WO2015115421A1 - Procédé de production d'une composition céramique semi-conductrice, composition céramique semi-conductrice, élément ctp et module d'élément de chauffage - Google Patents

Procédé de production d'une composition céramique semi-conductrice, composition céramique semi-conductrice, élément ctp et module d'élément de chauffage Download PDF

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WO2015115421A1
WO2015115421A1 PCT/JP2015/052182 JP2015052182W WO2015115421A1 WO 2015115421 A1 WO2015115421 A1 WO 2015115421A1 JP 2015052182 W JP2015052182 W JP 2015052182W WO 2015115421 A1 WO2015115421 A1 WO 2015115421A1
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calcined powder
tio
bia
tim
bar
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雄太郎 寺門
武司 島田
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日立金属株式会社
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Definitions

  • the present invention relates to a method for manufacturing a semiconductor ceramic composition, a semiconductor ceramic composition, a PTC element, and a heating element module used for heating element modules such as a PTC heater, a PTC thermistor, a PTC switch, and a temperature detector.
  • BaTiO 3 -based semiconductor ceramic compositions have a Curie temperature of around 120 ° C. These semiconductor porcelain compositions need to shift the Curie temperature depending on the application. For example, it has been proposed to shift the Curie temperature by adding SrTiO 3 oxide to BaTiO 3 oxide, but in this case, the Curie temperature is shifted only in the negative direction and in the positive direction. Do not shift.
  • PbTiO 3 is a material that is currently in practical use and is known as an additive that shifts the Curie temperature in the positive direction.
  • lead is an element that causes environmental pollution, a lead-free semiconductor ceramic composition containing no lead is desired.
  • Patent Document 1 discloses a semiconductor ceramic composition in which a part of Ba in BaTiO 3 is replaced with Bi-Na as a lead-free semiconductor ceramic composition.
  • step of preparing (BiNa) TiO 3 calcined powder step of mixing (BaQ) TiO 3 calcined powder and (BiNa) TiO 3 calcined powder, mixing
  • a method for producing a semiconductor porcelain composition including a step of forming and sintering a calcined powder.
  • the (BaQ) TiO 3 composition (Q is a semiconducting element) and the (BiNa) TiO 3 composition are prepared separately, the (BaQ) TiO 3 composition is at a relatively high temperature, and (BiNa) TiO 3 is prepared.
  • the composition is relatively calcined and calcined at the optimum temperature according to each. Thereby, the volatilization of Bi in the (BiNa) TiO 3 composition is suppressed, the composition shift of Bi—Na is prevented, and the generation of heterogeneous phases is suppressed. And, it is described that by mixing, calcining and sintering these calcined powders, a semiconductor ceramic composition having a low room temperature resistivity and a suppressed Curie temperature variation can be obtained (paragraph ( 0013)).
  • the semiconductor ceramic composition having PTC characteristics is desired to have a low resistivity at room temperature (hereinafter referred to as room temperature resistivity ⁇ ) so that power loss is small when used as a PTC element.
  • room temperature resistivity ⁇ room temperature
  • Tc Curie temperature
  • an object of the present invention is to provide a novel manufacturing method capable of adjusting the Curie temperature Tc of the semiconductor ceramic composition to be large and the room temperature resistivity ⁇ to be small. Moreover, it aims at providing the semiconductor ceramic composition, PTC element, and heat generating module which are obtained by the manufacturing method.
  • the present invention provides (BiA) TiO 3 (A is at least one of Na, Li, K) calcined powder and (BaR) [TiM] O 3 (R is at least one of rare earth elements including Y) as raw materials. , M is at least one of Nb, Ta, and Sb, and either R or M is indispensable) is prepared, and (BiA) TiO 3 calcined powder and (BaR) [TiM] A method of manufacturing a semiconductor porcelain composition in which O 3 calcined powder is mixed and then molded and sintered, and the (BiA) TiO 3 calcined powder and (BaR) [TiM] O 3 calcined powder are mixed Before, the BET value of the (BiA) TiO 3 calcined powder is a, the BET value of the (BaR) [TiM] O 3 calcined powder is b, a / b ⁇ 2.0 .
  • the (BiA) TiO 3 calcined powder is subjected to a treatment for increasing the BET value a, and / or Alternatively, the (BaR) [TiM] O 3 calcined powder may be subjected to a treatment for reducing the BET value b.
  • the (BiA) TiO 3 calcined powder is subjected to a treatment for increasing the BET value a, and / or The (BaR) [TiM] O 3 calcined powder may be subjected to a treatment for decreasing the BET value b.
  • (BaR) [TiM] O 3 wherein the calcining temperature of the calcined powder (BIA) TiO 3 calcined powder was higher than the calcination temperature, the (BaR) [TiM] O 3 Average grain calcined powder The diameter may be larger than the average particle diameter of the (BiA) TiO 3 calcined powder, and the BET value may be a / b ⁇ 2.0.
  • the (BiA) TiO 3 calcined powder is pulverized to give the (BiA) TiO 3 calcined powder.
  • the BET value a of the powder may be increased.
  • the BET value a is preferably 1.0 m 2 / g or more and 30 m 2 / g or less.
  • the BET value b is preferably 0.1 m 2 / g or more and 15 m 2 / g or less.
  • the semiconductor ceramic composition has a composition formula [(BiA) x (Ba 1-y R y ) 1-x ] [Ti 1-z M z ] O 3 (A is at least one of Na, Li, and K).
  • R is represented by at least one of rare earth elements including Y
  • M is represented by at least one of Nb, Ta, and Sb
  • x, y, and z are 0 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.05, It is preferable that 0 ⁇ z ⁇ 0.01 (where y + z> 0) is satisfied.
  • the sintering is preferably performed at 1300 ° C. or higher and 1450 ° C. or lower.
  • a semiconductor ceramic composition can be obtained by the above production method.
  • an electrode can be formed on this semiconductor ceramic composition to obtain a PTC element.
  • it can be set as a heat generating body module using this PTC element.
  • the present invention it is possible to provide a novel manufacturing method capable of adjusting the Curie temperature Tc of the semiconductor porcelain composition to be large and the room temperature specific resistance ⁇ to be small.
  • the method for producing a semiconductor ceramic composition of the present invention is such that the average particle diameter of the (BiA) TiO 3 calcined powder is smaller than the average particle diameter of the (BaR) [TiM] O 3 calcined powder by a predetermined value or more. Specifically by the so the difference more than twice the ratio of the BET value, after mixing when sintering (1300 ° C. or higher 1450 ° C. or less) (BaR) [TiM] O 3 in calcined powder ( BiA) TiO 3 calcined powder is easily dissolved, and (BiA) TiO 3 calcined powder suppresses the volatilization of Bi. As a result, the Curie temperature Tc of the semiconductor ceramic composition is increased, and the room temperature resistivity ⁇ Can be adjusted small.
  • the value of a / b is preferably 5 or more, and more preferably 10 or more.
  • the upper limit of a / b is not particularly limited, but a / b ⁇ 50 is preferable.
  • a / b exceeds 50, that is, when the BET value a of (BiA) TiO 3 calcined powder increases or the BET value b of (BaR) [TiM] O 3 calcined powder decreases.
  • the BET value a of the (BiA) TiO 3 calcined powder is too large, the pulverization time of the (BiA) TiO 3 calcined powder becomes longer, or the (BiA) TiO 3 calcined powder aggregates and the reactivity deteriorates.
  • Curie temperature Tc tends to be small because it is difficult to dissolve in (BaR) [TiM] O 3 calcined powder. If the BET value b of the (BaR) [TiM] O 3 calcined powder is too small, the particle size of the (BaR) [TiM] O 3 calcined powder is large, so that (BiA) TiO 3 calcined during sintering It becomes difficult to form a solid solution with the powder, and the room temperature resistivity ⁇ tends to increase.
  • the BET value is obtained by adsorbing molecules (usually N 2 gas) whose surface area is known on the surface of the powder particles, and obtaining the specific surface area of the powder particles from the amount of the molecules.
  • the specific surface area is obtained by measuring the unimolecular adsorption amount vm by the BET equation (Brunauer, Emmet and Teller's equation) from the relationship of the amount v.
  • a specific surface area measuring device Macsorb, manufactured by Mountec Co., Ltd.
  • the means for adjusting the BET values of the (BiA) TiO 3 calcined powder and the (BaR) [TiM] O 3 calcined powder is not particularly limited, but the following method can be applied.
  • the obtained (BiA) TiO 3 calcined powder is pulverized by a known means such as a ball mill, and the average particle size is reduced (BET value a is increased) relative to (BaR) [TiM] O 3 calcined powder. ) Method can be adopted.
  • (BiA) TiO 3 calcined powder is subjected to a treatment for increasing the BET value a, and / or The (BaR) [TiM] O 3 calcined powder may be subjected to a treatment for reducing the BET value b.
  • (BaR) [TiM] O 3 calcining temperature of calcined powder (BIA) TiO 3 calcined powder was higher than the calcination temperature, (BaR) [TiM]
  • the average particle size of O 3 calcined powder Can be made larger than the average particle diameter of the (BiA) TiO 3 calcined powder, and the BET value can be a / b ⁇ 2.0.
  • the time of calcining of (BaR) [TiM] O 3 calcined powder is lengthened and the average particle diameter of (BaR) [TiM] O 3 calcined powder is changed to the average particle diameter of (BiA) TiO 3 calcined powder. Can be larger.
  • (BiA) TiO 3 calcined powder is subjected to a treatment to increase the BET value a, and / or , (BaR) [TiM] O 3 calcined powder may be subjected to a treatment for decreasing the BET value b.
  • the BET value a of the baked powder can be increased.
  • the (BaR) [TiM] O 3 calcined powder can be heat treated again to reduce the BET value b of the (BaR) [TiM] O 3 calcined powder.
  • the BET value a of the (BiA) TiO 3 calcined powder is preferably 1.0 m 2 / g or more and 30 m 2 / g or less.
  • the BET value a is less than 1.0 m 2 / g, the average particle size of the (BiA) TiO 3 calcined powder is large, so that (BaR) [TiM] O 3 calcined powder (BiA)
  • the TiO 3 calcined powder is not easily dissolved, and the Curie temperature Tc tends to decrease.
  • the BET value a exceeds 30 m 2 / g, problems such as longer grinding time appear.
  • (BiA) TiO 3 calcined powder is agglomerated and the reactivity deteriorates, and (BiA) TiO 3 calcined powder is difficult to dissolve in (BaR) [TiM] O 3 calcined powder.
  • Curie temperature Tc tends to decrease.
  • a more preferable range of the BET value a is 1.5 m 2 / g or more and 25 m 2 / g or less.
  • the BET value b of the (BaR) [TiM] O 3 calcined powder is preferably 0.1 m 2 / g or more and 15 m 2 / g or less.
  • the BET value b is less than 0.1 m 2 / g, the particle size of the (BaR) [TiM] O 3 calcined powder is large, so that during sintering, the (BaR) [TiM] O 3 calcined powder is It becomes difficult to form a solid solution with the (BiA) TiO 3 calcined powder, and the room temperature resistivity ⁇ tends to increase.
  • the BET value b exceeds 15 m 2 / g, the crystal grain size of the sintered body becomes small due to the small particle size of the (BaR) [TiM] O 3 calcined powder, and the room temperature specific resistance ⁇ is also large. Prone.
  • a more preferable range of the BET value b is 0.2 m 2 / g or more and 2 m 2 / g or less.
  • step 1 of FIG. 1 before mixing (BiA) TiO 3 calcined powder and (BaR) [TiM] O 3 calcined powder, the BET value of (BiA) TiO 3 calcined powder is set to a, BaR) [TiM] O 3
  • the BET value of the calcined powder is b, and a / b ⁇ 2.0.
  • This step may include a step of preparing (BiA) TiO 3 calcined powder and a step of preparing (BaR) [TiM] O 3 calcined powder.
  • a manufacturing process including a step of providing a step, and (BaR) [TiM] O 3 calcined powder to prepare (BIA) TiO 3 calcined powder.
  • (BiA) TiO 3 (A is at least one of Na, Li, and K) calcined powder and (BaR) [TiM] O 3 (R is at least one of rare earth elements including Y, M is Nb, Prepare at least one of Ta and Sb, and either R or M is essential).
  • (BiA) TiO 3 calcined powder As raw materials for (BiA) TiO 3 calcined powder, A 2 CO 3 (Na 2 CO 3 , Li 2 CO 3 , K 2 CO 3 ), Bi 2 O 3 , TiO 2 and the like are used. Another A compound, Bi compound, or Ti compound may be used.
  • R element oxides such as BaCO 3 , TiO 2 , and La 2 O 3
  • M element oxides such as Nb 2 O 5 , and the like are used as raw materials for the (BaR) [TiM] O 3 calcined powder.
  • R and M are used as semiconducting elements.
  • the semiconductor ceramic composition finally obtained when the composition does not contain both R and M increases the room temperature resistivity ⁇ , so at least one of R and M is essential.
  • Another Ba compound or Ti compound may be used. These raw materials may be pulverized according to the particle size of the raw material powder.
  • the raw material powder may be mixed by either wet mixing using pure water or ethanol or dry mixing. However, when dry mixing is performed, compositional deviation is more easily prevented.
  • the raw material for the (BiA) TiO 3 calcined powder is preferably calcined at 700 ° C. or higher and 950 ° C. or lower.
  • the calcining temperature is less than 700 ° C, unreacted A 2 CO 3 , Bi, Ti and unreacted A 2 O react with the moisture in the furnace atmosphere or in the case of wet mixing, and generate heat and composition. Deviates from the desired value and the PTC characteristics tend to become unstable.
  • the calcination temperature exceeds 950 ° C.
  • the volatilization of Bi proceeds, causing a composition shift, and the generation of a heterogeneous phase is easily promoted.
  • the calcination time is preferably 0.5 hours or more and 10 hours or less.
  • the calcining time is less than 0.5 hours, the obtained PTC characteristics tend to be unstable for the same reason as when the calcining temperature is less than 700 ° C.
  • the calcination time exceeds 10 hours, the generation of a heterogeneous phase is likely to be promoted for the same reason as when the calcination temperature exceeds 950 ° C.
  • This calcination is preferably performed in the air.
  • the raw material for the (BaR) [TiM] O 3 calcined powder is preferably calcined at 900 ° C. or higher and 1300 ° C. or lower.
  • (BaR) [TiM] O 3 is not completely formed. For this reason, a part of BaO decomposed from BaCO 3 reacts with water, or a part of the remaining BaCO 3 dissolves in water, which may cause a composition shift and vary in characteristics.
  • the raw material of the (BaR) [TiM] O 3 calcined powder is preferably calcined at a higher temperature than the raw material of the (BiA) TiO 3 calcined powder.
  • the calcining time is preferably 0.5 hours or more. If the calcining time is less than 0.5 hours, it tends to cause a composition shift.
  • the calcination of the raw material of the (BaR) [TiM] O 3 calcined powder is preferably performed in the air.
  • the calcining temperature of the raw material of the (BaR) [TiM] O 3 calcined powder is 1100 ° C. or higher and 1300 ° C. or lower.
  • Step 1 the volatilization of Bi is suppressed, and the composition shift of Bi-A can be prevented to suppress the generation of a heterogeneous phase containing the A element. For this reason, while reducing the room temperature specific resistance (rho) of the obtained semiconductor ceramic composition, the variation in Curie temperature Tc can be suppressed.
  • Step 2 After mixing each calcined powder in a predetermined amount, they are mixed.
  • the mixed raw material may be referred to as a third raw material.
  • Mixing may be either wet mixing using pure water or ethanol, or dry mixing. However, it is preferable to perform dry mixing because the compositional deviation can be further prevented.
  • the third raw material is formed into a desired shape. You may granulate a pulverized powder with a granulator as needed before shaping
  • the compact density after molding is preferably 2.5 to 3.5 g / cm 3 .
  • Sintering is preferably performed at a sintering temperature of 1300 ° C. or higher and 1450 ° C. or lower. If the sintering temperature is less than 1300 ° C, the sintering will be insufficient. If the sintering temperature exceeds 1450 ° C., the temperature coefficient of resistance ⁇ decreases or the heat resistance decreases.
  • the sintering temperature is more preferably 1420 ° C. or lower.
  • the sintering atmosphere is preferably performed in the air, a reducing atmosphere, or an inert gas atmosphere having a low oxygen concentration.
  • a semiconductor ceramic composition having a large resistance temperature coefficient ⁇ can be obtained while keeping the room temperature specific resistance ⁇ at 200 ⁇ cm or less.
  • the sintering time is preferably 1 hour or more and 10 hours or less. If the sintering time is less than 1 hour, sintering is insufficient. When the sintering time exceeds 10 hours, there is a possibility that the Bi concentration in the crystal grains becomes uniform and the resistance temperature coefficient ⁇ becomes small. A more preferable sintering time is 2 hours or more and 6 hours or less.
  • This semiconductor ceramic composition has a composition formula of [(BiA) x (Ba 1-y R y ) 1-x ] [Ti 1-z M z ] O 3 (A is at least one of Na, Li, and K, R is represented by at least one of rare earth elements including Y, M is represented by at least one of Nb, Ta, and Sb), and x, y, and z are 0 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.05, 0 ⁇ Those satisfying z ⁇ 0.01 (where y + z> 0) are preferred.
  • ⁇ Curie temperature Tc can be set to 130 ° C to 200 ° C by setting the range of x to more than 0 and 0.2 or less. If x exceeds 0.2, it is not preferable because a different phase is easily formed.
  • the room temperature specific resistance ⁇ exceeds 200 ⁇ cm, so y + z> 0.
  • both R and M are not necessarily required, and at least one of them may be used.
  • y indicating the R amount is preferably in the range of 0 ⁇ y ⁇ 0.05. If y is 0, the composition does not become a semiconductor, and if it exceeds 0.05, the room temperature resistivity ⁇ increases, which is not preferable.
  • the valence can be controlled by changing the value of y. However, when the valence control of the composition is performed in a system in which a part of Ba in the BaTiO 3 oxide is substituted with Bi and A, the addition of a trivalent cation as a semiconducting element results in a monovalent effect. There is a problem that the room temperature resistivity ⁇ increases due to the presence of A ions. Therefore, a more preferable range is 0.002 ⁇ y ⁇ 0.03.
  • R is at least one element selected from rare earths (Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tb, Tm, Yb, Lu), particularly La and Y are preferable because excellent PTC characteristics can be obtained.
  • rare earths Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tb, Tm, Yb, Lu
  • z indicating the amount of M is preferably in the range of 0 ⁇ z ⁇ 0.01. If z is 0, the valence cannot be controlled and the composition does not become a semiconductor, and if z exceeds 0.01, the room temperature resistivity ⁇ increases or the Curie temperature Tc decreases, which is not preferable. A more preferable range is 0.001 ⁇ z ⁇ 0.005. As M, Nb is particularly preferable because an excellent PTC characteristic can be obtained.
  • (BiA) in the composition formula refers to (Bi 0.5 A 0.5 ).
  • Si raw materials and Ca raw materials can be used as sintering aids.
  • Si and Ca may be included in the composition formula of the semiconductor ceramic composition.
  • the temperature coefficient of resistance ⁇ was calculated by measuring the resistance-temperature characteristics of the semiconductor ceramic composition while raising the temperature from room temperature 25 ° C. to 270 ° C. in a thermostatic bath.
  • the Curie temperature T C is resistivity and a temperature of which becomes 2 times the room temperature resistivity [rho.
  • the room temperature specific resistance ⁇ ( ⁇ cm) of the semiconductor ceramic composition was measured at 25 ° C. by a four-terminal method.
  • Example 1 The following procedure was performed as (Step 1). First, as a raw material, a raw material of (BiA) TiO 3 calcined powder and a raw material of (BaR) [TiM] O 3 calcined powder were prepared. In this example, raw material powder of Na 2 CO 3 , Bi 2 O 3 and TiO 2 was prepared as a raw material for (BiA) TiO 3 calcined powder, and the Bi / Na molar ratio Bi / Na was 1.0 (Bi 0.5 Na 0.5 ) TiO 3 was blended and dry mixed.
  • raw material powders of BaCO 3 , TiO 2 , and La 2 O 3 were prepared as raw materials for (BaR) [TiM] O 3 calcined powder, blended to become (Ba 0.994 La 0.006 ) TiO 3, and pure water And dried.
  • the raw material of (BiA) TiO 3 calcined powder and the raw material of (BaR) [TiM] O 3 calcined powder were calcined at different temperatures.
  • the raw material of (BiNa) TiO 3 calcined powder was calcined in air at 800 ° C. for 2 hours, and the raw material of (BaLa) TiO 3 calcined powder was calcined in air at 1200 ° C.
  • the BET value of the (BiA) TiO 3 calcined powder was a and the BET value of the (BaR) [TiM] O 3 calcined powder was b
  • the BET value was adjusted so that a / b ⁇ 2.0.
  • the (BiNa) TiO 3 calcined powder was pulverized by using a ball having a media diameter of 5 mm, using pure water as a medium and changing the pulverization time by a pot mill, and then dried.
  • the (BaLa) TiO 3 calcined powder was used without being pulverized.
  • the BET value a (BiNa) TiO 3 calcined powder also described in Table 1 the ratio a / b of the BET value divided by the BET value b of (BaLa) TiO 3 calcined powder.
  • (BiA) TiO 3 calcined powder and (BaR) [TiM] O 3 calcined powder were mixed (Step 2).
  • (BiNa) TiO 3 calcined powder and (BaLa) TiO 3 calcined powder were mixed so as to be [(Bi 0.5 Na 0.5 ) 0.085 (Ba 0.994 La 0.006 ) 0.915 ] TiO 3 .
  • This material was mixed and pulverized with a pot mill using pure water as a medium, and then dried to obtain a third raw material.
  • the third raw material was heat-treated in air at 1150 ° C. for 4 hours (not shown). . Thereafter, 1.5 mol% of Y 2 O 3 , 0.74 mol% of Ba 6 Ti 17 O 40 and 2 mol% of CaCO 3 were added as the Y raw material to the third raw material. Thereafter, the mixture was mixed and pulverized with a pot mill using pure water as a medium, and then dried (not shown).
  • Step 3 10% by mass of PVA was added to the third raw material, mixed, and then granulated with a granulator.
  • the obtained granulated powder was molded with a uniaxial press machine, and then debindered at 700 ° C.
  • Step 4 sintering was performed at 1400 ° C. for 4 hours under nitrogen at an oxygen concentration of 0.01 vol% (100 ppm) to obtain a sintered body.
  • the obtained sintered body is processed into a plate of 10 mm x 10 mm x 1 mm to prepare a test piece, an ohmic electrode is applied, a cover electrode is further applied, dried at 180 ° C and then held at 600 ° C for 10 minutes. An electrode was formed by baking.
  • Table 1 shows the measured room temperature specific resistance ⁇ , Curie temperature Tc, and resistance temperature coefficient ⁇ .
  • the BET value a (BiNa) TiO 3 calcined powder 1.28, the BET value b of (BaLa) TiO 3 calcined powder is 0.81 (Sample No. 1-1).
  • the calcined powder of this comparative example has a BET value ratio a / b of 1.6, and the semiconductor ceramic composition obtained using this calcined powder has a room temperature resistivity ⁇ of 46.2 ⁇ ⁇ cm.
  • the BET value ratio a / b is 2.0 times or more.
  • sample number 1-9 of this embodiment has a slightly higher room temperature resistivity ⁇ and a lower Curie temperature Tc than sample number 1-8, but a lower room temperature than sample number 1-1 of the comparative example. It is a semiconductor ceramic composition having a specific resistance ⁇ and a high Curie temperature Tc.
  • Example 2 Experiments were performed by changing the BET value b of the (BaLa) TiO 3 calcined powder.
  • (BaLa) TiO 3 Example except that the calcining temperature of the raw material of calcined powder was 1150 ° C (sample number 2-1), 1175 ° C (sample number 2-2), 1300 ° C (sample number 2-3) The calcined powder was prepared in the same manner as in Sample No. 1-5.
  • (BiNa) a BET value b of TiO 3 and BET value a calcined powder (BaLa) TiO 3 calcined powder are shown in Table 2.
  • the BET value ratio a / b is also shown in Table 2.
  • Table 2 shows the measured room temperature specific resistance ⁇ , Curie temperature Tc, and resistance temperature coefficient ⁇ .
  • a novel method for producing a semiconductor ceramic composition capable of adjusting the Curie temperature Tc and increasing the room temperature specific resistance ⁇ .

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Abstract

L'invention concerne un nouveau procédé de production qui peut réaliser un ajustement tel que la température de Curie d'une composition céramique semi-conductrice s'élève et la résistivité à température ambiante ρ s'abaisse. Le procédé est un procédé de production d'une composition céramique semi-conductrice, dans lequel on prépare une poudre calcinée de (BiA)TiO3 (A est au moins l'un parmi Na, Li et K) et une poudre calcinée de (BaR)[TiM]O3 (R est au moins l'un parmi les éléments des terres rares comprenant Y, M est au moins l'un parmi Nb, Ta et Sb, et soit R, soit M est requis), on mélange la poudre calcinée de (BiA)TiO3 et la poudre calcinée de (BaR)[TiM]O3 et on réalise ensuite un moulage et un frittage, ledit procédé de production d'une composition céramique semi-conductrice étant caractérisé en ce que, avant le mélange de la poudre calcinée de (BiA)TiO3 et de la poudre calcinée de (BaR)[TiM]O3, la relation a/b ≥ 2,0 est satisfaite, a étant la valeur BET de la poudre calcinée de (BiA)TiO3 et b étant la valeur BET de la poudre calcinée de (BaR)[TiM]O3.
PCT/JP2015/052182 2014-01-31 2015-01-27 Procédé de production d'une composition céramique semi-conductrice, composition céramique semi-conductrice, élément ctp et module d'élément de chauffage WO2015115421A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02106903A (ja) * 1988-10-17 1990-04-19 Nippon Tungsten Co Ltd 高温ｐｔｃサーミスタ及びその製造方法
JPH10218660A (ja) * 1997-01-31 1998-08-18 Matsushita Electric Ind Co Ltd チタン酸バリウム系半導体磁器材料及びそれを用いた半導体磁器の製造方法
WO2013157649A1 (fr) * 2012-04-20 2013-10-24 日立金属株式会社 Composition de céramique semi-conductrice, son procédé de fabrication et un élément à coefficient positif de température (ptc)

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH02106903A (ja) * 1988-10-17 1990-04-19 Nippon Tungsten Co Ltd 高温ｐｔｃサーミスタ及びその製造方法
JPH10218660A (ja) * 1997-01-31 1998-08-18 Matsushita Electric Ind Co Ltd チタン酸バリウム系半導体磁器材料及びそれを用いた半導体磁器の製造方法
WO2013157649A1 (fr) * 2012-04-20 2013-10-24 日立金属株式会社 Composition de céramique semi-conductrice, son procédé de fabrication et un élément à coefficient positif de température (ptc)

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