing at 1500 ° C. to 1600 ° C. in the atmosphere for 2 to 4 hours.

  FIG. 4 is a diagram showing the composition of the conductive oxide sintered body and various characteristic values for a plurality of thermistor element samples. Samples S1 to S21 in FIG. 4 are examples, and samples S22 to S26 with the “*” mark attached to the sample numbers are comparative examples. These samples S1 to S26 were produced according to the process of FIG. The coefficients a to e of each element shown in FIG. 4 indicate components at the time of material mixing in step T110 (FIG. 3). In addition, although the value of the coefficient f is not described in FIG. 4, it confirmed that it was in the range of 2.80 <= f <= 3.30 from the composition ratio of each element using a fluorescent X ray analysis. FIG. 5 shows the X-ray diffraction result of the conductive oxide sintered body of Sample S6.

  The two columns at the right end of FIG. 4 show the experimental results of various characteristic values for each sample. Here, the B constant: B (−40 to 900) and the converted value CT (900) of the indicated temperature change amount before and after the high temperature durability test are shown.

The B constant (temperature gradient coefficient) was measured as follows. First, the thermistor element 202 of each sample is left in an environment of −40 ° C. (absolute temperature T (−40) = 233K), and the initial resistance value Rs (−40) between the element electrode lines 204 in that state is measured. did. Then. The thermistor element 202 was left in an environment of 900 ° C. (absolute temperature T (900) = 1173 K), and the initial resistance value Rs (900) between the element electrode lines 204 in that state was measured. The B constant B (-40 to 900) was calculated according to the following formula.
B (−40 to 900) = ln [Rs (900) / Rs (−40)] / [1 / T (900) −1 / T (−40)] (4)

The conversion value CT (900) of the indicated temperature change before and after the high temperature durability test was measured as follows. First, each sample before the high temperature durability test was left in an environment of 900 ° C., and the initial resistance value Rs (900) in that state was measured. Then, it hold | maintained in air | atmosphere 1050 degreeC * 50 hours as a high temperature endurance test. Thereafter, the resistance value Ra (900) after the high temperature durability test was measured in the same manner as described above. Then, from the initial resistance value Rs before the high temperature durability test and the resistance value Ra after the high temperature durability test, a converted value CT (900) of the indicated temperature change amount of the resistance change by the high temperature durability test was calculated according to the following equation.
CT (900) = [(B (−40 to 900) × T (100)) / [ln (Ra (900) / Rs (900)) × T (900) + B (−40 to 900)]] − T (900) ... (5)
Hereinafter, the converted value CT (900) is also referred to as “temperature change converted value CT (900)”.

  As shown in FIG. 4, the samples S1 to S21 have a B constant within a preferable range of 2000K to 3000K. Since the thermistor element 202 using such a conductive oxide sintered body has an appropriate resistance value in a wide temperature range from −40 ° C. to 900 ° C., it is possible to appropriately measure the temperature. . Moreover, in samples S1-S21, the absolute value of temperature change conversion value CT (900) is all 3.0 degrees or less, and it is very favorable at a sufficiently small point. From this result, it is understood that the thermistor elements 202 of the samples S1 to S21 can stably measure temperature over a wide range up to a high temperature range exceeding 900 ° C.

  In the samples S22 to S26 of the comparative example, the absolute value of the temperature change converted value CT (900) exceeds 3 deg, or the B constant is out of the range of 2000K to 3000K. S1 to S21 are preferred. More specifically, in the sample S22 in which the coefficients a and b are out of the range of the above expressions (2a) and (2b) and the sample S23 in which the coefficient c is out of the range of the above expression (2c), the temperature The absolute value of the change conversion value CT (900) is larger than 3 deg. In this case, the resistance change becomes large when the thermistor element 202 is exposed to a high temperature range of 900 ° C. or higher for a long time, and there is a possibility that the recently demanded heat resistance for the temperature sensor cannot be satisfied. Further, in the sample S24 in which the value of the Cr content ratio e / (c + e) is out of the range of the formula (2f), the B constant exceeds 3000K. In this case, since the resistance change of the thermistor element 202 in the temperature range of −40 ° C. to 900 ° C. becomes excessively large, it is difficult to perform appropriate resistance measurement over the entire temperature range, and it is difficult to perform appropriate temperature measurement. . Further, in the sample S25 in which the coefficients d and e are out of the range of the above expressions (2d) and (2e), and in the sample S26 in which the coefficients c and d are out of the range of the above expressions (2c) and (2d), The B constant is smaller than 2000K. In this case, resistance measurement over the entire temperature range of −40 ° C. to 900 ° C. is possible, but since the resistance change of the thermistor element 202 becomes excessively small, the measurement accuracy of the resistance value is reduced, Temperature measurement becomes difficult. In samples S25 and S26, since the absolute value of the temperature change converted value CT (900) is larger than 3 deg, the high heat resistance requirement may not be satisfied.

  In addition, sample S2, S16, S18 among samples S1-S21 of an Example has the absolute value of temperature change conversion value CT (900) more than 1.7 deg, and other sample S1, S3-S15, S17, It is slightly larger than S19 to S21. These samples S2, S16, and S18 are out of any of the above (3a) to (3g), and the other samples S1, S3 to S15, S17, and S19 to S21 are the above (3a) to (3g). Are all satisfied. Therefore, it can be understood that a conductive oxide sintered body and a thermistor element having higher heat resistance can be provided if the composition satisfies all of the above (3a) to (3g).

  Samples S1 and S9 differ from sample S4 containing only Nd as element M1 in that Y or Yb is included as element M1 in addition to Nd, and the other compositions are the same as sample S4. . The absolute value of the temperature change converted value CT (900) is slightly larger as 1.3 and 1.6 in the samples S1 and S9, whereas the sample S4 is 0.8. Therefore, from the viewpoint of heat resistance, it is preferable that the element M1 is composed only of Nd. The reason why the heat resistance is improved when Nd is used as the element M1 is presumably because Nd has a small ion radius difference from the element M2 and the perovskite crystal structure is stable. Samples S5, S19, and S20 are different in that they contain only Nd, Pr, and Sm as the element M1, and the other compositions are the same. The absolute value of the temperature change converted value CT (900) is 0.5, which is 0.5 for the sample S5 and 0.7 for the sample S19, whereas the absolute value of the sample S20 is 1.1. Therefore, from the viewpoint of heat resistance, it is more preferable that the element M1 is composed of one or more elements selected from Pr and Nd. Note that it is more preferable that Nd is mainly included as the element M1 in view of suppressing variation in temperature characteristics due to manufacturing variations when the conductive oxide sintered body (thermistor element) is mass-produced. The reason why the heat resistance is inferior when Sm is used as the element M1 is presumed to be that, among Pr, Nd, and Sm, Sm has the smallest ion radius and the stability of the perovskite crystal structure is inferior.

  The samples S10 and 13 are different from the sample S6 containing only Ca as the element M2 in that Mg or Ba is contained as the element M2 in addition to Ca, and the other compositions are the same as the sample S6. . The absolute value of the temperature change conversion value CT (900) is slightly larger as 1.2 and 1.1 in the samples S10 and S13 while the sample S6 is 0.2. Therefore, from the viewpoint of heat resistance, it is preferable to use Ca as the element M2. In sample S11 containing Sr in addition to Ca as element M2, the absolute value of temperature change converted value CT (900) remains as small as 0.4. Therefore, the element M2 is preferably composed of one or more elements selected from Ca and Sr, more preferably mainly contains Ca, and most preferably is composed only of Ca. The reason why the heat resistance is improved when Ca or Sr is used as the element M2 is that Ca or Sr has a smaller ionic radius difference from the element M1 (particularly Nd, Pr, Sm), and the perovskite crystal structure is more stable. Presumed to be.

・ Modification:
In addition, this invention is not restricted to said Example and embodiment, In the range which does not deviate from the summary, it is possible to implement in various aspects.

・ Modification 1:
In the above embodiment, the temperature sensor for measuring the exhaust gas temperature of the internal combustion engine has been described as an example of the device using the thermistor element. However, the thermistor element according to the present invention can be used for any other device.

Modification 2
In the above-described embodiment, the Pt—Rh alloy is used as the element electrode wire 204. However, the material of the element electrode wire is not limited to this, and for example, Pt or a Pt—Rh alloy containing Sr or Pt—Ir An alloy may be used, or an alloy mainly composed of a noble metal other than Pt may be used.

・ Modification 3:
When the thermistor element 202 is accommodated in the metal tube 212, the temperature sensor is configured by accommodating the thermistor element 202 and the sheath member 206 inside the metal tube 212 with the periphery of the thermistor element 202 sealed with glass. Also good.

DESCRIPTION OF SYMBOLS 200 ... Temperature sensor 202 ... Thermistor element 203 ... Thermistor part 204 ... Element electrode wire 206 ... Sheath member 212 ... Metal tube 240 ... Mounting member 250 ... Nut member 260 ... Cylindrical member

Claims (6)

One or more elements selected from Group 3 elements are M1,
When one or more elements selected from Mg, Ca, Sr, Ba are M2,
Composition _formula: M1 a _{a M2 b Mn c Al d Cr} e O conductive sintered oxide having a perovskite-type oxide crystal structure represented by _f,
The element M1 mainly contains one or more elements selected from Nd, Pr, and Sm,
A, b, c, d, e, f are
0.600 ≦ a <1.000
0 <b ≦ 0.400
0 ≦ c <0.150
0.400 ≦ d <0.950
0.050 <e ≦ 0.600
0.50 <e / (c + e) ≦ 1.00
2.80 ≦ f ≦ 3.30
A conductive oxide sintered body characterized by satisfying the above. The conductive oxide sintered body according to claim 1,
C and e are
0.65 ≦ e / (c + e) ≦ 1.00
A conductive oxide sintered body characterized by satisfying the above. The conductive oxide sintered body according to claim 1 or 2,
A, b, c, d, e, f are
0.700 ≦ a <1.000
0 <b ≦ 0.300
0 ≦ c <0.140
0.500 <d <0.950
0.050 <e ≦ 0.500
0.65 <e / (c + e) ≦ 1.00
2.80 ≦ f ≦ 3.30
A conductive oxide sintered body characterized by satisfying the above. The conductive oxide sintered body according to any one of claims 1 to 3,
The element M1 is one or more elements selected from Nd, Pr, and Sm,
The conductive oxide sintered body, wherein the element M2 is one or more elements selected from Ca and Sr.   The thermistor element provided with the thermistor part formed with the electroconductive oxide sintered compact as described in any one of Claims 1-4.   A temperature sensor comprising the thermistor element according to claim 5.