CN114573335A - Composition for forming dielectric ceramic and dielectric ceramic material - Google Patents

Composition for forming dielectric ceramic and dielectric ceramic material Download PDF

Info

Publication number
CN114573335A
CN114573335A CN202111440397.2A CN202111440397A CN114573335A CN 114573335 A CN114573335 A CN 114573335A CN 202111440397 A CN202111440397 A CN 202111440397A CN 114573335 A CN114573335 A CN 114573335A
Authority
CN
China
Prior art keywords
compound
dielectric ceramic
terms
forming composition
ltoreq
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202111440397.2A
Other languages
Chinese (zh)
Inventor
国枝武久
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Chemical Industrial Co Ltd
Original Assignee
Nippon Chemical Industrial Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Chemical Industrial Co Ltd filed Critical Nippon Chemical Industrial Co Ltd
Publication of CN114573335A publication Critical patent/CN114573335A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C04B35/4682—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 based on BaTiO3 perovskite phase
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/002—Details
    • H01G4/018—Dielectrics
    • H01G4/06—Solid dielectrics
    • H01G4/08—Inorganic dielectrics
    • H01G4/12—Ceramic dielectrics
    • H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
    • H01G4/1218—Ceramic dielectrics characterised by the ceramic dielectric material based on titanium oxides or titanates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G4/00—Fixed capacitors; Processes of their manufacture
    • H01G4/30—Stacked capacitors
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
    • C04B2235/3225—Yttrium oxide or oxide-forming salts thereof
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3239—Vanadium oxides, vanadates or oxide forming salts thereof, e.g. magnesium vanadate
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5409—Particle size related information expressed by specific surface values
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • 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
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/74—Physical characteristics
    • C04B2235/76—Crystal structural characteristics, e.g. symmetry
    • C04B2235/768—Perovskite structure ABO3

Abstract

Provided are a composition for forming a dielectric ceramic and a dielectric ceramic material obtained by firing the composition. The composition contains (Ba) as a main component1－xCax)mTiO3A perovskite-type composite oxide represented by (0. ltoreq. x. ltoreq.0.250, 0.980. ltoreq. M. ltoreq.1.020), an M compound (M is at least 1 of Ba and Ca), an Mg compound, an Mn compound, a Ma compound (Ma is at least 1 of V, Nb and Ta), an Mb compound (Mb is at least 1 of Y, Tb, Dy, Ho, Er, Tm and Yb), and an Mc compound (Mc is at least 1 of Si and Ge) as additional components, the amount of the additional components being 0.01 to 5.00mol in terms of MO, 0.20 to 2.00mol in terms of MgO, 0.05 to 0.40mol in terms of MnO, and Ma in terms of Ma based on 100mol of the perovskite-type composite oxide2O50.02-0.20 mol in terms of Mb2O30.20 to 3.00mol in terms of McO2Calculated by 0.18 to 3.50mol, Ma2O5/Mb2O3Is 0.010 or more, McO2/Mb2O3Is 0.90 or more.

Description

Composition for forming dielectric ceramic and dielectric ceramic material
Technical Field
The present invention relates to a dielectric ceramic-forming composition and a dielectric ceramic material obtained by firing the dielectric ceramic-forming composition.
Background
As the dielectric ceramic-forming composition for multilayer ceramic capacitor, BaTiO is generally used3Barium titanate and the like are used as the main components, and various elements are added as additive component elements for the purpose of imparting various properties such as reduction resistance, adjustment of temperature characteristics, and improvement of reliability.
As a dielectric ceramic-forming composition containing such additive element, for example, patent document 1 describes the following technique: in order to satisfy desired temperature characteristics and electrical characteristics and reduce short-circuit defect rates even when the dielectric layer thickness is an ultra-thin layer, a desired amount of a magnesium compound, an yttrium compound, a scandium compound, an europium compound, a gadolinium compound, a dysprosium compound, a holmium compound, an erbium compound, a thulium compound, an ytterbium compound, a lutetium compound, a terbium compound, a barium compound, a strontium compound, a calcium compound, a silicon compound, a manganese compound, a chromium compound, a vanadium compound, a molybdenum compound, a tungsten compound, a niobium compound, and a tantalum compound are added to barium titanate and calcined to obtain a dielectric ceramic composition. For the same purpose, several documents have proposed a technique of containing a secondary component such as a magnesium compound or a manganese compound in barium titanate (for example, see patent documents 2 to 4).
As another improvement of the characteristics, patent documents 5 and 6 describe a technique of adding a subcomponent such as magnesium oxide, dysprosium oxide, barium oxide, or calcium oxide to barium titanate as a main component in order to obtain a dielectric ceramic composition having a high electrostatic capacitance and a high relative permittivity and satisfying X7R characteristics.
Further, patent document 7 describes a dielectric ceramic composition having BaTiO as a main component, which is a small change in capacity with time under a dc electric field, a long accelerated lifetime of insulation resistance, and a small decrease in capacity under a dc bias3And SiO2MO (wherein M is selected from Ba, Ca, Sr and Mg)Contains at least one element selected from Li)2O and B2O3A second subcomponent and the other subcomponent in the dielectric ceramic composition. In addition, there has been proposed a technique for improving the life characteristics of a dielectric material to be obtained by including various subcomponents in a main component such as barium titanate (see, for example, patent documents 8 and 9).
Documents of the prior art
Patent document
Patent document 1: japanese unexamined patent application publication No. 2005-162557
Patent document 2: japanese unexamined patent publication No. 2005-129802
Patent document 3: japanese laid-open patent publication No. 2009-84111
Patent document 4: japanese laid-open patent publication No. 2009-203089
Patent document 5: japanese unexamined patent application publication No. 2002-187770
Patent document 6: japanese laid-open patent publication No. 2002-87879
Patent document 7: japanese unexamined patent publication No. 2002-60268
Patent document 8: japanese laid-open patent publication No. 2002-80275
Patent document 9: japanese unexamined patent publication No. 2017-28224
Disclosure of Invention
Technical problem to be solved by the invention
In recent years, electronic devices have been miniaturized, and it is necessary to miniaturize the components thereof, and thus it is necessary to make the dielectric layers of the multilayer ceramic capacitor thinner.
In the above patent documents 7 to 9, in order to solve the above problem, the life characteristics are improved by adding a plurality of elements as subcomponents to barium titanate which is a main component of the dielectric ceramic raw material powder, but there is still room for further improvement.
Accordingly, an object of the present invention is to provide a dielectric ceramic-forming composition for producing a multilayer ceramic capacitor having excellent life characteristics, and a dielectric ceramic material obtained by firing the dielectric ceramic-forming composition.
Technical solution for solving technical problem
The present inventors have made extensive studies in view of the above circumstances, and as a result, have found that a dielectric ceramic material having excellent life characteristics can be obtained from a dielectric ceramic forming composition in which a rare earth element and an element that becomes a vitreous component are added as additive components at a specific ratio to a perovskite-type composite oxide such as barium titanate that becomes a main component, and have completed the present invention.
That is, the present invention provides a dielectric ceramic-forming composition comprising:
as the main component (Ba)1－xCax)mTiO3(wherein x is 0. ltoreq. x.ltoreq.0.250, and m is 0.980. ltoreq. m.ltoreq.1.020); and
an M compound (M is at least one selected from Ba and Ca), an Mg compound, an Mn compound, a Ma compound (Ma is at least one selected from V, Nb and Ta), an Mb compound (Mb is at least one selected from Y, Tb, Dy, Ho, Er, Tm and Yb), and an Mc compound (Mc is at least one selected from Si and Ge) as additional components,
the content of the additive component is calculated in terms of the following oxide with respect to 100mol of the perovskite-type composite oxide,
0.01mol or more and 5.00mol or less in terms of MO;
0.20mol to 2.00mol in terms of MgO;
0.05mol or more and 0.40mol or less in terms of MnO;
with Ma2O50.02mol to 0.20mol in terms;
in Mb2O30.20mol to 3.00mol in terms;
with McO2Converted to 0.18mol or more and 3.50mol or less,
Ma2O5the number of moles of the converted Ma compound relative to Mb2O3Mb conversionMolar ratio of moles of compound (Ma)2O5/Mb2O3) Is 0.010 or more, and
McO2the number of moles of the Mc compound converted relative to the Mb2O3Molar ratio of moles of Mb compound converted (McO)2/Mb2O3) Is 0.90 or more.
The present invention also provides a dielectric ceramic material obtained by firing the dielectric ceramic forming composition.
Effects of the invention
According to the present invention, it is possible to provide a dielectric ceramic-forming composition for producing a multilayer ceramic capacitor having excellent life characteristics, and a dielectric ceramic material obtained by firing the dielectric ceramic-forming composition.
Detailed Description
The present invention will be described below based on preferred embodiments. The present invention provides a dielectric ceramic-forming composition, comprising:
as the main component (Ba)1－xCax)mTiO3(wherein x is 0. ltoreq. x.ltoreq.0.250, and m is 0.980. ltoreq. m.ltoreq.1.020); and
an M compound (M is at least one selected from Ba and Ca), an Mg compound, an Mn compound, a Ma compound (Ma is at least one selected from V, Nb and Ta), an Mb compound (Mb is at least one selected from Y, Tb, Dy, Ho, Er, Tm and Yb), and an Mc compound (Mc is at least one selected from Si and Ge) as additional components,
the content of the additive component is, in terms of the following oxide, based on 100mol of the perovskite-type composite oxide,
0.01mol or more and 5.00mol or less in terms of MO;
0.20mol to 2.00mol in terms of MgO;
0.05mol or more and 0.40mol or less in terms of MnO;
with Ma2O5Converted to 0.02mol or moreUpper 0.20mol or less;
in Mb2O30.20mol to 3.00mol in terms;
with McO2Converted to 0.18mol or more and 3.50mol or less,
Ma2O5the number of moles of the converted Ma compound relative to Mb2O3Molar ratio (Ma) of moles of Mb compound converted2O5/Mb2O3) Is 0.010 or more, and,
McO2the number of moles of the Mc compound converted relative to the Mb2O3Molar ratio of moles of Mb compound converted (McO)2/Mb2O3) Is 0.90 or more.
The main component of the dielectric ceramic-forming composition of the present invention is (Ba)1－xCax)mTiO3The perovskite type composite oxide is shown. The molar ratio (A/B) of the A-site atoms, i.e., Ba, and the Ca and B-site atoms, i.e., Ti, is represented by m in the above formula, and in the present invention, 0.980. ltoreq. m.ltoreq.1.020, preferably 0.990. ltoreq. m.ltoreq.1.010.
The molar ratio of Ba and Ca, which are atoms at the A position, is represented by x in the above formula, and in the present invention, x is 0. ltoreq. x.ltoreq.0.250, preferably 0. ltoreq. x.ltoreq.0.020. By setting x within this range, the temperature coefficient of capacitance or the relative dielectric constant is optimized.
The method for producing such a perovskite-type composite oxide is not particularly limited, and a perovskite-type composite oxide synthesized by a wet reaction, a solid-phase reaction or the like can be suitably used. Among them, from the viewpoint of improving the electrical characteristics of the obtained dielectric ceramic material, it is preferable to use a perovskite-type composite oxide prepared by a wet reaction. Examples of the wet reaction include oxalate method, coprecipitation method, hydrolysis method, hydrothermal synthesis method, and the like.
The dielectric ceramic-forming composition of the present invention contains, as additive components, an M compound (M is at least one selected from Ba and Ca), an Mg compound, an Mn compound, a Ma compound (Ma is at least one selected from V, Nb and Ta), an Mb compound (Mb is at least one selected from Y, Tb, Dy, Ho, Er, Tm, and Yb), and an Mc compound (Mc is at least one selected from Si and Ge) to the perovskite-type composite oxide as a main component.
In the dielectric ceramic forming composition of the present invention, the M compound is a compound containing at least one element selected from Ba and Ca. In the dielectric ceramic-forming composition of the present invention, the content of the M compound is 0.01mol or more and 5.00mol or less, preferably 0.25mol or more and 4.00mol or less in terms of MO with respect to 100mol of the perovskite-type composite oxide. When the content of the M compound is within the above range, the a site in the perovskite-type composite oxide as the main component can be made excessive when the composition for forming a dielectric ceramic of the present invention is formed into a dielectric ceramic material by firing, and therefore, the composition is excellent in reduction resistance.
In the dielectric ceramic-forming composition of the present invention, the content of the Mg compound (magnesium compound) is 0.20mol to 2.00mol, preferably 0.25mol to 1.50mol, in terms of MgO, based on 100mol of the perovskite-type composite oxide. By the content of the Mg compound being within the above range, the life characteristics are optimized.
In the dielectric ceramic-forming composition of the present invention, the content of the Mn compound (manganese compound) is 0.05mol or more and 0.40mol or less, preferably 0.10mol or more and 0.30mol or less in terms of MnO with respect to 100mol of the perovskite-type composite oxide. By the content of the Mn compound being within the above range, the lifetime characteristics are optimized.
The Ma compound is a compound containing at least one element selected from V, Nb and Ta, and preferably a compound containing a V element. In the dielectric ceramic-forming composition of the present invention, the content of the Ma compound is Ma based on 100mol of the perovskite-type composite oxide2O5The amount is 0.02mol to 0.20mol, preferably 0.03mol to 0.19 mol. When the content of the Ma compound is within the above range, the lifetime characteristics and the insulation resistance characteristics are optimized. In addition, in the case of containing 2 or more kinds of Ma compounds, Ma of each Ma compound is used2O5The total of the converted mol numbers is defined as the Ma2O5The converted content.
The Mb compound is a compound containing at least one element selected from Y, Tb, Dy, Ho, Er, Tm, and Yb, preferably a compound containing at least one element selected from Y and Dy, and particularly preferably a compound containing Y element. In the dielectric ceramic-forming composition of the present invention, the content of the Mb compound is Mb per 100mol of the perovskite-type composite oxide2O3The amount is 0.20mol to 3.00mol, preferably 0.30mol to 2.50 mol. When the content of the Mb compound is within the above range, the lifetime characteristics and the insulation resistance characteristics are optimized. In addition, when 2 or more Mb compounds are contained, Mb of each Mb compound is added2O5The total of the converted mol numbers is Mb2O5The converted content.
The Mc compound is a compound containing at least one element selected from Si and Ge, and preferably a compound containing an Si element. In the dielectric ceramic-forming composition of the present invention, the content of the Mc compound is Mco based on 100mol of the perovskite-type composite oxide2The amount is 0.18mol to 3.50mol, preferably 0.50mol to 3.00 mol. When the content of the Mc compound is within the above range, the dielectric ceramic forming composition of the present invention is easily sintered and a dielectric ceramic material is easily obtained, so that the life characteristics and the insulation resistance characteristics are optimized. In addition, when 2 or more Mc compounds are contained, the Mc of each Mc compound is added2O5The total of the converted mol numbers is defined as the above Mc2O5The converted content.
In the dielectric ceramic forming composition of the present invention, the content ratio of the Ma compound containing Ma as a vanadium group element to the Mb compound containing Mb as a rare earth element is determined by using Ma2O5conversion/Mb2O3The molar ratio is 0.010 or more, preferably 0.015 or more and 0.30 or less in terms of conversion. When the content ratio of the Ma compound to the Mb compound is within the above range, the insulation resistance characteristics and the lifetime characteristics are excellent.
In the dielectric ceramic form of the present inventionThe ratio of the content of Mc compound containing Mc as an element to be a vitreous component to the content of Mb compound containing Mb as a rare earth element is Mco2conversion/Mb2O3The molar ratio is 0.90 or more, preferably 1.00 or more and 2.0 or less in terms of conversion. When the content ratio of the Mc compound to the Mb compound is within the above range, the insulation resistance characteristics and the lifetime characteristics are excellent.
The dielectric ceramic forming composition of the present invention may further contain other additives depending on desired characteristics. For example, the dielectric ceramic-forming composition of the present invention may contain an Md compound (Md is at least one selected from W and Mo). When the dielectric ceramic-forming composition of the present invention contains an Md compound, the Md compound is contained in an amount of MdO per 100mol of the perovskite-type composite oxide3The amount of the catalyst is preferably 0.02mol to 0.20mol, and particularly preferably 0.05mol to 0.15 mol. When the content of the Md compound is within the above range, the desired characteristics are improved without impairing the effects of the present invention.
The average particle diameter of the dielectric ceramic-forming composition of the present invention as determined by Scanning Electron Micrographs (SEM) is preferably 0.1 to 2 μm, and more preferably 0.2 to 1.5 μm. When the average particle diameter of the dielectric ceramic forming composition is within the above range, a dielectric ceramic material having excellent electrical characteristics can be obtained.
The specific surface area (BET specific surface area) of the dielectric ceramic-forming composition of the present invention determined by the BET method is preferably 1.0m2A specific ratio of 1.5m to g230m above/g2The ratio of the carbon atoms to the carbon atoms is less than g. When the BET specific surface area of the dielectric ceramic forming composition is within the above range, a dielectric ceramic material having excellent electrical characteristics can be obtained.
The dielectric ceramic-forming composition of the present invention is prepared by mixing a raw material containing a main component and a raw material containing an additive component by a mechanical device under a strong shearing force by a wet method or a dry method so that the perovskite-type composite oxide as the main component and the additive component are uniformly mixed in the above mixing ratio. The wet method is performed by using a ball mill, a disperser, a homogenizer, a vibration mill, a sand mill, an attritor, a high-power stirrer, or the like. On the other hand, in the dry method, a high-speed mixer, a super mixer, a turbo mixer, a henschel mixer, an agate mixer, a ribbon mixer, or the like can be used. Among them, in the present invention, in view of obtaining a uniform mixture and also obtaining a dielectric ceramic material having higher electric characteristics, the preparation by a wet method is particularly preferable, and in this case, examples of the solvent used for wet mixing include: water, methanol, ethanol, propanol, butanol, toluene, xylene, acetone, dichloromethane, ethyl acetate, dimethylformamide, diethyl ether, and the like. Among them, when an alcohol such as methanol, ethanol, propanol, or butanol is used, a dielectric ceramic material with less composition change can be obtained, and the electrical characteristics of the obtained dielectric ceramic material can be improved.
These homogeneous mixing operations are not limited to the illustrated mechanical devices. In addition, a mixing operation with particle size adjustment may be performed by using a device capable of performing mixing and pulverization at the same time, such as a jet mill.
The dielectric ceramic-forming composition of the present invention is calcined and pulverized as necessary to prepare a product. The pre-sintering temperature is preferably 300 to 1100 ℃, more preferably 400 to 1050 ℃, and the pre-sintering time is preferably 1 to 15 hours, more preferably 2 to 12 hours. The pre-firing atmosphere may be any of, for example, an atmosphere, an oxygen atmosphere, or an inert atmosphere, and is not particularly limited. In the present invention, the burn-in may be performed as many times as necessary. Since the compound containing the additive element is present on the surface of the perovskite-type composite oxide particles in a more firmly bonded or adhered state in the dielectric ceramic forming composition obtained by the calcination, even if wet-grinding is performed for 30 hours or more by using, for example, a bead mill or a ball mill, the compound particles containing the additive element are not peeled off, and thus the composition of the dielectric ceramic forming composition is hardly changed.
The dielectric ceramic material of the present invention is obtained by firing the above dielectric ceramic-forming composition. The firing temperature is not particularly limited as long as the dielectric ceramic-forming composition can be fired, but is preferably 300 to 1100 ℃, and more preferably 400 to 1050 ℃. The firing time is preferably 1 to 30 hours, and more preferably 2 to 24 hours. The firing atmosphere may be, for example, any of an atmosphere, an oxygen atmosphere, and an inert atmosphere, and is not particularly limited. In the present invention, the firing may be performed as many times as necessary.
The dielectric ceramic material of the present invention can also be made into a multilayer ceramic capacitor by: the dielectric ceramic forming composition of the present invention is prepared by mixing and dispersing additives, organic binders, plasticizers, dispersants, and the like, which are conventionally known additives for producing multilayer ceramic capacitors, into a slurry, followed by sheet molding to obtain a ceramic sheet, printing an internal electrode forming conductive paste on one surface of the ceramic sheet, drying, laminating a plurality of ceramic sheets, pressing the ceramic sheets In the thickness direction to obtain a laminate, subjecting the laminate to heat treatment and binder removal treatment, and then firing to obtain a fired body, and then applying and firing In-Ga paste, Ni paste, Ag paste, nickel alloy paste, copper alloy paste, and the like to the fired body.
The dielectric ceramic material of the present invention can be used, for example, by blending the dielectric ceramic forming composition of the present invention in a resin such as an epoxy resin, a polyester resin, or a polyimide resin, as a material for a printed wiring board or a multilayer printed wiring board used as a resin sheet, a resin film, an adhesive, or the like, a common material for suppressing a difference in shrinkage between an internal electrode and a dielectric layer, an electrode ceramic circuit board, a base material and a circuit peripheral material of a glass ceramic circuit board, a catalyst used in a reaction of removing waste gas, chemical synthesis, or the like, and a surface modification material of a printing toner, and can be used as a material for imparting antistatic or cleaning effects.
[ examples ]
The present invention will be described in detail with reference to examples, but the present invention is not limited to these examples.
(examples 1 to 3 and comparative example 1)
Barium titanate (BaTiO) having an average particle diameter of 0.4 μm obtained by oxalate method was used3) As the main component. The additive components were added to the barium titanate so that the proportions thereof were as shown in table 1 in terms of oxide conversion, and wet-mixed with a ball mill for 2 hours, and then pulverized and dried to obtain a dielectric ceramic-forming composition. The dielectric ceramic-forming composition had an average particle diameter of 0.38 μm and a BET specific surface area of 3.4m2/g。
Example 4 and comparative example 2
Barium calcium titanate ((Ba) obtained by oxalate method and having an average particle size of 0.25 μm) was used0.9Ca0.1)TiO3) As the main component. The barium calcium titanate was blended with additive components so that the proportions thereof were as shown in table 1, wet-mixed with a ball mill for 2 hours, and then pulverized and dried to obtain a dielectric ceramic-forming composition. The dielectric ceramic-forming composition had an average particle diameter of 0.23 μm and a BET specific surface area of 5.10m2/g。
[ Table 1]
Figure BDA0003382644550000091
(evaluation of Life characteristics)
A PVA binder was added in an amount of 5 mass% to the dielectric ceramic-forming compositions obtained in examples and comparative examples, followed by mixing and pasting, followed by pressure molding to prepare disks 15mm in diameter and 1mm in thickness. The disk was subjected to binder removal treatment, firing and annealing treatment to obtain a ceramic fired body.
The high-temperature load life was evaluated by applying a DC voltage to the ceramic fired body at a temperature of 175 ℃ under an electric field of 25V/. mu.m and measuring the insulation resistance value. The time from the time of application start to the time when the insulation resistance value becomes one of 10 minutes is taken as the lifetime time. The results are shown in table 2.
[ Table 2]
High temperature load life (hours)
Example 1 300
Example 2 250
Example 3 200
Example 4 350
Comparative example 1 50
Comparative example 2 60
As is clear from Table 2, the high-temperature load life of the ceramic fired body obtained from the dielectric ceramic-forming composition of the example was better than that of the comparative example.

Claims (5)

1. A dielectric ceramic-forming composition comprising:
as the main component (Ba)1－xCax)mTiO3Wherein x is 0. ltoreq. x.ltoreq.0.250, and m is 0.980. ltoreq. m.ltoreq.1.020; and
an M compound, an Mg compound, an Mn compound, a Ma compound, an Mb compound and an Mc compound as additive components, wherein M is at least one selected from Ba and Ca, Ma is at least one selected from V, Nb and Ta, Mb is at least one selected from Y, Tb, Dy, Ho, Er, Tm and Yb, Mc is at least one selected from Si and Ge,
the content of the additive component is calculated as the following oxide with respect to 100mol of the perovskite-type composite oxide,
0.01mol or more and 5.00mol or less in terms of MO;
0.20mol to 2.00mol in terms of MgO;
0.05mol or more and 0.40mol or less in terms of MnO;
with Ma2O50.02mol to 0.20mol in terms;
in Mb2O30.20mol to 3.00mol in terms;
with McO2Converted to 0.18mol or more and 3.50mol or less,
Ma2O5the number of moles of the converted Ma compound relative to Mb2O3Molar ratio of moles of Mb Compound converted (Ma)2O5/Mb2O3) Is 0.010 or more, and
McO2the number of moles of the Mc compound converted relative to the Mb2O3Molar ratio of moles of Mb compound converted (McO)2/Mb2O3) Is 0.90 or more.
2. The dielectric ceramic forming composition according to claim 1, wherein:
the additive component further contains an Md compound in an amount of MdO per 100mol of the perovskite-type composite oxide30.02mol or more and 0.20mol or less in terms of the molar ratio, wherein Md is at least one selected from W and Mo.
3. The dielectric ceramic forming composition according to claim 1, wherein:
the average particle diameter is 0.1 to 2 μm.
4. The dielectric ceramic forming composition according to claim 1, wherein:
BET specific surface area of 1.0m2More than g.
5. A dielectric ceramic material obtained by firing the dielectric ceramic forming composition according to claim 1.
CN202111440397.2A 2020-12-01 2021-11-30 Composition for forming dielectric ceramic and dielectric ceramic material Pending CN114573335A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN2020113812582 2020-12-01
CN202011381258 2020-12-01

Publications (1)

Publication Number Publication Date
CN114573335A true CN114573335A (en) 2022-06-03

Family

ID=81770950

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202111440397.2A Pending CN114573335A (en) 2020-12-01 2021-11-30 Composition for forming dielectric ceramic and dielectric ceramic material

Country Status (1)

Country Link
CN (1) CN114573335A (en)

Similar Documents

Publication Publication Date Title
US7678724B2 (en) Electronic device, dielectric ceramic composition and the production method
KR100631995B1 (en) Dielectric ceramic compositions for low temperature sintering and multilayer ceramic condenser using the same
EP1767507B1 (en) Dielectric ceramic composition and laminated ceramic capacitor
JP4821357B2 (en) Electronic component, dielectric ceramic composition and method for producing the same
CN102060521B (en) Hexagonal type barium titanate powder, producing method thereof, dielectric ceramic composition and electronic component
KR101134751B1 (en) Semiconductor ceramic powder, semiconductor ceramic, and laminated semiconductor capacitor
JP6996320B2 (en) Dielectric Porcelain Compositions and Multilayer Ceramic Capacitors
JP4165893B2 (en) Semiconductor ceramic, multilayer semiconductor ceramic capacitor, and method of manufacturing semiconductor ceramic
JP6696266B2 (en) Dielectric ceramic composition and multilayer ceramic capacitor
WO1996013046A1 (en) Multilayer ceramic chip capacitor
KR101310069B1 (en) Hexagonal type barium titanate powder, producing method thereof, dielectric ceramic composition and electronic component
US8450230B2 (en) Dielectric ceramic composition and electronic component
US20120075768A1 (en) Dielectric ceramic composition and manufacturing method thereof, and ceramic electronic device
WO2008013236A1 (en) Dielectric porcelain and capacitor
JP5685931B2 (en) Multilayer ceramic capacitor
JP2006232629A (en) Dielectric ceramic, method for manufacturing the same, and multilayer ceramic capacitor
CN107266071B (en) Dielectric ceramic composition and multilayer ceramic capacitor
JP4349007B2 (en) Multilayer electronic components
JP5488118B2 (en) Dielectric porcelain composition and electronic component
JP2005162557A (en) Method of manufacturing dielectric ceramic composition, method of manufacturing dielectric layer-containing electronic component, and dielectric layer-containing electronic component
CN114907113A (en) Dielectric composition, electronic component, and laminated electronic component
CN114573335A (en) Composition for forming dielectric ceramic and dielectric ceramic material
KR100703080B1 (en) Method for Manufacturing Dielectric Powder for Low Temperature Sintering and Method for Manufacturing Multilayer Ceramic Condenser Using the Same
JP2005272262A (en) Dielectric ceramic composition, multilayer ceramic capacitor and method of manufacturing the same
JP4893361B2 (en) Dielectric porcelain composition and electronic component

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination