WO2016002714A1 - Composition de céramique semi-conductrice et élément à ctp - Google Patents

Composition de céramique semi-conductrice et élément à ctp Download PDF

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WO2016002714A1
WO2016002714A1 PCT/JP2015/068678 JP2015068678W WO2016002714A1 WO 2016002714 A1 WO2016002714 A1 WO 2016002714A1 JP 2015068678 W JP2015068678 W JP 2015068678W WO 2016002714 A1 WO2016002714 A1 WO 2016002714A1
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mol
raw material
semiconductor ceramic
ceramic composition
amount
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武司 島田
健太郎 猪野
到 上田
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日立金属株式会社
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
    • H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient

Definitions

  • the present invention relates to a semiconductor ceramic composition and a PTC element used for a PTC heater, a PTC thermistor, a PTC switch, a temperature detector and the like.
  • 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 As a semiconductor porcelain composition that is lead-free and has a high Curie temperature, a part of Ba in the BaTiO 3 oxide is substituted with Bi—Na.
  • Patent Document 1 at least one of the composition formula [(BiA) x (Ba 1 -y R y) 1-x] [Ti 1-z M z] O 3 (A is Na, Li, K, R Is at least one of rare earth elements including Y, M is at least one of Nb, Ta, and Sb), and x, y, and z are 0 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.02, and 0 ⁇ z A semiconductor ceramic composition having crystal grains satisfying ⁇ 0.01 (where y + z> 0) is described.
  • Patent Document 1 describes, as a manufacturing method thereof, (BiA) TiO 3 -based first raw material and (BaR) [TiM] O 3 (R is at least one of rare earth elements including Y, M is Nb, Ta, A second raw material of each system is prepared, and the first raw material is calcined at 700 ° C. or higher and 950 ° C. or lower; The raw material of 2 is calcined at 900 ° C or higher and 1300 ° C or lower, and the calcined materials are mixed to form a third raw material. The third raw material is heat treated at 900 ° C or higher and 1250 ° C or lower, and then sintered. It is described to do.
  • a semiconductor ceramic composition in which part of Ba in the BaTiO 3 oxide is substituted with Bi—Na is effective for shifting the Curie temperature in the positive direction.
  • the temperature coefficient of resistance ⁇ may not be sufficiently high.
  • an object of the present invention is to provide a semiconductor ceramic composition having a high temperature coefficient of resistance ⁇ .
  • Another object of the present invention is to provide a PTC element in which an electrode is formed on the semiconductor ceramic composition.
  • the present invention is a lead-free semiconductor ceramic composition in which a part of Ba in a BaTiO 3 -based oxide is replaced with Bi and A (A is at least one element of an alkali metal and contains Na as an essential element).
  • the amount of Na at the grain boundaries of the crystal grains is 3 mol% or more.
  • the semiconductor ceramic composition of the present invention can have a temperature coefficient of resistance of 4.5% / ° C. or higher.
  • the semiconductor ceramic composition of the present invention at least one composition formula of the crystal grains is [(BiA) x (Ba 1 -y R y) 1-x] [Ti 1-z M z] O 3 (A is an alkali metal Wherein R is at least one of rare earth elements including Y, M is at least one of Nb, Ta, and Sb), and x, y, and z are 0 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.02, and 0 ⁇ z ⁇ 0.01 may be satisfied. Electrodes can be formed on these semiconductor ceramic compositions to form PTC elements.
  • the semiconductor ceramic composition of the present invention can obtain a high resistance temperature coefficient ⁇ when the amount of Na at the grain boundary of the crystal grains is 3 mol% or more even if the composition is the same. Therefore, when an electrode is formed on this semiconductor ceramic composition, a PTC element having an excellent resistance temperature coefficient ⁇ can be obtained.
  • the present invention is a lead-free semiconductor ceramic composition in which a part of Ba in a BaTiO 3 -based oxide is replaced with Bi and A (A is at least one element of an alkali metal and contains Na as an essential element).
  • A is at least one element of an alkali metal and contains Na as an essential element.
  • the crystal grain boundary refers to a boundary surface between two different tetragonal crystal grains (BaTiO 3 -based oxides) 1a and 1b as shown in FIG.
  • the amount of grain boundary Na was measured at the center of the cross section of the boundary surface with a scanning transmission electron microscope (STEM) at a field of view of 100,000 times. Details of the measurement method will be described later.
  • the resistance temperature coefficient ⁇ does not exceed 4.5% / ° C.
  • the grain boundary Na amount is preferably 5 mol% or more, more preferably 7 mol% or more.
  • the upper limit of the amount of grain boundary Na is not particularly limited, but if it exceeds 20 mol%, it becomes a shape of a fired body different from that during molding due to melting or softening, or the processing object in the furnace is installed. There is a problem that it reacts with a table or a container. Therefore, the grain boundary Na content is preferably 20 mol% or less.
  • the semiconductor ceramic composition of the present invention has crystal grains in which a part of Ba in a BaTiO 3 oxide is substituted with Bi and A.
  • the composition formula is [(BiA) x (Ba 1-y R y ) 1-x ] [Ti 1-z M z ] O 3 (A is at least one element of an alkali metal and Na is essential.
  • 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 ⁇ 0.02, Those having crystal grains satisfying 0 ⁇ z ⁇ 0.01 are preferable.
  • ⁇ Curie temperature can be increased from 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. x is more preferably 0.03 or more and 0.1 or less.
  • both R and M are not necessarily required, and at least one of them may be used.
  • the value of y in R may be in the range of 0 ⁇ y ⁇ 0.02, but 0 ⁇ y ⁇ 0.02 is a preferable range.
  • y the composition is not sufficiently semiconducting, and when it exceeds 0.02, the room temperature resistivity tends to increase.
  • the valence can be controlled by changing the value of y.
  • 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.
  • the room temperature resistivity increases due to the presence of A ions.
  • 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.
  • Z indicating the amount of M may be in a range of 0 ⁇ z ⁇ 0.01, but 0 ⁇ z ⁇ 0.01 is a preferable range.
  • z the valence cannot be controlled and the composition is not sufficiently semiconducting.
  • z is more than 0.01, the room temperature resistivity increases or the Curie temperature tends to decrease.
  • a more preferable range is 0.001 ⁇ z ⁇ 0.005.
  • M is preferable because Nb can obtain particularly excellent PTC characteristics among Nb, Ta, and Sb.
  • the ratio of Bi and A should be 1: 1. However, even when this ratio is 1: 1 when blending the materials, Bi is volatilized by the calcination or sintering process, and the ratio of Bi and A is shifted, resulting in a 1: 1 ratio in the sintered body. This is also included in the present invention.
  • An allowable range of Bi: A 0.78 to 1.55: 1 is acceptable, and an increase in heterogeneous phase can be suppressed within this range, so that an increase in room temperature resistivity and a change with time can be suppressed.
  • a site: B site 0.9 to 1.0: 1, more preferably 0.990 to 1.000: 1.
  • the effect of reducing the change with time and the effect of improving the resistance temperature coefficient ⁇ can be expected.
  • Si raw materials and Ca raw materials can be used as sintering aids.
  • Si and Ca may be included in the above composition formula.
  • the semiconductor ceramic composition of this invention is demonstrated.
  • the semiconductor ceramic composition can be obtained by using a Na compound having a melting point of 865 ° C. or higher.
  • a Na compound having a melting point of less than 865 ° C. is used, Na cannot be precipitated at 3 mol% or more at the grain boundary.
  • the Na compound preferably has a melting point of 1000 ° C. or higher, more preferably 1100 ° C. or higher.
  • Na 2 Ti 3 O 7 (melting point: about 1130 ° C), Na 2 Ti 6 O 13 (melting point: about 1300 ° C), or Na 0.5 Bi 4.5 Ti 4 O 15 (melting point: 1300 ° C or higher) should be used. Can do.
  • a Na compound with a high melting point when NaTiO 3 -based oxide crystal grains are formed, some of the Na in the Na compound is not taken into the crystal grains and remains at the crystal grain boundaries. Na can be segregated at grain boundaries. As a result, the semiconductor ceramic composition having a large resistance temperature coefficient ⁇ according to the present invention is obtained.
  • Step 1 a manufacturing method having steps (Step 1) to (Step 7) shown in FIG. 5 below can be adopted.
  • Step 1 (BiA) TiO 3 system (A is at least one element of alkali metal and contains Na essential) and (BaR) [TiM] O 3 (R is a rare earth element containing Y) At least one of them, M is at least one of Nb, Ta, and Sb, and at least one of R and M is essential).
  • Step 2 The first raw material is calcined at 700 ° C. or higher and 950 ° C. or lower, the second raw material is calcined at 900 ° C. or higher and 1300 ° C.
  • Step 3 Mix each calcined material to make the third raw material, (Step 4)
  • the third raw material is heat-treated at 900 ° C. or higher and 1250 ° C. or lower, and then (Step 5)
  • a Na compound having a melting point of 865 ° C. or higher is added, (Step6) Molding, (Step 7) Sinter at 1200 ° C or higher and 1500 ° C or lower.
  • the production method for obtaining the semiconductor ceramic composition of the present invention particularly has (Step 5) “step of adding a Na compound having a melting point of 865 ° C. or higher to the heat-treated third raw material”. .
  • Step 5 a semiconductor ceramic composition having an excellent resistance temperature coefficient ⁇ is obtained.
  • the third raw material is heat-treated at 900 ° C. or higher and 1250 ° C.
  • the [(BiA) (BaR)] [TiM] O 3 compound has a composition that is stable to some extent even at high temperatures, fluctuations in the composition are suppressed even in subsequent sintering. Since the added Na compound has a high melting point, the time for Na to volatilize can be shortened, and the time during which the Na component is in a liquid phase during sintering can be shortened. It is suppressed that Na is contained in the grains. By this mechanism, Na is likely to segregate at the grain boundaries of the crystal, and the Schottky barrier at the grain boundaries increases, so it is assumed that the temperature coefficient of resistance increases.
  • the steps (Step 1) to (Step 7) will be described below.
  • (Step 1) will be described in detail.
  • the (BiA) TiO 3 -based first raw material is prepared by mixing A 2 CO 3 , Bi 2 O 3 , and TiO 2 as raw material powders.
  • the (BiA) TiO 3 -based first raw material refers to a raw material for forming the (BiA) TiO 3 oxide.
  • the (BaR) [TiM] O 3 -based second raw material is a raw material powder of BaCO 3 , TiO 2 , R, M, for example, an R element oxide such as La 2 O 3 , Nb 2 O 5, etc. It is made by mixing the M element oxide. R and M are used as semiconducting elements.
  • the (BaR) [TiM] O 3 -based second raw material refers to a raw material for forming the (BaR) [TiM] O 3 oxide.
  • both the first raw material and the second raw material may be pulverized according to the particle size of the raw material powder when the raw material powder is mixed.
  • 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.
  • a 2 CO 3 , Bi 2 O 3 , TiO 2, etc. another A compound, Bi compound, or Ti compound may be used as the first raw material.
  • other Ba compounds and Ti compounds may be used for the second raw material in addition to BaCO 3 , TiO 2 and the like.
  • the calcination of the (BiA) TiO 3 -based first raw material in (Step 2) will be described in detail.
  • the calcining temperature of the first raw material is 700 ° C. or higher and 950 ° C. or lower.
  • the calcining temperature is less than 700 ° C, unreacted A 2 CO 3 and Bi or Ti and unreacted A 2 O react with the solvent in the case of moisture in the furnace atmosphere or wet mixing, and generate heat, The composition tends to deviate from the desired value and PTC characteristics tend to become unstable.
  • the calcining temperature exceeds 950 ° C., the volatilization of Bi proceeds, causing a composition shift and promoting the generation of a different phase.
  • the calcination time is preferably 0.5 hours or more and 10 hours or less.
  • the calcination time is less than 0.5 hours, the obtained PTC characteristics are likely to be unstable for the same reason as when the calcination temperature is less than 700 ° C.
  • the calcining time exceeds 10 hours, the generation of a heterogeneous phase is easily promoted for the same reason as when the calcining temperature exceeds 950 ° C.
  • the calcination time is preferably 1 hour or more and 8 hours or less.
  • the calcination of the first raw material is preferably performed in the air. In order to suppress the volatilization of Bi, the calcining temperature of the first raw material is preferably lower than the calcining temperature of the second raw material.
  • the composition of the second raw material is such that neither R nor M is added, the room temperature resistivity increases. Therefore, it is preferable that at least one of R and M is essential.
  • the calcination of the (BaR) [TiM] O 3 -based second raw material in (Step 2) will be described in detail.
  • the calcining temperature of the second raw material is 900 ° C. or higher and 1300 ° C. or lower.
  • (BaR) [TiM] O 3 is not completely formed, and some BaO decomposed from BaCO 3 reacts with water, or a part of the remaining BaCO 3 is water. Or the like, it may cause a compositional deviation and the characteristics may vary.
  • the calcining time is preferably 0.5 hours or more. If the calcining time is less than 0.5 hours, it causes a composition shift.
  • the upper limit is not particularly limited, but it is preferable that the upper limit is 100 hours or less because solid solution with the (BiA) TiO 3 calcined powder to be mixed later can be promoted.
  • the calcination of the second raw material is preferably performed in the air.
  • Step 3 Each calcined powder is blended in a predetermined amount and then mixed to obtain a third raw material.
  • Mixing may be either wet mixing using pure water or ethanol or dry mixing.
  • pulverization may be performed after mixing, or mixing and pulverization may be performed simultaneously.
  • the average particle size of the calcined powder after mixing and pulverization is preferably 0.5 ⁇ m to 7.0 ⁇ m. Furthermore, 0.8 ⁇ m to 5.0 ⁇ m is preferable, and 1.0 ⁇ m to 4.0 ⁇ m is more preferable.
  • the third raw material is heat-treated at 900 ° C. to 1250 ° C.
  • the composition of the first calcined powder and the second calcined powder can be made uniform, and the homogenized state is close to the state immediately before the crystal grains are grown.
  • the temperature of the heat treatment is preferably set to a temperature at which the diffraction line peaks of the X-ray diffraction of both compositions are in the same position, that is, a solid solution state by this step. Below 900 ° C, Bi is not sufficiently diffused.
  • the melting point of the (BiA) TiO 3 system is around 1250 ° C, so Bi evaporates into the furnace atmosphere.
  • a more preferable heat treatment temperature is 1000 ° C. or higher and 1200 ° C. or lower.
  • the heat treatment time is preferably 0.5 hours or more and 20 hours or less.
  • the time is shorter than 0.5 hours, the solid solution of the (BaR) [TiM] O 3 type calcined powder and the (BiA) TiO 3 type calcined powder is not stable, and the obtained PTC characteristics are not stable.
  • the volatilization of Bi increases and the composition shift tends to occur.
  • the heat treatment time is preferably 1 hour or more and 12 hours or less, more preferably 1.5 hours or more and 6 hours or less.
  • the heat treatment of the third raw material is preferably performed in the atmosphere.
  • Step 5 A Na compound having a melting point of 865 ° C. or higher is added to the heat-treated third raw material.
  • Na 2 Ti 3 O 7 (melting point: about 1130 ° C), Na 2 Ti 6 O 13 (melting point: about 1300 ° C), or Na 0.5 Bi 4.5 Ti 4 O 15 (melting point: 1300 ° C or higher) should be used as the Na compound.
  • a Na compound after the heat treatment of (Step 4) above it is possible to suppress the inclusion of Na in the crystal grains, compared with a case where a Na compound having a melting point of less than 865 ° C. (for example, Na 2 CO 3 ) is used. And the amount of grain boundary Na can be increased.
  • the Na compound When Na 2 Ti 3 O 7 or Na 2 Ti 6 O 13 is used as the Na compound, it is preferable to add 0.005 mol% or more with the third raw material as 100 mol%. If it is less than 0.005 mol%, the amount of grain boundary Na generated at the crystal grain boundary does not exceed 3 mol%, and as a result, the effect of increasing the resistance temperature coefficient ⁇ cannot be obtained.
  • the upper limit is not particularly limited, but if it exceeds 5 mol%, there is a problem that the material melts or softens during firing to form a fired body different from that during molding or reacts with the container of the firing furnace. is there. Therefore, the upper limit is preferably 5 mol% or less.
  • a more preferable amount of Na compound added is 0.5 mol% or more and 3 mol% or less.
  • Na 0.5 Bi 4.5 Ti 4 O 15 is used, it is preferably added in a range of 0.1 mol% or more.
  • the upper limit is not particularly limited, but is preferably 5 mol% or less. The reason for limiting the upper limit and the lower limit is the same as that when Na 2 Ti 3 O 7 or Na 2 Ti 6 O 13 is used.
  • a preferable addition amount of Na 0.5 Bi 4.5 Ti 4 O 15 is 0.5 mol% or more and 3.5 mol% or less.
  • a known method can be adopted to mix the third raw material and the Na compound.
  • an organic solvent and a third raw material are mixed to form a slurry having a solid solution concentration of 30 to 60%, and a Na compound is added to the slurry until the center particle diameter becomes 1.0 to 5.0 ⁇ m by a ball mill or a pot mill.
  • a means for mixing while pulverizing can be used.
  • a Y raw material such as Y 2 O 3 .
  • Y material is preferably added in the third Y 2 0 3 4.0 mol% or less of the range of 0.5 mol% in terms of the raw material.
  • an oxide containing Ba and Ti that is in a liquid phase at a temperature higher than 1250 ° C. and not higher than 1500 ° C. (hereinafter referred to as BaTi oxide) may be mixed. It can.
  • BaTi oxide By adding BaTi oxide, even if the sintering temperature varies, the resistance temperature coefficient ⁇ can be suppressed from decreasing, and the obtained characteristics are stabilized. Further, the addition of BaTi oxide can reduce the change with time in the PTC characteristics.
  • BaTi oxide is represented by the composition formula Ba 6 Ti 17 O 40 , BaTi 2 O 5 , Ba 4 Ti 13 O 30 , BaTi 3 O 7 , BaTi 4 O 9 , Ba 2 Ti 9 O 20 , Ba 2 TiO 5. Can be applied. Even if the sintering temperature is low, the resistance temperature coefficient ⁇ can be suppressed from decreasing. It is particularly preferable to use Ba 6 Ti 17 O 40 as the BaTi oxide.
  • the BaTi oxide is preferably added in an amount of 0.1 mol% or more and 1.0 mol% or less in terms of the above composition formula with respect to the third raw material.
  • Step 6 A mixture of the third raw material and the Na compound is formed. You may granulate a mixture with a granulator as needed before shaping
  • Step 7 Sintering can be performed at a sintering temperature of 1200 ° C to 1500 ° C. If the sintering temperature is less than 1200 ° C., the sintering tends to be insufficient. If the sintering temperature exceeds 1500 ° C., it becomes soft during sintering and does not become a desired shape, and the temperature coefficient of resistance ⁇ tends to decrease.
  • the sintering temperature is more preferably 1250 ° C. or higher and 1460 ° C. or lower.
  • the sintering temperature is more preferably 1200 ° C. or higher and 1380 ° C. or lower.
  • the sintering temperature is more preferably 1200 ° C. or higher and 1500 ° C. or lower.
  • the atmosphere during sintering is preferably the air, a reducing atmosphere, or an inert gas atmosphere having a low oxygen concentration.
  • 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, Na precipitated at the grain boundary diffuses from the grain boundary and forms another phase that is not tetragonal between the crystals, resulting in a low resistance temperature coefficient ⁇ . There is a possibility of becoming.
  • a more preferable sintering time is 2 hours or more and 6 hours or less.
  • the amount of Na at the crystal grain boundary, the temperature coefficient of resistance ⁇ , the evaluation method of the room temperature specific resistance R 25 , and the composition analysis of the crystal grains were performed as follows.
  • the temperature coefficient of resistance ⁇ was calculated by measuring the resistance-temperature characteristics while raising the temperature of the semiconductor ceramic composition to 260 ° C.
  • ⁇ (lnR L -lnR C ) ⁇ 100 / (T L -T C )
  • R L is the specific resistance at 260 ° C
  • T L is 260 ° C
  • T C is the Curie temperature
  • R C is T C
  • the Curie temperature T C was set to a temperature at which the non-resistance is twice the room temperature specific resistance R 25 .
  • the room temperature resistivity R 25 ( ⁇ cm) of the semiconductor ceramic composition was measured at 25 ° C. by a four-terminal method.
  • composition analysis of crystal grains Using an atomic resolution analytical electron microscope (model number JEM-ARM200F) manufactured by JEOL, the inside of the crystal grains was subjected to elemental analysis by STEM-EDX. The measurement conditions were the same as the measurement of the grain boundary Na amount.
  • Example 1 By changing the amount of Na compound added, the relationship between the change in grain boundary Na amount and the accompanying temperature coefficient of resistance ⁇ was investigated.
  • a (BiA) TiO 3 -based first material and a (BaR) [TiM] O 3 -based second material were prepared as raw materials (Step 1).
  • raw material powder of Na 2 CO 3 , Bi 2 O 3 , TiO 2 was prepared as the first raw material of (BiA) TiO 3 system, and the molar ratio Bi / Na Bi / Na of 1.05 ( Bi 0.525 Na 0.500 ) TiO 3 was blended and dry mixed.
  • a raw material powder of BaCO 3 , TiO 2 , and La 2 O 3 was prepared as the second raw material of the (BaR) [TiM] O 3 system, blended so as to be (Ba 0.994 La 0.006 ) TiO 3, and pure Mixed with water.
  • the first raw material was calcined at 700 to 950 ° C.
  • the second raw material was calcined at 900 to 1300 ° C. (Step 2).
  • the obtained first raw material was calcined in the air at 800 ° C. for 2 hours to prepare a (BiA) TiO 3 -based calcined powder.
  • the second raw material was calcined at 1200 ° C.
  • (BaR) [TiM] O 3 -based calcined powder The calcined materials were mixed to obtain a third raw material (Step 3).
  • (BiA) TiO 3 -based calcined powder and (BaR) [TiM] O 3 -based calcined powder were converted into [(Bi 0.5 Na 0.5 ) 0.085 (Ba 0.994 La 0.006 ) 0.915 ] TiO 3 It mixed so that it might become.
  • This material was mixed and pulverized with a pot mill using pure water as a medium until the average particle size became 2.0 ⁇ m to 3.0 ⁇ m, and then dried to obtain a third raw material.
  • the third raw material was heat-treated at 900 ° C. to 1250 ° C. (Step 4).
  • the third raw material, with 4 hours in the air went.
  • the third raw material heat-treated at this temperature has one diffraction line for each of the (BaR) [TiM] O 3 type calcined powder and the (BiA) TiO 3 type calcined powder as measured by X-ray diffraction. It was.
  • a Na compound having a melting point of 865 ° C. or higher was added to the heat-treated third raw material (Step 5).
  • a Na 2 Ti 3 O 7 compound was used as the Na compound, and 0.01 mol%, 0.5 mol%, 2.0 mol%, 4.0 mol%, and 5.0 mol% were added with the third raw material as 100 mol%.
  • BaTi oxide represented by Ba 6 Ti 17 O 40 , Y 2 O 3 and CaCO 3 were added.
  • the addition amount of Ba 6 Ti 17 O 40 , Y 2 O 3 and CaCO 3 is that the third raw material is 100 mol%, Ba 6 Ti 17 O 40 is 0.6 mol%, Y 2 O 3 is 1.0 mol%, CaCO 3 Was 2 mol%.
  • a product without addition of Na compound (0 mol%) was also produced.
  • Comparative Example 1 a semiconductor ceramic composition was produced in the same manner as in Example 1 except that no Na compound was added. The same applies to the following steps. Thereafter, molding was performed (Step 6). In this example, PVA was added, mixed, and granulated. The obtained granulated powder was molded with a single screw press machine and subjected to binder removal treatment by heating at 700 ° C.
  • Step 7 sintering was performed in nitrogen at an oxygen concentration of 0.007 vol% (70 ppm) by holding at 1420 ° C. for 4 hours to obtain a sintered body.
  • the obtained sintered body is processed into a plate of 10 mm ⁇ 10 mm ⁇ 1.0 mm to produce a test piece, a base metal ohmic electrode is applied, and a cover electrode mainly composed of Ag is further applied to 180 ° C. After drying, the electrode was formed by baking at 600 ° C. for 10 minutes to form a PTC element.
  • Table 1 shows the results of the amount of Na compound added, the amount of grain boundary Na, the resistance temperature coefficient ⁇ , the room temperature resistivity R 25 , and the Curie temperature Tc.
  • the comparative examples are marked with *.
  • composition formula was [(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 at least one of rare earth elements including Y, M is at least one of Nb, Ta and Sb), and x, y and z are 0 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.02, and 0 ⁇ z ⁇ 0.01 were satisfied.
  • No. 1-1 is a comparative semiconductor porcelain composition prepared without adding a Na compound, but the amount of grain boundary Na was less than 3 mol%.
  • the temperature coefficient of resistance ⁇ was as low as 4.4% / ° C.
  • the grain boundary Na amount was all 3 mol% or more, and the resistance temperature coefficient ⁇ was all 4.5% / ° C. or more.
  • Fig. 4 shows the result of observation of the grain boundaries of No. 1-3 by STEM.
  • crystal grains 1a and 1b on the left and right, and the grain boundary 2 of the crystal grains can be confirmed.
  • the amount of Na in the grain boundary 2 was measured in the same field of view, it was confirmed that the amount of Na in the grain boundary was larger than that in the crystal grains.
  • Example 2 The relationship between the change in the grain boundary Na amount and the accompanying resistance temperature coefficient ⁇ was investigated by changing the sintering temperature.
  • (Step 1) to (Step 4) were performed under the same conditions as in the production methods of No. 1-3 and No. 1-4 of Example 1 (the addition amounts of Na compound were 0.5 mol% and 2.0 mol%). Thereafter, a Na compound having a melting point of 865 ° C. or higher was added to the third raw material heat-treated in (Step 4) (Step 5). In this example, a Na 2 Ti 3 O 7 compound was used as the Na compound, and the third raw material was added at 0.5 mol% with 100 mol% and 2.0 mol% added.
  • BaTi oxide represented by Ba 6 Ti 17 O 40 , Y 2 O 3 and CaCO 3 were added.
  • the amount of addition was 100 mol% for the third raw material, 0.6 mol% for Ba 6 Ti 17 O 40 , 1.0 mol% for Y 2 O 3 and 2 mol% for CaCO 3 .
  • molding was performed (Step 6).
  • PVA was added, mixed, and granulated.
  • the obtained granulated powder was molded with a single screw press machine and subjected to binder removal treatment by heating at 700 ° C. for 10 hours. Thereafter, sintering was performed (Step 7).
  • the sintering temperature was changed in the range of 1300 ° C. to 1460 ° C., and the oxygen concentration was 0.007 vol% in nitrogen after holding for 4 hours. Sintering was performed under the condition of (70 ppm) to obtain respective sintered bodies (2-1 to 2-7).
  • the oxygen concentration was 0.007vol% (70ppm) in nitrogen after holding for 4 hours. Sintering was performed under the conditions to obtain sintered bodies (2-8 to 2-13).
  • Table 2 shows the results of the Na compound addition amount, sintering temperature, grain boundary Na amount, resistance temperature coefficient ⁇ , room temperature resistivity R 25 , and Curie temperature Tc.
  • the semiconductor ceramic composition of the present invention having a grain boundary Na amount of 3.0 mol% or more had a high resistance temperature coefficient ⁇ , and in this example, all were 4.5% / ° C. or more.
  • the resistance temperature coefficient ⁇ is more preferably 5.0% / ° C. or more.
  • Step 1 A Na compound having a melting point of less than 865 ° C. was used, and the relationship between the change in grain boundary Na amount and the accompanying temperature coefficient of resistance ⁇ was investigated. (Step 1) to (Step 4) were performed under the same conditions as in No. 2-3 of Example 2 (the amount of Na compound added was 0.5 mol%). Thereafter, Na 2 CO 3 having a melting point of 851 ° C. was added to the heat-treated third raw material at 0.4 mol% with the third raw material as 100 mol% (corresponding to Step 5).
  • the BaTi oxide and Y 2 O 3 and CaCO 3 represented by Ba 6 Ti 17 O 40 with respect to the third material, BaTi oxide 0.6 mol%, Y 2 O 3 is 1.0 mol%, CaCO 3 was added at 2 mol%. Thereafter, a PTC element was manufactured through the same process as the manufacturing method of Example 1 and evaluated. Table 3 shows the results of the amount of Na compound added, the amount of grain boundary Na, the resistance temperature coefficient ⁇ , the room temperature specific resistance R 25 , and the Curie temperature Tc.
  • the amount of grain boundary Na was less than 3.0 mol%. Further, the temperature coefficient of resistance ⁇ was low, which was 2.3% / ° C. in this comparative example.
  • Example 3 The composition formula changes the amount of R (La amount) in [(BiA) x (Ba 1-y R y ) 1-x ] [Ti 1-z M z ] O 3 and changes the amount of grain boundary Na and accompanying it The relationship of the resistance temperature coefficient ⁇ was examined. As shown in FIG. 5, a (BiA) TiO 3 -based first material and a (BaR) [TiM] O 3 -based second material were prepared as raw materials (Step 1).
  • raw material powder of Na 2 CO 3 , Bi 2 O 3 , TiO 2 was prepared as the first raw material of (BiA) TiO 3 system, and the molar ratio Bi / Na Bi / Na of 1.05 ( Bi 0.525 Na 0.500 ) TiO 3 was blended and dry mixed.
  • raw material powders of BaCO 3 , TiO 2 , and La 2 O 3 are prepared as (BaR) [TiM] O 3 -based second raw materials, and (Ba 0.999 La 0.001 ) TiO 3 , (Ba 0.998 La 0.002 ) TiO 3 and (Ba 0.997 La 0.003 ) TiO 3 , respectively, and mixed with pure water (Step 1).
  • Step 2 and subsequent steps were manufactured under the same conditions as in the manufacturing method of Example 1, then processed, formed electrodes, manufactured PTC elements, and evaluated.
  • Table 4 shows the results of the Na compound addition amount, R amount y, grain boundary Na amount, resistance temperature coefficient ⁇ , room temperature resistivity R 25 , and Curie temperature Tc.
  • composition formula was [(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 at least one of rare earth elements including Y, M is at least one of Nb, Ta and Sb), and x, y and z are 0 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.02, and 0 ⁇ z ⁇ 0.01 were satisfied.
  • the semiconductor ceramic composition of the present invention having a grain boundary Na amount of 3.0 mol% or more has a higher resistance temperature coefficient ⁇ than that of the comparative example (No. 1-1). All were above 4.5% / ° C.
  • FIG. 1 shows the relationship between the amount of grain boundary Na and the temperature coefficient of resistance ⁇ of the semiconductor ceramic composition of the present invention.
  • the amount of grain boundary Na and the resistance temperature coefficient ⁇ used in FIG. 1 are the values in Tables 1, 2, and 4 of Examples 1 to 3.
  • the black points are the comparative example (No. 1-1).
  • the temperature coefficient of resistance ⁇ tends to increase as the grain boundary Na amount increases.
  • No. 1-1 having a grain boundary Na amount of less than 3 mol% has a small grain temperature Na amount of 2.7 mol% and a small temperature coefficient of resistance ⁇ , specifically less than 4.5% / ° C.
  • the resistance temperature coefficient ⁇ is 4.5% / ° C.
  • the resistance temperature coefficient ⁇ tends to increase as the grain boundary Na amount increases.
  • the grain boundary Na amount is 5 mol% or more
  • the grain boundary Na amount and the resistance temperature coefficient ⁇ are proportionally improved, and the resistance temperature coefficient ⁇ is further increased.
  • FIG. 7 is a diagram schematically showing measurement locations when sample No. 2-12 is subjected to line analysis by STEM-EDX. Each measurement point is the position of a round point on a line drawn in the center lateral direction. The magnification is 100,000 times.
  • FIG. 8 shows the Na concentration and Bi concentration when Sample No. 2-12 was subjected to line analysis. The Na concentration tends to increase from the inside of the grain toward the interface. On the other hand, such a tendency was not seen in the Bi concentration. Although not shown in the figure, Ti also tends to have a higher concentration at the interface than in the grains. However, the concentration of Ba tended to decrease as the concentration of Ti increased.
  • the temperature coefficient of resistance ⁇ of Sample No. 2-12 is 6.0% / ° C.
  • Example 4 The type of Na compound was changed, and the relationship between the change in grain boundary Na content and the accompanying temperature coefficient of resistance ⁇ was investigated.
  • (Step 1) to (Step 4) were performed under the same conditions as in the manufacturing method of Example 1. Thereafter, a Na compound having a melting point of 865 ° C. or higher was added to the heat-treated third raw material (Step 5). Na 2 Ti 6 O 13 was used as the Na compound. A material obtained by adding 0.5 mol% the Na 2 Ti 6 O 13 a third raw material as 100 mol%, was prepared which was added 2.0 mol%. Thereafter, in this example, BaTi oxide represented by Ba 6 Ti 17 O 40 , Y 2 O 3 and CaCO 3 were added.
  • the addition amount of Ba 6 Ti 17 O 40 , Y 2 O 3 and CaCO 3 is that the third raw material is 100 mol%, Ba 6 Ti 17 O 40 is 0.6 mol%, Y 2 O 3 is 1.0 mol%, CaCO 3 Was 2 mol%. Thereafter, molding was performed (Step 6). In this example, PVA was added, mixed, and granulated. The obtained granulated powder was molded with a uniaxial press machine and subjected to binder removal treatment at 700 ° C. for 10 hours. Thereafter, sintering was performed (Step 7).
  • composition formula was [(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 at least one of rare earth elements including Y, M is at least one of Nb, Ta, and Sb), and x, y, and z are 0 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.02, and 0 ⁇ z ⁇ 0.01 were satisfied.
  • the semiconductor ceramic composition of the present invention having a grain boundary Na amount of 3.0 mol% or more had a high resistance temperature coefficient ⁇ , and in this example, it was all 4.5% / ° C. or more.
  • These semiconductor porcelain compositions having a large room temperature specific resistance can be used for PTC elements that require withstand voltage, such as electric vehicles.
  • FIG. 2 is a graph showing the relationship between the amount of grain boundary Na and the temperature coefficient of resistance ⁇ in the semiconductor ceramic composition shown in Table 5. As in FIG. 1, it was found that the temperature coefficient of resistance ⁇ tends to increase as the grain boundary Na amount increases in the semiconductor ceramic composition of this example.
  • Example 5 By further changing the kind of Na compound, the relationship between the change in grain boundary Na amount and the accompanying temperature coefficient of resistance ⁇ was investigated. As in Example 1, (Step 1) to (Step 4) were performed. Thereafter, a Na compound having a melting point of 865 ° C. or higher was added to the heat-treated third raw material (Step 5). Na 0.5 Bi 4.5 Ti 4 O 15 was used as the Na compound. As a Na 0.5 Bi 4.5 Ti 4 O 15 was added 0.5 mol% of a third material as 100 mol%, and those obtained by adding 2.0 mol%, was prepared which was added 5.0 mol%. In addition, for comparison, a sample without Na compound (0 mol%) was also prepared.
  • BaTi oxide represented by Ba 6 Ti 17 O 40 , Y 2 O 3 and CaCO 3 were added.
  • the third raw material was 100 mol%
  • the addition amount of Ba 6 Ti 17 O 40 was 0.6 mol%
  • the addition amount of Y 2 O 3 was 1.0 mol%
  • the addition amount of CaCO 3 was 2 mol%.
  • molding was performed (Step 6).
  • PVA was added, mixed, and granulated.
  • the obtained granulated powder was molded with a uniaxial press machine and subjected to binder removal treatment at 700 ° C. for 10 hours. Thereafter, sintering was performed (Step 7).
  • Step 5 Na 0.5 Bi 4.5 Ti 4 O 15 with 5.0 mol% was added at a sintering temperature of 1420 ° C. and maintained for 4 hours under nitrogen at an oxygen concentration of 0.007 vol% (70 ppm). Sintered to obtain a sintered body (6-15). Subsequent processing, electrode formation, and evaluation were performed in the same manner as in Example 1. Table 6 shows the results of the Na compound addition amount, sintering temperature, grain boundary Na amount, resistance temperature coefficient ⁇ , room temperature resistivity R 25 , and Curie temperature Tc. Comparative examples are marked with *.
  • composition formula was [(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 at least one of rare earth elements including Y, M is at least one of Nb, Ta, and Sb), and x, y, and z are 0 ⁇ x ⁇ 0.2, 0 ⁇ y ⁇ 0.02, and 0 ⁇ z ⁇ 0.01 were satisfied.
  • No. 6-1 is a comparative semiconductor porcelain composition prepared without adding a Na compound, but the grain boundary Na content was less than 3 mol%.
  • the temperature coefficient of resistance ⁇ was 4.1% / ° C.
  • the grain boundary Na amount was all 3 mol% or more, and the temperature coefficient of resistance ⁇ was 4.5% / ° C. or more.
  • FIG. 3 is a diagram showing the relationship between the amount of grain boundary Na and the resistance temperature coefficient ⁇ in the semiconductor ceramic composition shown in Table 6. Similar to FIG. 2, it was found that the temperature coefficient of resistance ⁇ tends to increase as the grain boundary Na amount increases in the semiconductor ceramic composition of this example.
  • a PTC element can be obtained by processing the semiconductor ceramic composition of the present invention into a plate shape and forming electrodes on both sides of the plate.
  • a method for forming the electrode a known means can be adopted, but a means for baking after applying the electrode paste is low in cost, and this means is adopted in this embodiment.
  • the semiconductor ceramic composition obtained by the present invention is optimal as a material for PTC heaters, PTC thermistors, PTC switches, temperature detectors and the like.

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Abstract

L'objet de la présente invention est de fournir une composition de céramique semi-conductrice présentant un coefficient de température de résistance α élevé. De plus, l'objet de l'invention est de fournir un élément à CTP dans lequel la composition de céramique semi-conductrice forme une électrode. L'invention concerne une composition de céramique semi-conductrice qui est exempte de plomb et dans laquelle une partie du Ba dans un oxyde de type BaTiO3 a été remplacée par du Bi et A (A représentant au moins un élément de métal alcalin et Na étant essentiel), la composition de céramique semi-conductrice étant caractérisée en ce que la quantité de Na au niveau du joint des grains des cristaux est supérieure ou égale à 3 % en moles. Le coefficient de température de résistance est de préférence supérieur ou égal à 4,5 %/°C.
PCT/JP2015/068678 2014-07-02 2015-06-29 Composition de céramique semi-conductrice et élément à ctp WO2016002714A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008038538A1 (fr) * 2006-09-28 2008-04-03 Murata Manufacturing Co., Ltd. Composition de porcelaine semiconductrice de titanate de baryum et dispositif ptc utilisant celle-ci
WO2008050875A1 (fr) * 2006-10-27 2008-05-02 Hitachi Metals, Ltd. Composition céramique de semi-conducteur et son procédé de fabrication
JP2009155145A (ja) * 2007-12-26 2009-07-16 Hitachi Metals Ltd 半導体磁器組成物
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 (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008038538A1 (fr) * 2006-09-28 2008-04-03 Murata Manufacturing Co., Ltd. Composition de porcelaine semiconductrice de titanate de baryum et dispositif ptc utilisant celle-ci
WO2008050875A1 (fr) * 2006-10-27 2008-05-02 Hitachi Metals, Ltd. Composition céramique de semi-conducteur et son procédé de fabrication
JP2009155145A (ja) * 2007-12-26 2009-07-16 Hitachi Metals Ltd 半導体磁器組成物
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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