WO2010110331A1 - Composition céramique pour semi-conducteurs, élément générateur de chaleur, et module générateur de chaleur - Google Patents

Composition céramique pour semi-conducteurs, élément générateur de chaleur, et module générateur de chaleur Download PDF

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WO2010110331A1
WO2010110331A1 PCT/JP2010/055108 JP2010055108W WO2010110331A1 WO 2010110331 A1 WO2010110331 A1 WO 2010110331A1 JP 2010055108 W JP2010055108 W JP 2010055108W WO 2010110331 A1 WO2010110331 A1 WO 2010110331A1
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temperature
composition
resistivity
calcined powder
room temperature
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年紀 木田
武司 島田
健太郎 猪野
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日立金属株式会社
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Definitions

  • the present invention relates to a semiconductor ceramic composition having a positive resistance temperature used for a PTC thermistor, a PTC heater, a PTC switch, a temperature detector, and the like, and a heating element and a heating module using the same.
  • PTC material semiconductor porcelain compositions in which various semiconducting elements are added to BaTiO 3 have been proposed as a material exhibiting PTCR characteristics (positive temperature coefficient: positive temperature of resistance) (hereinafter referred to as PTC material).
  • the Curie temperature of these compositions is around 120 ° C.
  • PbTiO 3 is known as an additive element that shifts the Curie temperature in the positive direction.
  • PbTiO 3 contains the element Pb that causes environmental pollution, a material that does not use PbTiO 3 has been demanded in recent years.
  • Patent Document 1 in a structure of Ba 1-2x (BiNa) x TiO 3 in which a part of Ba of BaTiO 3 is substituted with Bi—Na, a composition in which x is in the range of 0 ⁇ x ⁇ 0.15 is used.
  • a method for producing a BaTiO 3 -based semiconductor ceramic composition in which at least one of Nb, Ta or rare earth elements is added and sintered in nitrogen, followed by heat treatment in an oxidizing atmosphere.
  • Patent Document 2 a positive thermistor in which 0.003 mol or less of a trivalent or pentavalent transition metal element is added as a semiconducting agent to 1 mol of a BaTiO 3 composition in which part of Ba is substituted with Sr.
  • a positive temperature coefficient thermistor in which 0.001 mol or less of a trivalent rare earth metal element is further added to 1 mol of the raw material has been proposed.
  • a major feature of the PTC material is a jump characteristic in which the resistivity of the PTC material rapidly increases at the Curie temperature Tc (° C.). That is, a PTC material having a large resistivity change with respect to a temperature change can be said to be a PTC material having excellent jump characteristics.
  • This jump characteristic is considered to occur because when the PTC material is heated to a temperature above the Curie temperature, the resistance formed at the crystal grain boundary (resistance due to the Schottky barrier) rapidly increases.
  • a material having excellent jump characteristics has a large room temperature resistivity (hereinafter referred to as room temperature resistivity), and a material having poor jump characteristics has room temperature resistance.
  • Patent Document 1 discloses a semiconductor ceramic composition in which x and y satisfy 0 ⁇ x ⁇ 0.2 and 0 ⁇ z ⁇ 0.01. It was proposed in.
  • Patent Document 4 Patent In the production of semiconductor ceramic composition of the Reference 3, was prepared (BaQ) and TiO 3 composition (BiNa) TiO 3 composition separately, (BaQ) TiO 3 composition compared When the (BiNa) TiO 3 composition is calcined at a relatively low temperature and the optimum temperature corresponding to each, the volatilization of Bi in the (BiNa) TiO 3 composition is suppressed, and the composition of Bi—Na.
  • the production of a semiconductor porcelain composition formed by mixing these calcined powders and molding and sintering (split calcining method) was proposed, which can prevent the deviation and prevent the generation of heterogeneous phases.
  • Patent Document 4 Furthermore, in manufacturing the (BaQ) TiO 3 composition of the calcined powder in Patent Document 4, a manufacturing method (residual method) for calcining so that TiO 3 and BaCO 3 as raw materials slightly remain is disclosed in Patent Document 5.
  • Patent Document 6 proposes a production method (addition method) in which TiO 3 and BaCO 3 as raw materials are slightly added to the (BaQ) TiO 3 composition that is calcined powder. As a result, a semiconductor ceramic composition having a low room temperature resistivity and a suppressed variation in Curie temperature can be obtained.
  • the composition formula is represented as [(BiNa) w (Ba 1-xy Sr x R y ) 1-w ] TiO 3 , where R is La, Nd , Dy, Eu, Gd, Y, Sb, and Ce), w, x, and y are 0.04 ⁇ w ⁇ 0.3, 0.03 ⁇ x ⁇ 0.2, and 0 ⁇ y ⁇ .
  • a semiconductor porcelain composition satisfying 0.02 and 3x / 5 ⁇ w is provided.
  • the w, x, and y preferably satisfy 0.06 ⁇ w ⁇ 0.25, 0.05 ⁇ x ⁇ 0.15, and 0.002 ⁇ y ⁇ 0.015.
  • 0.06 ⁇ w ⁇ 0.15, 0.05 ⁇ x ⁇ 0.15, 0.002 ⁇ y ⁇ 0.015 are satisfied, and more preferably 0.06 ⁇ w ⁇ 0.05. 10, 0.05 ⁇ x ⁇ 0.10, 0.002 ⁇ y ⁇ 0.010.
  • the composition formula is represented as [(BiNa) w Ba 1- wx Sr x ] (Ti 1-z M z ) O 3 (where M is Nb, Ta). At least one of them), w, x, z are semiconductor ceramics satisfying 0.04 ⁇ w ⁇ 0.3, 0.03 ⁇ x ⁇ 0.2, 0 ⁇ z ⁇ 0.02, 3x / 5 ⁇ w A composition is provided.
  • the w, x, and z preferably satisfy 0.06 ⁇ w ⁇ 0.25, 0.05 ⁇ x ⁇ 0.15, and 0.002 ⁇ z ⁇ 0.015.
  • 0.06 ⁇ w ⁇ 0.15, 0.05 ⁇ x ⁇ 0.15, 0.002 ⁇ z ⁇ 0.015 are satisfied, and more preferably 0.06 ⁇ w ⁇ 0. .10, 0.05 ⁇ x ⁇ 0.10, 0.004 ⁇ z ⁇ 0.008.
  • a heating element provided with an ohmic electrode for passing a current to the semiconductor ceramic composition, and a heating module using this heating element is provided.
  • the present invention it is possible to provide a semiconductor ceramic composition having a low room temperature resistivity, an excellent jump characteristic, and a reduced change with time in room temperature resistivity.
  • the semiconductor ceramic composition can be used as an element for sensor applications and heater applications. When this semiconductor ceramic composition is used in a sensor, it becomes a highly sensitive PTC thermistor over a wide temperature range. Further, when used as a heater, a PTC heater element and a heat generating module capable of stably obtaining a constant heat energy are obtained.
  • a composition formula in which a part of Ba of BaTiO 3 is substituted with Bi—Na and Sr is represented by [(BiNa) w (Ba 1 ⁇ xy Sr x R y ) 1 ⁇ w ] TiO 3 (wherein R is at least one of La, Nd, Dy, Eu, Gd, Y, Sb, and Ce), 0.04 ⁇ w ⁇ 0.3, 0.03 ⁇ x ⁇ 0.0.
  • the composition satisfies 2, 0 ⁇ y ⁇ 0.02, and 3x / 5 ⁇ w.
  • w represents the component range of (BiNa). If w is 0.04 or less, the Curie temperature cannot be shifted to the high temperature side, and if it is 0.3 or more, the room temperature resistivity exceeds 10 3 ⁇ cm, which makes it difficult to apply to a PTC heater or the like of a low voltage source. Therefore, it is not preferable.
  • 0.06 ⁇ w ⁇ 0.25, but when w is 0.15 or more, the room temperature resistivity increases, more preferably 0.06 ⁇ w ⁇ 0.15, and even more preferably 0. 0.06 ⁇ w ⁇ 0.10.
  • the temperature range for expressing the PTCR effect can be expanded by further substituting Ba with Sr, and the change in room temperature resistivity over time can be reduced.
  • . x represents the component range of Sr.
  • x 0.03 or less, the change in room temperature resistivity with time cannot be reduced.
  • x 0.2 or more, the change with time can be reduced, but since the Curie temperature is lower than 120 ° C., it is difficult to apply to a PTC heater or the like used at a high temperature of 120 ° C. or more.
  • a more preferable range is 0.05 ⁇ x ⁇ 0.15, and further preferably 0.05 ⁇ x ⁇ 0.10.
  • the temperature range in which the PTCR characteristics can be expressed can be expanded.
  • Such a semiconductor porcelain composition exhibits jump characteristics over a wide range, that is, the resistance change with respect to a minute temperature change is very large over a wide range, so that a temperature sensor, for example, temperature sensing of 120 to 260 ° C. Suitable for use.
  • a thermistor for use in a temperature sensor is required to have a characteristic with an absolute value of 2.3 or more when the change in resistivity per 100 ° C. is ⁇ which is an index of the PTC characteristic. If such characteristics are satisfied, sensor sensitivity equivalent to that of the current NTC (Negative Temperature Coefficient) thermistor can be obtained.
  • part of BaTiO 3 is replaced with Bi—Na and Sr
  • part of Ba is further replaced with the semiconducting element R.
  • This R is a semiconducting element and is at least one of La, Nd, Dy, Eu, Gd, Y, Sb, and Ce, and La is most preferable.
  • y represents the component range of R, and valence control is performed by changing the value of y. When y is 0, electrons which are carriers of current in the composition are insufficient and the room temperature resistivity is increased. If y is 0.02 or more, the room temperature resistivity increases, which is not preferable.
  • the semiconducting element R Even if the semiconducting element R is excessively added to the composition, the semiconducting element R is not replaced by Ba and is not incorporated into BaTiO 3. As a result, the semiconducting element R concentrates on the grain boundary of the composition, and thus the material. This is because it is estimated that the overall resistance is increased.
  • the addition of a trivalent cation as a semiconducting element has the effect of making it semiconducting. There is a problem that the room temperature resistivity is increased due to volatilization of Bi and Bi.
  • a more preferable range is 0.002 ⁇ y ⁇ 0.015, and further preferably 0.002 ⁇ y ⁇ 0.010. Note that 0.002 ⁇ y ⁇ 0.010 is 0.2 mol% to 1.0 mol% in terms of mol%.
  • the composition formula is represented as [(BiNa) w Ba 1- wx Sr x ] (Ti 1-z M z ) O 3 (where M is Nb And at least one of Ta), 0 ⁇ w ⁇ 0.3, 0.03 ⁇ x ⁇ 0.2, 0 ⁇ z ⁇ 0.02, and 3x / 5 ⁇ w.
  • w represents the component range of (BiNa), and w is 0.04 or less as described above. Then, the Curie temperature cannot be shifted to the high temperature side, and if it is 0.3 or more, the room temperature resistivity approaches 10 3 ⁇ cm, which makes it difficult to apply to a PTC heater or the like.
  • 0.06 ⁇ w ⁇ 0.25 but when w is 0.15 or more, the room temperature resistivity increases, more preferably 0.06 ⁇ w ⁇ 0.15, and even more preferably 0. 0.06 ⁇ w ⁇ 0.10.
  • X indicates the component range of Sr.
  • x 0.03 or less, the change in room temperature resistivity with time cannot be reduced. Further, when x is 0.2 or more, the change with time can be reduced, but since the Curie temperature becomes low, it becomes difficult to apply to a PTC heater or the like used at a high temperature.
  • a more preferable range is 0.05 ⁇ x ⁇ 0.15, and further preferably 0.05 ⁇ x ⁇ 0.10.
  • the Curie temperature also falls outside this range (about 120 ° C.), the temperature range in which the PTCR characteristics can be exhibited can be expanded, so that it is suitable for the application of the temperature sensor for the same reason as described above.
  • M is a semiconducting element and is at least one of Nb and Ta, and Nb is preferable.
  • z represents the component range of M. If z is 0, the valence cannot be controlled and the composition does not become a semiconductor, and if it exceeds 0.02, the room temperature resistivity is undesirably increased.
  • Ti is replaced with an M element in order to control the valence.
  • the addition of the M element is intended to control the valence of the Ti site that is a tetravalent element. It is possible to control the valence with a smaller amount than the preferable R addition amount of the above composition using as a semiconducting element, and there is an advantage that the internal strain of the semiconductor ceramic composition can be reduced.
  • a more preferable range is 0.002 ⁇ z ⁇ 0.015, and a further preferable range is 0.004 ⁇ z ⁇ 0.008.
  • the room temperature resistivity is 100 ⁇ ⁇
  • Semiconductor porcelain composition having a temperature coefficient of resistivity ⁇ of 4% / ° C. or higher at a Curie temperature of 120 ° C. or higher, a resistivity ratio of 2 or higher, and a time-dependent change rate ⁇ of room temperature resistivity of 10% or lower.
  • the room temperature resistivity is 50 ⁇ .
  • the temperature coefficient of resistance (jump characteristics) ⁇ is 5% / ° C. or more at a Curie temperature of 120 ° C. or higher, a resistivity ratio ⁇ of 3 or more, and a room temperature resistivity change rate ⁇ over time of 10%.
  • the following semiconductor ceramic composition can be provided.
  • the production of a semiconductor ceramic composition having the composition formula [(BiNa) w Ba 1- wx Sr x ] (Ti 1-z M z ) O 3 also includes (BaSr) (TiM) O 3 calcined powder (
  • BT calcined powder) and (BiNa) TiO 3 calcined powder (hereinafter referred to as BNT calcined powder) are prepared separately.
  • BNT calcined powder a molded body is manufactured using the mixed calcined powder obtained by mixing the BT calcined powder and the BNT calcined powder, and the molded body is sintered.
  • a separate calcining method is employed in which BT calcined powder and BNT calcined powder are separately prepared, and mixed calcined powder obtained by mixing these is formed and sintered.
  • Both of the above two compositions are semiconductor porcelain compositions in which a part of BaTiO 3 is replaced with Bi—Na and Sr, and the process for preparing BNT calcined powder is common.
  • BT calcined powder and BNT calcined powder are obtained by calcining each raw material powder at an appropriate temperature according to each.
  • TiO 3 , Bi 2 O 3 , and Na 2 CO 3 are usually used as the raw material powder for BNT calcined powder, but Bi 2 O 3 has the lowest melting point among these raw material powders, so it volatilizes by firing. Is more likely to occur. Therefore, the Bi is calcined at a relatively low temperature of 700 to 950 ° C.
  • the melting point of the BNT powder itself is high, so that it can be fired at a higher temperature even if mixed with the BT calcined powder.
  • the advantage of the divided calcining method is that it suppresses the volatilization of Bi and the overreaction of Na, and can produce a BNT calcined powder having a small composition deviation of Bi—Na with respect to the measured value.
  • the molar ratio of Bi and Na in the BNT calcined powder is basically 1: 1. Therefore, the composition formula is [(BiNa) w (Ba 1-xy Sr x R y ) 1-w ] TiO 3 and [(BiNa) w Ba 1- wx Sr x ] (Ti 1-z M z ) Indicated as O 3 .
  • the Bi / Na ratio can be accurately obtained by the divided calcination method, the sintered body after firing has a Bi / Na ratio of 0.78 to 1, or conversely, the Bi / Na ratio is 1 to The case of 1.2 is also included in the present invention.
  • the change in room temperature resistivity over time can be reduced by relatively reducing the amount of Na in anticipation of the volatilization of Bi, while the amount of Bi is relatively increased, thereby reducing the room temperature resistivity. This is because it has been found that there is also an effect of lowering.
  • the Bi / Na ratio exceeds 1.2, the resistance temperature coefficient ⁇ tends to decrease.
  • the molar ratio Bi / Na in the mixed calcined powder state is preferably about 1.01 to 1.22.
  • the volatilization of Bi in the BNT calcined powder is suppressed, or the Bi-Na composition deviation is prevented by appropriately weighing the Bi amount and the Na amount in anticipation of volatilization.
  • the molar ratio Bi / Na can be accurately controlled.
  • the BT calcined powder Ba 1-X Sr X TiO 3 in which the Ba site is replaced with Sr using, for example, BaCO 3 , SrCO 3 , and TiO 2 raw material powder is formed.
  • the Curie temperature can be easily shifted to the low temperature side by the target value by first dissolving Sr in BaTiO 3 .
  • a Ba—Ti—Bi—Na—Sr-based main phase containing Sr is generated in the sintered semiconductor ceramic composition, but Sr is first dissolved in BT calcined powder. Generation of a heterogeneous phase containing Sr can be avoided.
  • BT calcined powder and BNT calcined powder are mixed and sintered, and a part of Ba of BaTiO 3 is replaced with Bi—Na, a semiconducting element, and Sr.
  • this Sr is considered to affect the reduction of the room temperature resistivity. Therefore, by controlling the Sr substitution amount x and the BNT calcined powder amount w, the temperature range where the PTCR effect is exhibited ⁇ can be expanded to 120 ° C. or higher.
  • the residual method of the patent document 5 mentioned above and the addition method of the patent document 6 can be implemented together. That is, (1) In the process of preparing BT calcined powder in the divided calcining method, preparation is performed so that BaCO 3 and TiO 2 partially remain in the BT calcined powder. This is the residual method. Alternatively, (2) BaCO 3 and / or TiO 2 are added to BT calcined powder or BNT calcined powder or mixed calcined powder prepared in the divided calcining method. This is the addition method. The resistance value of the semiconductor ceramic composition can be lowered by using these remaining methods or addition methods.
  • Each raw material powder of BaCO 3 , SrCO 3 , TiO 2 , La 2 O 3 , Nd 2 O 3 , Nb 2 O 5 , and Ta 2 O 5 is prepared and becomes (Ba 1-xy Sr x R y ) TiO 3. Or (Ba 1-x Sr x ) (Ti 1 ⁇ z M z ) O 3, and the powders were mixed with pure water.
  • R is La or Nd
  • M is Nb or Ta.
  • the subscripts x, y, and z are the values shown in Tables 1 to 5.
  • the obtained mixed raw material powder was calcined in the atmosphere at 900 ° C. for 4 hours to prepare BT calcined powder.
  • raw material powders of Na 2 CO 3 , Bi 2 O 3 and TiO 2 were prepared, weighed and blended so as to be (Bi 0.5 Na 0.5 ) TiO 3, and dry-mixed.
  • the obtained mixed raw material powder was calcined in the air at 800 ° C. for 2 hours to prepare BNT calcined powder.
  • the prepared BT calcined powder and BNT calcined powder are blended so that the molar ratio is 1-w: w, and the center particle diameter of the mixed calcined powder is 1.0 ⁇ m to 2.
  • the mixture was mixed and pulverized to 0 ⁇ m, and then dried. Note that w is a value shown in Tables 1 to 5.
  • 10% by weight of PVA (Polyvinil Alcohol) was added to the pulverized powder of the mixed calcined powder, mixed, and granulated by a granulator.
  • the obtained granulated powder was molded with a uniaxial press machine to obtain a molded body.
  • This molded body was debindered at 700 ° C., then held in a nitrogen atmosphere with an oxygen concentration of 0.01% (100 ppm) at 1340 ° C. for 4 hours, and then gradually cooled to obtain a 40 ⁇ 25 ⁇ 4 mm sintered body. It was.
  • the sintered compact is not heat-treated in an oxidizing atmosphere.
  • the obtained sintered body was processed into a plate shape of 10 mm ⁇ 10 mm ⁇ 1 mm to prepare a test piece, and an electrode agent (manufactured by NAMICS, model number: SR5051) was applied to apply an ohmic electrode, An electrode agent (manufactured by NAMICS, model number: SR5080) was applied, dried at 180 ° C. and then baked at 600 ° C. for 10 minutes to form a surface electrode. Measure the temperature change of the resistivity of each of these test pieces in the range from room temperature to 260 ° C with a resistance meter, and obtain the room temperature resistivity Rt, Curie temperature Tc, resistance temperature coefficient ⁇ , and resistivity ratio ⁇ as follows. It was. Moreover, the time-dependent change was calculated
  • the room temperature resistivity was calculated from the resistance value measured by the 4-terminal method at 25 ° C. In addition, 25 degreeC was made into room temperature.
  • Resistance temperature coefficient ⁇ (Resistance temperature coefficient ⁇ ) It was calculated by measuring the resistance-temperature characteristics while raising the temperature to 260 ° C. in a thermostatic bath.
  • R1 is the resistivity at 260 ° C.
  • Rc is the resistivity at Tc
  • Tc is the Curie temperature.
  • the room temperature resistivity was defined as the resistivity at 25 ° C.
  • the temperature Tc at which the resistivity was twice the room temperature resistivity was defined as the Curie temperature for convenience.
  • 260-Tc 260 ⁇ Tc (° C.)
  • the expression temperature region ⁇ is preferably 120 ° C. or higher.
  • the test piece was assembled in a heater with an aluminum fin, and an energization test for 100 hours was performed by applying 13 V while cooling at room temperature (25 ° C.) at a wind speed of 4 m / s. The temperature of the fin at this time was 70 degreeC. Only at the time of measurement at 25 ° C. after the current test, the room temperature resistivity was measured, and the change rate ⁇ of the resistivity with time was examined as compared with that before the current test.
  • Table 1 shows that in (Ba 0.994-x Sr x La 0.006 ) TiO 3 , x is 0, 0.01, 0.03, 0.05, 0.10, 0.15, 0.20.
  • the rate of change ⁇ with time shows a value after 72 hours.
  • the energization test was extended for compositions with Sr substitution amounts x of 0.01 and 0.05.
  • FIG. 1 shows the time-dependent change rate ⁇ of the room temperature resistivity with respect to the energization time lapse t in this case.
  • the Sr substitution amount x is suitably selected from the range of 0.03 ⁇ x ⁇ 0.2, and is effective in the range of 0.03 ⁇ x ⁇ 0.15. Preferably, 0.05 ⁇ x ⁇ 0.15.
  • Examples 7 to 12 and Comparative Examples 8 to 13 shown in Table 3 are examples having different composition formulas from Examples 1 to 6 and Comparative Examples 1 to 7 in Tables 1 and 2 described above.
  • x is 0.01, 0.03, 0.05, 0.10, 0.15, 0.20.
  • M is Ta and Nb. The results are shown in Table 3.
  • the mixing ratio w of the BT calcined powder made of (Ba 0.944 Sr 0.05 La 0.006 ) TiO 3 and the BNT calcined powder of (Bi 0.5 Na 0.5 ) TiO 3 is set to 0, 0.0. 02, 0.04, 0.06, 0.08, 0.09, 0.10, 0.15, 0.20, 0.25, 0.30
  • Examples 13 to 19 and Comparative Examples 14 to 17 were obtained.
  • These PTCR characteristics are shown in Table 4. In the table, in Comparative Example 14, there was no Curie temperature, and the temperature coefficient of resistance ⁇ , the resistivity ratio ⁇ , and the rate of change ⁇ with time could not be measured.
  • BT calcined powder made of (Ba 0.944 Sr 0.05 ) (Ti 0.994 Nb 0.006 ) O 3 and (Bi 0 .5 Na 0.5 )
  • the mixing ratio w of the BNT calcined powder of TiO 3 is 0, 0.02, 0.04, 0.06, 0.08, 0.09, 0.10, 0.15, 0 .20, 0.25, and 0.30 were mixed, and Examples 20 to 26 and Comparative Examples 18 to 21 were obtained as sintered bodies by the same method.
  • These PTCR characteristics are shown in Table 5. In the table, in Comparative Example 18, there was no Curie temperature, and it was impossible to measure the resistance temperature coefficient ⁇ , the resistivity ratio ⁇ , and the temporal change rate ⁇ .
  • the BNT calcined powder amount w is suitably selected from the range of 0.04 ⁇ w ⁇ 0.3, and 0.06 ⁇ w ⁇ 0.25 is a preferable range.
  • w 0.15 or more
  • the room temperature resistivity is high, but it is desirable that the room temperature resistivity is about 50 or less in order to apply to a PTC heater or the like. Therefore, a preferable range for the heater is 0.06 ⁇ w ⁇ 0.15.
  • Dy, Eu, Gd, Y, Sb, and Ce other than La and Nd.
  • trivalent metals such as Dy, Eu, Gd, Y, Sb, and Ce are Dy 2 O 3 , Eu 2 O 3 , Gd 2 O 3 , Y 2 O 3 , Sb 2 O 3 , and Ce 2 O 3. This is because it is an ion and contributes as a donor when substituted with a Ba site.
  • FIG. 2 is a correlation diagram of the above Examples 1 to 48 and Comparative Examples 1 to 47 (excluding Comparative Examples 22 to 25) with the Sr substitution amount x on the horizontal axis and the BNT calcined powder amount w on the vertical axis. is there. Focusing on the horizontal axis of the Tc shifter described above, if the Sr substitution amount x is 0.2 or more, the Sr low temperature shifter is superior and Tc is shifted to less than 120 ° C., which is not preferable. In addition, the temperature coefficient of resistance also decreases. Depending on the application, the Sr substitution amount x is suitably 0.15 or less. If the lower limit is less than 0.05, the change with time cannot be suppressed.
  • the Sr substitution amount x as the Tc shifter is preferably 0.05 ⁇ x ⁇ 0.15. That is, a region surrounded by the straight lines a and b in FIG. 2 is preferable.
  • the BNT calcined powder amount w is not suitable if it is 0.3 or more because the room temperature resistivity becomes high. For this reason, the BNT calcined powder amount w is preferably 0.25 or less. Further, if the BNT calcined powder amount w is less than 0.06, the effect of the high-temperature shifter is not obtained, and a sufficient Curie temperature Tc cannot be obtained. Therefore, 0.06 ⁇ w ⁇ 0.25 is preferable as the Tc shifter.
  • a region surrounded by the straight lines c and d in FIG. 2 is preferable. Furthermore, in the case of a heater application, 0.06 ⁇ w ⁇ 0.15 is preferable because the BNT calcined powder amount w is 0.15 or more and the room temperature resistivity is increased. That is, a region surrounded by the straight lines c and e in FIG. 2 is preferable.
  • the region surrounded by the straight lines a, b, c, and d in FIG. 2 is preferable.
  • the comparative example 31 is included in the region surrounded by the straight lines a, b, c, and d, the Tc characteristic is not preferable (see Table 8). This is considered because the boundary of the shift effect in which Tc becomes less than 120 ° C. by x and w is in the vicinity of this comparative example 31.
  • the boundary where the shift effects of the low temperature shift due to Sr and the high temperature shift due to the BNT calcined powder are balanced and the Curie temperature Tc becomes 120 ° C. or higher is the straight line g connecting the third and fourth embodiments.
  • the straight line g connecting the third and fourth embodiments.
  • the region surrounded by the straight lines a, b, c, d, and g in FIG. 2 has a room temperature resistivity Rt of 100 ⁇ ⁇ cm or less, a Curie temperature Tc of 120 ° C. or more, and a resistivity ratio ⁇ of 2.
  • Rt room temperature resistivity
  • Tc Curie temperature
  • ⁇ resistivity ratio
  • the semiconductor ceramic composition when used for a heater, 0.06 ⁇ w ⁇ 0.15 is preferable because the BNT calcined powder amount w is 0.15 or more and the room temperature resistivity is increased. That is, a region surrounded by the straight lines c and e in FIG. 2 is preferable. That is, the semiconductor ceramic composition in the region surrounded by the straight lines a, b, c, e, and g has a room temperature resistivity Rt of 50 or less and is excellent for applications such as a PTC heater.
  • the resistivity ratio ⁇ is 3 or more and the resistance temperature coefficient ⁇ is 5% / ° C. or more.
  • a semiconductor ceramic composition having excellent PTCR characteristics can be obtained. (See Examples 1, 4, 5, 7, 10, 13-16, 27-31, 39, 44). That is, a region surrounded by straight lines a, b, c, f, and g is more preferable.
  • the structure and manufacturing method of the heating element using the above semiconductor ceramic composition will be described. Since the surface of the sintered semiconductor ceramic composition is rough, it is processed using a surface grinder or a slicer. It is also effective to perform burrs and chamfering by barrel polishing as appropriate. This processing is performed also for the purpose of adjusting the dimensions to keep the dimensional accuracy at a predetermined value when the semiconductor ceramic composition is attached to a circuit board as a small element or incorporated in a heating device.
  • an element made of the processed semiconductor ceramic composition (hereinafter simply referred to as an element) is mounted on a tray, and an electrode is formed on the element by a screen printing method.
  • the tray may be provided with a spring mechanism or the like for aligning the elements in one direction so that the elements mounted on the tray are correctly aligned and fixed at predetermined positions.
  • a paste prepared by mixing silver fine particles and zinc fine particles and adjusting with an organic binder, a dispersant and an organic solvent is printed on the surface of the element and dried to form an ohmic electrode at a desired position. It is also effective to mix a small amount of glass, oxide or the like in order to improve the adhesion between the element and the electrode and the denseness of the electrode.
  • a surface electrode is formed by printing and drying a paste prepared by using silver fine particles as a main component and an organic binder, a dispersant and an organic solvent. A small amount of glass, oxide, or the like can also be mixed with the surface electrode to obtain an effect of improving adhesion and denseness.
  • the electrode was sintered in a sintering furnace at 600 ° C. for 10 minutes.
  • a sintering furnace at 600 ° C. for 10 minutes.
  • the atmosphere during sintering may be adjusted.
  • the electrode adhesion strength and electrical characteristics may be improved by adjusting the oxygen concentration.
  • each of the ohmic electrode and the surface electrode formed by printing and sintering methods after sintering was set to about 5 to 20 ⁇ m.
  • These electrodes can be formed not only by printing and sintering, but also by thin film methods such as vacuum deposition, ion plating, sputtering, and plating. It is reasonable to remove the electrode attached to the undesired part after forming the electrode by using a surface grinder or slicer because the electrode may adhere to the undesired part when the thin film method is used. It is.
  • this element is used as a heating element, basically, two electrodes are arranged to face each other with the element interposed therebetween. However, sometimes the electrodes may be provided separately in three or more places.
  • FIG. 3 shows a heating element 10 in which the strip electrodes 1a to 1c each having a width w (2 mm) are provided at three positions with a distance d (10 mm) on the element 1 produced as described above.
  • the DC resistance at room temperature between the electrode 1a and the electrode 1b was 20 ⁇ .
  • the DC resistance at room temperature between the electrode 1a and the electrode 1c was 40 ⁇ .
  • the current was measured to be 2.6 A and the power consumption was 52 W. Similar current and power consumption were obtained even when a voltage of 20 V was applied with alternating current.
  • the current in the stable state was reduced to 1.3 A and the power consumption was reduced to 26 W.
  • the central electrode 1b was used as a common electrode and the same voltage (voltage having the same phase and the same amplitude in the case of alternating current) 20V was applied to the electrodes 1a and 1c, the current was 5.2A and the power consumption was 104W. .
  • the temperature of the heat generating element 10 in the stable state was stable in the vicinity of the Curie temperature of the element 1 which is a semiconductor ceramic composition, irrespective of the power consumption. If the electrodes are provided separately in two or more places (three places in the example of FIG. 3), the power consumption can be changed in several stages by appropriately selecting the electrodes to which the voltage is applied. A simple external switch or the like can be selected in accordance with the load status of the apparatus and the desired degree of heating speed.
  • FIG. 4 shows the heating element 11.
  • electrodes 2 a to 2 c are separately provided at three locations of the element 2.
  • the element 2 after firing and processing has a plate shape of 10 mm ⁇ 23 mm and a thickness of 0.7 mm.
  • the electrode 2a and the electrode 2c were each formed to be a square having a side (W) of 10 mm and to be aligned on the same surface of the element 2 with a gap D (3 mm).
  • the electrode 2b was formed over almost the entire surface opposite to the electrode 2a or the electrode 2c with the flat element 2 interposed therebetween.
  • the heating element 11 was sandwiched and fixed between metal radiation fins 20 a 1, 20 b 1, and 20 c 1 to obtain a heating module 20.
  • the electrodes 2a and 2c formed on one surface of the heating element 11 are in thermal and electrical contact with the power supply electrodes 20a and 20c, respectively, and the electrode 2b formed on the other surface is thermally and electrically connected to the power supply electrode 20b. Is closely attached.
  • the power supply electrodes 20a, 20b, and 20c are thermally connected to the radiation fins 20a1, 20b1, and 20c1, respectively.
  • the insulating layer 2d is provided between the power supply electrode 20a and the power supply electrode 20c, and electrically insulates them.
  • Heat generated in the heating element 11 is transmitted in the order of the electrodes 2a, 2b, 2c, the power supply electrodes 20a, 20b, 20c, and the radiation fins 20a1, 20b1, 20c1, and is mainly released from the radiation fins 20a1, 20b1, 20c1 into the atmosphere. . If the power supply 30c is connected between the power supply electrode 20a and the power supply electrode 20b, or between the power supply electrode 20c and the power supply electrode 20b, the power consumption is reduced, and both the power supply electrode 20a and the power supply electrode 20c If it connects between the electric power supply electrodes 20b, power consumption will become large. That is, the power consumption can be changed in two stages. In this way, the heat generating module 20 can switch the heating capacity according to the load condition of the power source 30c and the desired degree of heating.
  • the heating device 30 can be configured by connecting the heating module 20 capable of switching the heating capacity to the power source 30c.
  • the power source 30c may be either direct current / alternating current.
  • the power supply electrode 20a and the power supply electrode 20c of the heat generating module 20 are connected in parallel to one electrode of the power supply 30c via separate switches 30a and 30b, respectively, and the power supply electrode 20b is connected to the other electrode of the power supply 30c as a common terminal. Connected.
  • the heating capacity can be reduced to reduce the load of the power source 30c, and if both are made conductive, the heating capacity can be increased.
  • the element 2 can be maintained at a constant temperature without providing a special mechanism to the power source 30c. That is, when the element 2 having PTCR characteristics is heated to near the Curie temperature, the resistance value of the element 2 rapidly increases, the current flowing through the element 2 decreases, and the element 2 is not automatically heated any more. Further, when the temperature of the element 2 decreases from around the Curie temperature, the current 2 flows again to the element, and the element 2 is heated.
  • the temperature of the element 2 and thus the entire heating module 20 can be made constant, so that a circuit for adjusting the phase and amplitude of the power supply 30c, a temperature detection mechanism and a comparison mechanism with a target temperature, A heating power adjustment circuit or the like is also unnecessary.
  • the heating device 30 may flow air between the radiation fins 20a1 to 20c1 to warm the air, or connect a metal tube through which a liquid such as water passes between the radiation fins 20a1 to 20c1 to warm the liquid. it can. Also at this time, the element 2 is kept at a constant temperature, so that a safe heating device 30 can be obtained.
  • the heat generating module 12 is a substantially flat rectangular parallelepiped module.
  • the element 3 is obtained by processing the semiconductor ceramic composition of Example 1 into a substantially rectangular parallelepiped shape, electrodes 3a and 3b provided on the upper and lower surfaces of the element 3, and the element. 3 and the insulating coating layer 5 covering the electrodes 3a and 3b, and lead electrodes 4a and 4b connected to the electrodes 3a and 3b and exposed to the outside from the insulating coating layer 5, respectively.
  • the heat generating module 12 is provided with a plurality of through holes 6 that penetrate the upper and lower surfaces of the heat generating module 12 and whose inner peripheral surface is covered with the insulating coating layer 5.
  • the heat generating module 12 can be created as follows. First, a plurality of holes penetrating in the thickness direction of the element 3 are formed in the element 3 processed from the semiconductor ceramic composition of Example 1. Next, electrodes 3 a and 3 b are formed on both surfaces of the element 3 except for the opening periphery where the holes open on the upper and lower surfaces of the element 3. The electrodes 3a and 3b are formed by printing an ohmic electrode and a surface electrode in the same manner as described above.
  • the insulating coating layer 5 is formed by covering the entire element 3 and the electrodes 3a and 3b with an insulating coating agent so that the extraction electrodes 4a and 4b are exposed to the outside.
  • the heat generating module 12 is obtained.
  • the through hole 6 is formed by covering the inner peripheral surface of the hole of the element 3 with the insulating coating layer 5.
  • the heating module 12 can heat the fluid by flowing the fluid through the through hole 6. At this time, since the element 3 and the electrodes 3a and 4a through which the current flows are covered with the insulating coating layer 5, the conductive liquid can be heated because it is not in direct contact with the fluid. Therefore, the heat generating module 12 is suitable for an application that instantaneously heats a fluid such as salt water having electrical conductivity.
  • Semiconductor porcelain composition, heating element, and heating module obtained by the present invention include an automotive air conditioner auxiliary heater, a current limiting element of several amperes, a PTC thermistor such as an instantaneous water vapor generator, a PTC heater, a PTC switch, and a temperature detector. It is ideal for applications that require PTCR characteristics, such as overcurrent protection elements.

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Abstract

Cette invention concerne une composition céramique pour semi-conducteurs, Ba de la formule BaTiO3 étant partiellement substitué par Bi-Na, un élément formant les semi-conducteurs et Sr. La composition céramique pour semi-conducteurs ne subit pas de changement en fonction du temps, elle présente une faible résistivité à température ambiante et d'excellentes caractéristiques de transition. La composition céramique pour semi-conducteurs est de formule suivante : [(BiNa)w(Ba1-x-ySrxRy)1-w]TiO3 (R représentant au moins un élément sélectionné parmi La, Nd, Dy, Eu, Y, Sb et Ce), w, x et y satisfaisant aux inégalités suivantes : 0,04 < w < 0,3, 0,03 < x < 0,2, 0 < y < 0,02 et 3x/5 = w. La composition céramique pour semi-conducteurs peut, en variante, être de formule suivante : [(BiNa)w(Ba1-xSrx)1-w](Ti1-zMz)O3 (M représentant Nb et/ou Ta), w, x et z satisfaisant aux inégalités suivantes 0,04 < w < 0,3, 0,03 < x < 0,2, 0 < z < 0,020 et 3x/5 = w.
PCT/JP2010/055108 2009-03-27 2010-03-24 Composition céramique pour semi-conducteurs, élément générateur de chaleur, et module générateur de chaleur WO2010110331A1 (fr)

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WO2015119205A1 (fr) * 2014-02-06 2015-08-13 独立行政法人科学技術振興機構 Composition de résine pour capteur de température, élément pour capteur de température ainsi que procédé de fabrication de celui-ci, et capteur de température
CN112430084A (zh) * 2020-12-03 2021-03-02 西南大学 一种高耐电场强度、高储能密度的nbt-bt基驰豫铁电陶瓷薄膜材料及其制备方法

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EP1876157A4 (fr) * 2005-04-28 2011-10-26 Hitachi Metals Ltd Composition de porcelaine semi-conductrice et procede de fabrication correspondant
JP5228916B2 (ja) * 2006-10-27 2013-07-03 日立金属株式会社 半導体磁器組成物とその製造方法
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Publication number Priority date Publication date Assignee Title
CN102887705A (zh) * 2012-10-24 2013-01-23 浙江大学 一种四方相钛酸钡BaTiO3中空纳米晶的制备方法
WO2015119205A1 (fr) * 2014-02-06 2015-08-13 独立行政法人科学技術振興機構 Composition de résine pour capteur de température, élément pour capteur de température ainsi que procédé de fabrication de celui-ci, et capteur de température
JPWO2015119205A1 (ja) * 2014-02-06 2017-03-23 国立研究開発法人科学技術振興機構 温度センサー用樹脂組成物、温度センサー用素子、温度センサーおよび温度センサー用素子の製造方法
US10302506B2 (en) 2014-02-06 2019-05-28 Japan Science And Technology Agency Resin composition for temperature sensor, element for temperature sensor, temperature sensor, and method for producing element for temperature sensor
CN112430084A (zh) * 2020-12-03 2021-03-02 西南大学 一种高耐电场强度、高储能密度的nbt-bt基驰豫铁电陶瓷薄膜材料及其制备方法
CN112430084B (zh) * 2020-12-03 2022-07-08 西南大学 一种高耐电场强度、高储能密度的nbt-bt基驰豫铁电陶瓷薄膜材料及其制备方法

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