CN1791562A - Dielectric ceramic composition, process for producing the same, dielectric ceramic employing it and multilayer ceramic component - Google Patents
Dielectric ceramic composition, process for producing the same, dielectric ceramic employing it and multilayer ceramic component Download PDFInfo
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- CN1791562A CN1791562A CN 200480013842 CN200480013842A CN1791562A CN 1791562 A CN1791562 A CN 1791562A CN 200480013842 CN200480013842 CN 200480013842 CN 200480013842 A CN200480013842 A CN 200480013842A CN 1791562 A CN1791562 A CN 1791562A
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Abstract
A dielectric ceramic composition having a relative dielectric constant [epsilon]r of 15-25 allowing formation of a multilayer ceramic component having an appropriate size, capable of being sintered at a temperature lower than 800-1000 DEG C allowing incorporation and lamination of low resistance conductors of Cu or Ag through simultaneous sintering, and having a low dielectric loss tan delta (high Q-value) and a temperature coefficient tauf of resonance frequency has an absolute value not larger than 50 ppm/ DEG C. The dielectric ceramic composition, 3-30 pts.wt. of lead-free low melting point glass contains 50-75 wt.% of ZnO, 5-30 wt.% of B2O3, 6-15 wt.% of SiO2, 0.5-5 wt.% of Al2O3, and 3-10 wt.% of BaO , based on 100 pts.wt. of principal component represented by a general formula x'Zn2TiO4-(1-x'-y')ZnTiO3-y'TiO2 where 0.15<x'<0.8, and 0<=y'<=0.2.
Description
Technical field
The present invention relates to relative permittivity and be about 15-25, and the temperature factor τ of resonant frequency
fThe media ceramic that absolute value is less, described media ceramic can with Au, Ag, Cu etc. simultaneously sintering as low resistance conductor, and has a less dielectric loss (high Q value) that is applicable to the laminated ceramic parts, and relate to the composition that obtains described media ceramic, make the method for described dielectric ceramic composition, and the laminated ceramic parts that adopt described dielectric ceramic composition, described parts are lamination dielectric capacitor, LC wave filter etc. for example.
Especially, the present invention relates to comprise the dielectric ceramic composition of principal constituent and glass ingredient, described principal constituent contains Zn
2TiO
4And ZnTiO
3And necessary words contain TiO in addition
2, and relate to the manufacture method of described dielectric ceramic composition and the media ceramic and the laminated ceramic parts that adopt described dielectric ceramic composition; And further relating to the dielectric ceramic composition that comprises principal constituent and glass ingredient, wherein said principal constituent contains Zn
2TiO
4, ZnTiO
3And Al
2O
3And necessary words contain TiO in addition
2, its manufacture method, and the media ceramic and the laminated ceramic parts that adopt described dielectric ceramic composition.
Background technology
In recent years, the integrated progress of microwave circuit has proposed the requirement of small size, less dielectric loss (tan δ) and stable dielectric characteristics to dielectric resonator.It is very fast that inside has the laminated chip parts thereby the Market Growth of the lamination electrode conductor that is used for the dielectric resonator parts.The inner wire of described laminated chip parts adopts the precious metal such as Au, Pt, Pd etc.But from saving the viewpoint of cost, existingly adopt than more cheap relatively Ag or the Cu of above-mentioned conductor material or contain Ag or Cu replaces above-mentioned conductor material as the alloy of principal constituent.Especially, Ag or contain Ag and direct current is had lower resistance as the alloy of principal constituent, more favourable to the Q characteristic of improving dielectric resonator etc., thereby there is tight demand in it.Yet, Ag or contain Ag and have about 960 ℃ low melting point as the alloy of principal constituent, needing can the agglomerating dielectric materials in the temperature that is lower than this fusing point.
To adopting dielectric resonator to form the situation of delectric filter, the desired characteristic of dielectric materials is had: the temperature factor τ of the resonant frequency of (1) dielectric materials
fAbsolute value is less, thereby reduces the characteristic variations that is caused by temperature change as much as possible; (2) the Q value of dielectric materials is higher, inserts loss thereby reduce as far as possible as desired to delectric filter.In addition, for used microwave environs such as portable phones, syntonizer length is subjected to the relative permittivity ε of dielectric materials
rLimit.Thereby, require dielectric materials to have high relative permittivity ε in order to miniaturize the elements
rIn the case, determine syntonizer length according to used electromagnetic wavelength.By having relative permittivity ε
rIts wavelength X of hertzian wave of propagating of dielectric materials with λ=λ
0/ (ε
r)
1/2Expression, wherein λ
0Be the electromagnetic wavelength of propagating by vacuum.
Therefore, increase the specific inductivity of used dielectric materials, can make element miniaturization more.Yet if element is too small, desired working accuracy is extremely strict.Thereby make often variation and influenced by the printing precision of electrode of actual working accuracy.For some purpose, require relative permittivity ε
rBe in the OK range (for example about 10-40 or more preferably from about 15-25), thereby make the element can be too not little.
In order to satisfy these requirements, can be the inorganic dielectric particle to be scattered in material in the resin (JP (A)-6-132621) is by BaO-TiO not being higher than known dielectric materials that 1000 ℃ of temperature can prepare dielectric element
2-Nd
2O
3The glass-ceramic (JP (A)-10-330161, page 3, [0005] section and table 1) that the matrix material of base pottery and glass is formed, etc.Be well known that equally and contain TiO
2Also further contain B with ZnO
2O
3The media ceramic (JP (B)-3103296) of base glass.
Yet, being limited to about 400 ℃ on the allowable temperature that disclosed element has among JP (A)-6-132621, its problem that causes is can not be by implementing multiple stratification and forming fine wiring with the while sintering such as Ag that are used as the wiring conductor.
Disclosed glass ceramic material has following problem among JP (A)-10-330161.The relative permittivity ε of this material
rGreater than 40, thereby make element too small.Its result, the working accuracy of requirement are too strict, thereby make actual working accuracy variation, and are subjected to the influence of the printing precision of electrode easily.
In addition, disclosed composition has the relative permittivity up to about 25-70 among the JP (B)-3103296, as finding out from embodiment.The temperature factor of dielectric characteristics depend on form and change bigger, thereby its absolute value exceeds 700ppm/ ℃ under some situation.In order to obtain being used for high-frequency dielectric components, require above-mentioned materials to have suitable relative permittivity, dielectric characteristics is less to dependence on temperature, and has high Q value.
In addition, change owing to the change of sintering temperature and composition usually or have difference through the dielectric characteristics of sintered medium ceramic composition gained media ceramic.Described characteristic variations that causes owing to the change of sintering temperature and composition and difference cause productive rate in mass production variation.
Summary of the invention
The purpose of this invention is to provide relative permittivity is about 10-40, the media ceramic of about 15-25 more preferably, thereby make laminated ceramic parts etc. can form suitable dimension, described media ceramic can be at 800-1000 ℃ temperature sintering, sintering under this temperature make such as the low resistance conductor of Cu, Ag etc. based on synchronous sintering can in encapsulationization and multiple stratification, described media ceramic has less dielectric loss tan δ (high Q value), and the temperature factor τ of its resonant frequency
fAbsolute value is 50ppm/ ℃ or following, and provide the dielectric ceramic composition that can obtain above-mentioned media ceramic, perhaps particularly provide the characteristic variations and the variant that cause by the sintering temperature change less, and form the less dielectric ceramic composition of variation during sintering, and the manufacture method of described dielectric ceramic composition.Another purpose of the present invention provides has medium layer and interior electrode, and described medium layer is by making such as above-mentioned media ceramic, described in electrode contain Cu or Ag laminated ceramic parts, for example laminated ceramic compacitor or LC wave filter as principal constituent.
(1) first embodiment of the invention
For addressing the above problem, the inventor has done further investigation, and has found following result.That is, if will contain ZnO, B at least
2O
3, SiO
2, Al
2O
3Be added to the glass of BaO and contain ZnTiO
3And Zn
2TiO
4And contain TiO if necessary in addition
2Mixture in, then can obtain the ε in the 15-25 scope
rWith less dielectric loss tan δ (high Q value), even and if behind 800-1000 ℃ of sintering, also can not change ZnTiO
3, Zn
2TiO
4And TiO
2Between generation compare.Employing contains the glass of ZnO, can suppress the ZnO composition as much as possible from ZnTiO
3And Zn
2TiO
4Be dissolved in the glass, thereby change the dielectric characteristics cause and change and to be suppressed by forming.Thus, adopt Cu, Ag etc. can be able to laminationization and the linearize of fine pattern cloth as the wiring conductor.
The present invention relates to dielectric ceramic composition, described composition comprises 100 weight parts with general formula x ' Zn
2TiO
4-(1-x '-y ') ZnTiO
3-y ' TiO
2The principal constituent of expression, wherein x ' satisfies 0.15＜x '＜0.8, and y ' satisfies 0≤y '≤0.2; And comprising 3-30 weight part Unlead low-smelting point glass, described Unlead low-smelting point low melting glass contains the ZnO of 50-75 weight %, the B of 5-30 weight %
2O
3, the SiO of 6-15 weight %
2, the Al of 0.5-5 weight %
2O
3And the BaO of 3-10 weight %.
The invention still further relates to and contain Zn
2TiO
4, ZnTiO
3And TiO
2Crystallization phases (TiO wherein
2Can save mutually, below situation also be suitable for) and the media ceramic of glassy phase, described media ceramic obtains by the sintered medium ceramic composition.
In addition, the present invention relates to the manufacture method of dielectric ceramic composition, it comprises following steps: with ZnO raw material powder and TiO
2Raw material powder mixes, and its calcining is obtained containing Zn
2TiO
4, ZnTiO
3And TiO
2(TiO wherein
2Content can be 0) ceramic powder; The gained ceramic powder is mixed with Unlead low-smelting point glass, and described Unlead low-smelting point glass contains the ZnO of 50-75 weight %, the B of 5-30 weight %
2O
3, the SiO of 6-15 weight %
2, the Al of 0.5-5 weight %
2O
3And the BaO of 3-10 weight %.
In addition, the present invention relates to comprise the laminated ceramic parts of a plurality of medium layers; Be formed at the interior electrode between the medium layer; With with described in the outer electrode that is electrically connected of electrode, wherein said medium layer is made of the media ceramic that obtains by the sintered medium ceramic composition, described interior electrode is by element Cu or elements A g or contain Cu or Ag forms as the alloy material of principal constituent.
(2) second embodiment of the invention
For addressing the above problem, the inventor has also done further investigation, and obtains following result.That is, if will contain ZnO and B at least
2O
3Glass be added to and contain ZnTiO
3, Zn
2TiO
4And Al
2O
3And contain TiO if necessary in addition
2Mixture in, then can obtain to be in the ε in the preferable range
rWith less dielectric loss tan δ (high Q value), even and if behind 800-1000 ℃ of sintering, also can not change ZnTiO
3, Zn
2TiO
4, TiO
2And Al
2O
3Between generation compare.Employing contains the glass of ZnO, can suppress the ZnO composition as much as possible from ZnTiO
3And Zn
2TiO
4Be dissolved in the glass, thereby change the dielectric characteristics cause and change and to be suppressed by forming.Thus, adopt Cu, Ag etc. can be able to laminationization and the linearize of fine pattern cloth as the wiring conductor.
The present invention relates to dielectric ceramic composition, described composition comprises 100 weight parts with general formula xZn
2TiO
4-yZnTiO
3-zTiO
2-wAl
2O
3The principal constituent of expression, wherein x satisfies 0.15＜x＜1.0 and the satisfied 0＜y of y＜0.85, and z satisfies 0≤z≤0.2, and w satisfies 0＜w≤0.2, and satisfies x+y+z+w=1; And comprising 3-30 weight part Unlead low-smelting point glass, described Unlead low-smelting point glass contains the ZnO of 50-75 weight %, the B of 5-30 weight %
2O
3, the SiO of 6-15 weight %
2, the Al of 0.5-5 weight %
2O
3And the BaO of 3-10 weight %.In the preferred embodiment of dielectric ceramic composition of the present invention, x satisfies 0.15＜x＜0.99, and y satisfies 0.05＜y＜0.85, and w satisfies 0.005＜w≤0.2.
The invention still further relates to and contain Zn
2TiO
4, ZnTiO
3, TiO
2And Al
2O
3Crystallization phases (TiO wherein
2Can save mutually) and the media ceramic of glassy phase, described media ceramic obtains by the sintered medium ceramic composition.
In addition, the present invention relates to the manufacture method of dielectric ceramic composition, it comprises following steps: with ZnO raw material powder and TiO
2Raw material powder mixes, and its calcining is obtained containing Zn
2TiO
4, ZnTiO
3And TiO
2(TiO wherein
2Content can be 0) ceramic powder; With gained ceramic powder and Al
2O
3Mix with Unlead low-smelting point glass, described Unlead low-smelting point glass contains the ZnO of 50-75 weight %, the B of 5-30 weight %
2O
3, the SiO of 6-15 weight %
2, the Al of 0.5-5 weight %
2O
3And the BaO of 3-10 weight %.
In addition, the present invention relates to comprise the laminated ceramic parts of a plurality of medium layers; Be formed at the interior electrode between the medium layer; With with described in the outer electrode that is electrically connected of electrode, wherein said medium layer is made of the media ceramic that obtains by the sintered medium ceramic composition, described interior electrode is by element Cu or elements A g or contain Cu or Ag forms as the alloy material of principal constituent.
Dielectric ceramic composition of the present invention comprises crystallised component and particular glass composition, and described crystallised component contains Zn
2TiO
4, ZnTiO
3With TiO as optional member
2Thereby, can carry out sintering 1000 ℃ or following temperature.By the media ceramic that the sintered medium ceramic composition obtains, its relative permittivity ε
rCan be about 15-25, its dielectric loss can be less, and the absolute value temperature coefficient of its resonant frequency can be 50ppm/ ℃ or following.The laminated ceramic parts of electrode in its result can obtain having, described in electrode by element Cu, elements A g or contain Cu or Ag makes as the alloy material of principal constituent.
Another dielectric ceramic composition of the present invention comprises crystallised component and particular glass composition, and described crystallised component contains Zn
2TiO
4, ZnTiO
3, Al
2O
3With TiO as optional member
2Thereby, can carry out sintering 1000 ℃ or following temperature.By the media ceramic that the sintered medium ceramic composition obtains, its relative permittivity ε
rCan be about 10-40, be preferably about 15-25, its dielectric loss can be less, and the absolute value temperature coefficient of its resonant frequency can be 50ppm/ ℃ or following.In addition, can obtain the less dielectric ceramic composition that influenced by sintering temperature and change of above-mentioned characteristic.The laminated ceramic parts of electrode in its result can obtain having, described in electrode by element Cu, elements A g or contain Cu or Ag makes as the alloy material of principal constituent.
The accompanying drawing summary
Figure 1 shows that perspective diagram according to three ply board (tri-plate) the type syntonizer of the invention process form;
Fig. 2 is the cross sectional representation of Fig. 1 syntonizer;
Figure 3 shows that the X-ray diffractogram that the dielectric ceramic composition of the embodiment of the invention 1 is carried out the obtained bead of sintering;
Figure 4 shows that the X-ray diffractogram that the dielectric ceramic composition of the embodiment of the invention 15 is carried out the obtained bead of sintering;
Wherein label 1 refers to medium layer, and 2 refer to interior electrode, and 3 refer to outer electrode.
The optimum embodiment of the present invention
(1) first embodiment of the invention
The following dielectric ceramic composition that will specify first embodiment of the invention.
Composition of the present invention is the dielectric ceramic composition that contains principal constituent and glass ingredient, and described principal constituent contains Zn
2TiO
4, ZnTiO
3With TiO as optional member
2Principal constituent is with general formula x ' Zn
2TiO
4-(1-x '-y ') ZnTiO
3-y ' TiO
2Expression, wherein x ' is in 0.15＜x '＜0.8 scope and y ' is in 0≤y '≤0.2 scope.Described glass ingredient is a Unlead low-smelting point glass, and it contains the ZnO of 50-75 weight %, the B of 5-30 weight %
2O
3, the SiO of 6-15 weight %
2, the Al of 0.5-5 weight %
2O
3, and the BaO of 3-10 weight %.With respect to the principal constituent of per 100 weight parts, the contained glass ingredient of dielectric ceramic composition of the present invention is the 3-30 weight part.
In above-mentioned composition, x ' should be preferably greater than 0.15 and less than 0.8.For x ' smaller or equal to 0.15 or more than or equal to 0.8 situation, τ
fAbsolute value can exceed 50ppm/ ℃, and this is unfavorable.
In addition, in above-mentioned composition, y ' should preferably be in the 0-0.2 scope.Owing to contain TiO
2, thereby certain dielectric constant tends to rise slightly.Yet, equal composition for y ' less than 0.2, can obtain target effect of the present invention.If y ' is greater than 0.2, τ then
fExceed+50ppm/ ℃, this is unfavorable.
In dielectric ceramic composition of the present invention, corresponding to the principal constituent of per 100 weight parts formation ceramic base material, the amount of glass ingredient should preferably be in the 3-30 weight part scope.Be lower than the situation of 3 weight parts for the amount of glass ingredient, then sintering temperature be equal to or higher than Ag or Cu or contain Ag or Cu as the fusing point of the alloy of principal constituent.Thereby the electrode of being made by this class material just can not use ideally.If the amount of glass ingredient exceeds 30 weight parts, then good agglomerating trend appears being difficult to carrying out in the stripping owing to glass.
Used Zn among the present invention
2TiO
4Can pass through zinc oxide ZnO and titanium oxide TiO
2With 2: 1 mixed in molar ratio and calcine the gained mixture and make.ZnTiO
3Can pass through zinc oxide ZnO and titanium oxide TiO
2With 1: 1 mixed in molar ratio and calcine the gained mixture and make.Remove TiO
2Outside ZnO, can adopt the nitrate that contains Zn and/or Ti, carbonate, oxyhydroxide, muriate, organometallic compound etc. as Zn
2TiO
4And ZnTiO
3Raw material, in order to form oxide compound in when calcining.
Described dielectric ceramic composition is characterized in that containing the particular glass of predetermined amount.Used glass contains the ZnO of 50-75 weight % among the present invention, the B of 5-30 weight %
2O
3, the SiO of 6-15 weight %
2, the Al of 0.5-5 weight %
2O
3, and the BaO of 3-10 weight %.These oxide components are with estimated rate mixing and fusing, cooling and vitrifying.
To narrate the composition of used glass among the present invention below.For ZnO, if its ratio is lower than 50 weight %, then the softening temperature of glass is too high so that can not carry out good sintering, and if its ratio is higher than 75 weight %, then is difficult to carry out vitrifying under desired temperature.To B
2O
3, if its ratio is lower than 5 weight %, then the softening temperature of glass is too high so that can not carry out good sintering, if its ratio is higher than 30 weight %, then because the stripping of glass and can not carry out good sintering.To SiO
2, if its ratio is lower than 6 weight % or is higher than 15 weight %, then the softening temperature of glass is too high so that can not carry out good sintering.To Al
2O
3, if its ratio is lower than 0.5 weight %, then the chemical durability variation of gained media ceramic if its ratio is higher than 5 weight %, then is difficult to carry out vitrifying under desired temperature.For BaO,, then under desired temperature, be difficult to carry out vitrifying if its ratio is lower than 3 weight % or is higher than 10 weight %.If glass contains Pb or Bi composition, then the Q value of dielectric ceramic composition tends to reduce.Because the glass in the dielectric ceramic composition of the present invention does not contain Pb, thereby can not cause the environmental pollution due to the Pb.
According to the present invention, to 100 weight parts with general formula x ' Zn
2TiO
4-(1-x '-y ') ZnTiO
3-y ' TiO
2The principal constituent of expression, wherein x ' is in 0.15＜x '＜0.8 scope and y ' is in 0≤y '≤0.2 scope, contains 3-30 weight part Unlead low-smelting point glass, and described Unlead low-smelting point glass contains the ZnO of 50-75 weight %, the B of 5-30 weight %
2O
3, the SiO of 6-15 weight %
2, the Al of 0.5-5 weight %
2O
3, and the BaO of 3-10 weight %.Therefore, can realize sintering at 800-1000 ℃ lesser temps.By above-mentioned dielectric ceramic composition is carried out sintering, can obtain media ceramic of the present invention.Media ceramic of the present invention is characterised in that its relative permittivity ε
rBe about 15-25, have high unloaded Q, and the temperature factor τ of its resonator frequency
fAbsolute value be 50ppm/ ℃ or following.The composition of described media ceramic and the raw material of dielectric ceramic composition are formed basic identical, all contain Zn
2TiO
4, ZnTiO
3And TiO
2Crystallization phases and glassy phase.According to dielectric ceramic composition of the present invention, low-temperature sintering can be carried out and the media ceramic that obtains having above-mentioned characteristic.
In the present invention, Zn
2TiO
4, ZnTiO
3Particle and as the TiO of optional member
2Particle and glass particle carry out single pulverizing before sintering, and mix.Perhaps, each raw material particle is mixed with each other before the sintering and pulverizes.In order to obtain improved dispersiveness, high unloaded Q and stable relative permittivity ε
r, the median size of above-mentioned raw materials preferably should be and is equal to or less than 2.0 μ m before the sintering, more preferably is equal to or less than 1.0 μ m.If median size is too small, then be difficult under some situation handle.Thereby median size also should be preferably and be equal to or higher than 0.05 μ m.
To introduce the manufacture method of dielectric ceramic composition of the present invention and media ceramic subsequently.With ZnO raw material powder and TiO
2Raw material powder mixes and calcining, thereby obtains containing Zn
2TiO
4And ZnTiO
3Reach TiO as optional member
2Ceramic powder.This ceramic powder is mixed with Unlead low-smelting point glass, and described low melting glass contains the ZnO of 50-75 weight %, the B of 5-30 weight %
2O
3, the SiO of 6-15 weight %
2, the Al of 0.5-5 weight %
2O
3, and the BaO of 3-10 weight %.Promptly obtain dielectric ceramic composition thus.Ceramic powder Zn
2TiO
4, ZnTiO
3And TiO
2Can prepare separately separately.Perhaps, can regulate ZnO and TiO
2Thereby the ratio between the raw material directly obtains containing the Zn of admixture
2TiO
4, ZnTiO
3And TiO
2Powder.
Will be further described below in order to obtain the Zn of dielectric ceramic composition of the present invention
2TiO
4And ZnTiO
3The independent preparation method of each powder.At first, the mol ratio of weighing is 2: 1 zinc oxide and a titanium dioxide, and mixes with the solvent such as water, alcohol etc.Subsequently, from gains, remove anhydrate, alcohol etc., containing under the oxygen atmosphere (for example in air atmosphere) in 900-1200 ℃ of temperature calcining 1-5 hour then.The calcined powder that obtains thus is by Zn
2TiO
4Form.Then, the mol ratio of weighing is 1: 1 titanium dioxide and a zinc oxide.With with Zn
2TiO
4Identical preparation method makes ZnTiO
3The Zn that contains of predetermined amount weighs
2TiO
4, ZnTiO
3And TiO
2Principal constituent.Further, the Unlead low-smelting point glass of weighing, to satisfy the predetermined ratio to principal constituent, described low melting glass contains the ZnO of 50-75 weight %, the B of 5-30 weight %
2O
3, the SiO of 6-15 weight %
2, the Al of 0.5-5 weight %
2O
3, and the BaO of 3-10 weight %.Glass is mixed with solvent such as water, alcohol etc. with principal constituent.Remove subsequently anhydrate, alcohol etc., pulverize afterwards, thereby make the dielectric ceramic composition of expection, it is the raw material powder that is used for media ceramic.
Dielectric ceramic composition sintering of the present invention is formed the media ceramic bead, and measure its dielectric characteristics.More particularly, will mix with raw material powder with media ceramic such as the organic binder bond of polyvinyl alcohol, thereby make it to homogenize.Implement dry and pulverizing, then gains are compressed into coccoid (at 100-1000Kg/cm
2Under the pressure).With gained form thing under such as the oxygen-containing gas atmosphere of air in 800-1000 ℃ of sintering, thereby obtain Zn
2TiO
4Phase, ZnTiO
3Phase and TiO
2Media ceramic with the glassy phase coexistence.
As required, will be processed into suitable shape and suitable dimension, or adopt described dielectric ceramic composition based on formation sheets such as scraping blade methods according to the dielectric ceramic composition of the present invention of first embodiment, and the lamination of implementing thin slice and electrode.Thus, can be with described dielectric ceramic composition as the material that constitutes all kinds lamination ceramic component.The laminated ceramic parts can be laminated ceramic compacitor, LC wave filter, dielectric resonator, dielectric substrate or the like.
Laminated ceramic parts according to first embodiment of the invention have a plurality of medium layers, are formed at the interior electrode between the medium layer, and the outer electrode that is electrically connected with described interior electrode.Medium layer is made of the dielectric ceramic composition gained media ceramic of sintering first embodiment of the invention.Interior electrode is perhaps contained Cu or Ag and is made as the alloy material of principal constituent by element Cu or elements A g.Medium layer and element Cu, the elements A g that laminated ceramic parts of the present invention can be made up of media ceramic by the while sintering or contain Cu or Ag makes as the alloy material of principal constituent.
According to the example of the laminated ceramic parts of the present invention of first embodiment can be as depicted in figs. 1 and 2 three ply board type syntonizer.Figure 1 shows that perspective diagram according to the three ply board type syntonizer of the invention process form.Fig. 2 is the cross sectional representation of Fig. 1.As depicted in figs. 1 and 2, described three ply board type syntonizer is the laminated ceramic parts, has a plurality of medium layers 1, is formed at the interior electrode 2 between the medium layer, and the outer electrode 3 that is electrically connected with described interior electrode.Described three ply board type syntonizer is for making interior electrode 2 laminations of a plurality of medium layers 1 with the centering part.The generation type of interior electrode 2 is through to and first second B that A is relative for first A from syntonizer.Having only first A is open surface.Outer electrode 3 is formed on the syntonizer on five faces except that first A.Interior electrode 2 and outer electrode 3 are interconnection on second B.The material of interior electrode 2 comprises Cu or Ag, perhaps contains Cu or the Ag alloy material as principal constituent.Because dielectric ceramic composition of the present invention is sintering at low temperatures, thereby can adopt the above-mentioned materials that uses for interior electrode.
(2) second embodiment of the invention
Hereinafter will describe dielectric ceramic composition in detail according to second embodiment of the invention.
Composition of the present invention is a dielectric ceramic composition, and it comprises principal constituent and glass ingredient, and described principal constituent contains Zn
2TiO
4, ZnTiO
3And Al
2O
3Reach TiO as optional member
2Principal constituent is with general formula xZn
2TiO
4-yZnTiO
3-zTiO
2-wAl
2O
3Expression, wherein x is in 0.15＜x＜1.0 scopes, and y is in 0＜y＜0.85 scope, and z is in 0≤z≤0.2 scope, and w is in 0＜w≤0.2 scope, and satisfies x+y+z+w=1.Zn
2TiO
4, ZnTiO
3, Al
2O
3And TiO
2Has crystal habit separately.On the other hand, described glass ingredient can be to contain 50-75 weight %ZnO and 5-30 weight %B
2O
3Glass.In dielectric ceramic composition of the present invention, whenever contain 100 weight part principal constituents corresponding to the glass ingredient that contains the 3-30 weight part.
In above-mentioned composition, Zn
2TiO
4The preferred scope of living in of molar fraction x be greater than 0.15 and less than 1.0, be greater than 0.15 and less than 0.99 especially.If x be equal to or less than 0.15 or x be 1.0, τ then
fAbsolute value exceed 50ppm/ ℃, this is unfavorable.
Equally in above-mentioned composition, ZnTiO
3The preferred scope of living in of molar fraction y be greater than 0 and less than 0.85, be greater than 0.005 and less than 0.85 especially.If y be 0 or y be equal to or greater than 0.85, τ then
fAbsolute value exceed 50ppm/ ℃, this is unfavorable.
Equally in above-mentioned composition, TiO
2The preferred scope of living in of molar fraction z be 0-0.2.Owing to contain TiO
2, thereby specific inductivity tends to increase slightly.But z is equal to or less than 0.2 arbitrary composition and all can obtains target advantage of the present invention.If z is greater than 0.2, τ then
fAbsolute value exceed+50ppm/ ℃, this is unfavorable.
Equally in above-mentioned composition, Al
2O
3Molar fraction w be preferably greater than 0 and be not more than 0.2, especially for greater than 0.005 and be not more than 0.2.If w is 0, then changing caused dielectric characteristics variation by sintering temperature can become greatly, thereby sintering range is narrowed down, and this is unfavorable.If w is greater than 0.2, then sintering temperature can be equal to or higher than Ag or Cu or contain Ag or Cu as the fusing point of the alloy of principal constituent.This has hindered the use as the made electrode of above-mentioned materials of the object of the invention, thereby is unfavorable.
In dielectric ceramic composition of the present invention, corresponding to the per 100 weight part principal constituents that constitute ceramic base material, the preferred scope of living in of the consumption of glass ingredient is the 3-30 weight part equally.If the glass ingredient consumption is lower than 3 weight parts, then sintering temperature can be equal to or higher than Ag or Cu or contain Ag or Cu as the fusing point of the alloy of principal constituent.Thereby can not use the made electrode of above-mentioned materials, this is unfavorable.If the consumption of glass ingredient surpasses 30 weight %, then good agglomerating trend appears being difficult to carrying out in the stripping owing to glass.
Used Zn among the present invention
2TiO
4Can pass through zinc oxide ZnO and titanium dioxide TiO
2With 2: 1 mixed in molar ratio and calcine the gained mixture and make.ZnTiO
3Can pass through zinc oxide ZnO and titanium dioxide TiO
2With 1: 1 mixed in molar ratio and calcine the gained mixture and make.Remove TiO
2Outside ZnO, can adopt the nitrate that contains Zn and/or Ti, carbonate, oxyhydroxide, muriate, organometallic compound etc. as Zn
2TiO
4And ZnTiO
3Raw material, in order to form oxide compound in when calcining.
Used glass is preferably the glass that contains 50-75 weight %ZnO among the present invention.Owing to contain the ZnO composition in the glass, thereby can suppress to constitute the Zn of principal constituent
2TiO
4And ZnTiO
3The ZnO composition be transferred in the glassy phase.Thereby can reduce in the sintering process by forming the variation that changes caused dielectric characteristics.In addition, if described glass contains the B of 5-30 weight %
2O
3, then can carry out low-temperature sintering easily ideally.Particularly preferred glass ingredient contains the ZnO of 50-75 weight %, the B of 5-30 weight %
2O
3, the SiO of 6-15 weight %
2, the Al of 0.5-5 weight %
2O
3, and the BaO of 3-10 weight %.For the situation with described glass ingredient and above-mentioned principal constituent blended dielectric ceramic composition, relative permittivity ε
rCan preferably be in the scope of 15-25.Preparation method as glass to be mixed is to melt, to cool off and vitrifying with above-mentioned each oxide components of predetermined proportion blended.To narrate the composition of used glass among the present invention below.For ZnO, if its ratio is lower than 50 weight %, then the softening temperature of glass is too high so that can not carry out good sintering, and if its ratio is higher than 75 weight %, then is difficult to carry out vitrifying under desired temperature.To B
2O
3, if its ratio is lower than 5 weight %, then the softening temperature of glass is too high so that can not carry out good sintering, if its ratio is higher than 30 weight %, then because the stripping of glass and can not carry out good sintering.To SiO
2, if its ratio is lower than 6 weight % or is higher than 15 weight %, then the softening temperature of glass is too high so that can not carry out good sintering.To Al
2O
3, if its ratio is lower than 0.5 weight %, then the chemical durability variation of gained media ceramic if its ratio is higher than 5 weight %, then is difficult to carry out vitrifying under desired temperature.For BaO,, then under desired temperature, be difficult to carry out vitrifying if its ratio is lower than 3 weight % or is higher than 10 weight %.If glass contains Pb or Bi composition, then the Q value of dielectric ceramic composition tends to reduce.Because the glass in the dielectric ceramic composition of the present invention does not contain Pb, thereby can not cause the environmental pollution due to the Pb.
According to the present invention, to per 100 weight parts with general formula xZn
2TiO
4-yZnTiO
3-zTiO
2-wAl
2O
3The principal constituent of expression, wherein x satisfies 0.15＜x＜1.0, and y satisfies 0＜y＜0.85, and z satisfies 0≤z≤0.2, and w satisfies 0＜w≤0.2, and satisfies x+y+z+w=1, contains the 3-30 weight part and contains ZnO and B
2O
3Glass ingredient.Therefore, can under 800-1000 ℃ lesser temps, finish sintering.By the above-mentioned dielectric ceramic composition of sintering, can obtain media ceramic of the present invention.Media ceramic of the present invention is characterised in that relative permittivity ε
rBe 10-40, be preferably about 15-25, have high unloaded Q, and the temperature factor τ of its resonant frequency
fAbsolute value be 50ppm/ ℃ or lower.The composition of media ceramic and the raw material of dielectric ceramic composition are formed basic identical, all contain Zn
2TiO
4, ZnTiO
3, TiO
2And Al
2O
3Crystallization phases and glassy phase.According to dielectric ceramic composition of the present invention, can carry out low-temperature sintering, thus the media ceramic that obtains having above-mentioned characteristic.
Dielectric ceramic composition of the present invention representation before sintering is Zn
2TiO
4, ZnTiO
3, TiO
2, Al
2O
3Mixture with glass.Even in preparation process this mixture is further mixed with the additive such as solvent, organic materials etc. of adding, gained mixing resultant is still the desired dielectric ceramic composition of the present invention.Even if the mixture of ceramic composition of the present invention is after sintering, the composition of its crystallization phases and glassy phase changes still less.Thereby, be the media ceramic that constitutes by dielectric ceramic composition of the present invention by the resulting media ceramic of sintering mix.
In the present invention, Zn
2TiO
4, ZnTiO
3, TiO
2And Al
2O
3Particle and glass particle carry out single pulverizing before sintering, and mix.Perhaps, preceding each raw material particle is mixed with each other of sintering pulverized then.In order to obtain improved dispersiveness, high unloaded Q and stable relative permittivity ε
r, the median size of above-mentioned raw materials preferably should be and is equal to or less than 2.0 μ m before the sintering, more preferably is equal to or less than 1.0 μ m.If median size is too small, then be difficult under some situation handle.Thereby median size also should be preferably and be equal to or higher than 0.05 μ m.
To introduce the manufacture method of dielectric ceramic composition of the present invention and media ceramic subsequently.Constitute each Zn of a principal constituent part
2TiO
4, ZnTiO
3And TiO
2Powder can singlely prepare.Perhaps, by regulating ZnO and TiO
2Ratio between the raw material can be calcined and directly obtained Zn
2TiO
4, ZnTiO
3And TiO
2Mixed powder.In order to obtain Zn with a calcining step
2TiO
4, ZnTiO
3And TiO
2Mixed powder, can preset ratio with ZnO and TiO
2Raw material powder mix and calcine.The gained material can with the Al of predetermined amount
2O
3Mix, can be used as the principal constituent of dielectric ceramic composition of the present invention then.In order to obtain dielectric ceramic composition of the present invention, the principal constituent of 100 weight parts can be mixed with the glass ingredient of 3-30 weight part, described glass ingredient contains the ZnO of 50-75 weight % and the B of 5-30 weight %
2O
3
In the preferable production process of dielectric ceramic composition, with ZnO raw material powder and TiO
2Raw material powder mixes and calcining, thereby obtains containing Zn
2TiO
4, ZnTiO
3And TiO
2Ceramic powder.This ceramic powder is mixed with the predetermined amount Unlead low-smelting point glass, and described low melting glass contains the ZnO of 50-75 weight %, the B of 5-30 weight %
2O
3, the SiO of 6-15 weight %
2, the Al of 0.5-5 weight %
2O
3, and the BaO of 3-10 weight %.
If single preparation Zn
2TiO
4, ZnTiO
3Ceramic powder separately, can be with titanium dioxide (TiO
2) and zinc oxide (ZnO) be mixed for preparing Zn with 2: 1 and 1: 1 molar ratio respectively
2TiO
4And ZnTiO
3, calcine then.The gained Zn of predetermined amount weighs
2TiO
4, ZnTiO
3, TiO
2And Al
2O
3And mix, subsequently can be with the principal constituent of gained mixture as dielectric ceramic composition of the present invention.
To describe Zn in detail below
2TiO
4, ZnTiO
3The single preparation method of powder separately is in order to prepare dielectric ceramic composition of the present invention.At first, the mol ratio of weighing is 2: 1 titanium dioxide (TiO
2) and zinc oxide (ZnO), and it is mixed with the solvent such as water, alcohol etc.Subsequently, from the gained material, remove anhydrate, alcohol etc.Afterwards the gained material is pulverized, and in containing oxygen atmosphere (for example air atmosphere) in 900-1200 ℃ of temperature lower calcination 1-5 hour.The gained calcined powder is by Zn thus
2TiO
4Form.Then, the mol ratio of weighing is 1: 1 titanium dioxide and a zinc oxide.With with Zn
2TiO
4Identical preparation method makes ZnTiO
3The Zn of the predetermined proportion of weighing
2TiO
4, ZnTiO
3And further TiO
2, Al
2O
3And glass, it is mixed with the solvent such as water, alcohol etc.Remove subsequently anhydrate, alcohol etc., afterwards the gained material is pulverized, thereby is made desired dielectric ceramic composition, it is the raw material powder that is used for media ceramic.
Dielectric ceramic composition sintering of the present invention is formed the media ceramic bead, and measure its dielectric characteristics.More particularly, will mix with raw material powder with media ceramic such as the organic binder bond of polyvinyl alcohol, thereby make it to homogenize.Implement dry and pulverizing, then gains are compressed into coccoid (at 100-1000Kg/cm
2Under the pressure).With gained form thing under such as the oxygen-containing gas atmosphere of air in 800-1000 ℃ of sintering, thereby obtain Zn
2TiO
4Phase, ZnTiO
3Phase, TiO
2Phase and Al
2O
3Media ceramic with the glassy phase coexistence.
Dielectric ceramic composition according to second embodiment can be used as various laminated ceramic parts, as in the first embodiment.
Acquisition mode according to the laminated ceramic parts of the present invention of second embodiment is identical with the mode of first embodiment, and the media ceramic that difference is to make medium layer is that the dielectric ceramic composition of the present invention by sintering second embodiment obtains.
Embodiment
Various details embodiment and relevant Comparative Examples.
[embodiment 1]
(embodiment that belongs to first embodiment of the invention)
With 0.33 mole of titanium dioxide (TiO
2) place ball mill with ethanol and mixed 12 hours with 0.66 mole of zinc oxide (ZnO).From solution, remove and desolvate, then the gained material is pulverized and under air atmosphere in 1000 ℃ of calcinings, thereby obtain Zn
2TiO
4Calcined powder.Then, with 0.5 mole of TiO
2Mix in mode same as described above with 0.5 mole of ZnO and calcine, thereby obtain ZnTiO
3Calcined powder.With the Zn that obtains thus
2TiO
4And ZnTiO
3Calcined powder and TiO
2With mixed shown in the table 1, thereby make base material (principal constituent).The glass powder that in the above-mentioned base material of 100 weight parts, adds 10 weight parts, the ZnO that consists of 63.5 weight % of described glass powder, the SiO of 8 weight %
2, the Al of 1.5 weight %
2O
3, the BaO of 7 weight %, and the B of 20 weight %
2O
3, the gained material placed ball mill and mixed 24 hours.Remove from solution and desolvate, then the gained material being pulverized until median size is 1 μ m.In the gained crushed material, add the polyvinyl alcohol solution of appropriate amount, carry out drying afterwards.Subsequently, the gained material is shaped to the bead of diameter 12mm, thickness 4mm, and with the gained bead in air atmosphere in 900 ℃ of sintering 2 hours.Fig. 3 shows the X-ray diffraction pattern of obtained sintering bead.As can be seen from Figure 3, Zn
2TiO
4Phase, ZnTiO
3Phase and TiO
2Be present in jointly mutually in the sintering bead of dielectric ceramic composition of the present invention.
The media ceramic of gained thus is processed into the size of diameter 7mm, thickness 3mm.Measure unloaded Q, the relative permittivity ε at resonant frequency 7-11GHz place then according to the dielectric resonance method
rTemperature factor τ with resonant frequency
fTable 2 shows the result.
[table 1]
| Base material is formed (molar fraction) | Glass is formed (weight %) | Base material consumption (weight part) | Glass consumption (weight part) | Median size after the pulverizing (μ m) | ||||||||||
| Zn 2TiO 4 x’ | ZnTiO 3 1-x’-y’ | TiO 2 y’ | SiO 2 | Al 2O 3 | ZnO | BaO | B 2O 3 | Bi 2O 3 | PbO | |||||
| Embodiment | 1 | 0.22 | 0.77 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 10 | 1 |
| 2 | 0.40 | 0.59 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 3 | 0.75 | 0.24 | 0.01 | 8.0 | 15 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 4 | 0.22 | 0.78 | 0.00 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 5 | 0.20 | 0.70 | 0.10 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 6 | 0.18 | 0.62 | 0.20 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 7 | 0.22 | 0.77 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 10 | 2 | |
| 8 | 0.22 | 0.77 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 10 | 0.5 | |
| 9 | 0.22 | 0.77 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 10 | 0.1 | |
| 10 | 0.22 | 0.77 | 0.01 | 6.0 | 1.5 | 71.0 | 3.5 | 18.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 11 | 0.22 | 0.77 | 0.01 | 8.0 | 5.0 | 50.0 | 10.0 | 27.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 12 | 0.22 | 0.77 | 0.01 | 10.0 | 5.0 | 50.0 | 5.0 | 30.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 13 | 0.22 | 0.77 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 5 | 1 | |
| 14 | 0.22 | 0.77 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 25 | 1 | |
| Comparative Examples | 1 | 0.10 | 0.86 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 10 | 1 |
| 2 | 0.85 | 0.14 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 3 | 0.16 | 0.54 | 0.30 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 4 | 0.11 | 0.39 | 0.50 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 5 | 0.22 | 0.77 | 0.01 | 8.0 | 1.5 | 18.5 | 7.0 | 20.0 | 45.0 | 0.0 | 100 | 10 | 1 | |
| 6 | 0.22 | 0.77 | 0.01 | 8.0 | 1.5 | 20.5 | 7.0 | 20.0 | 0.0 | 43.0 | 100 | 10 | 1 | |
| 7 | 0.22 | 0.77 | 0.01 | 20.0 | 0.5 | 75.0 | 2.5 | 2.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 8 | 0.22 | 0.77 | 0.01 | 17.0 | 7.0 | 42.0 | 1.0 | 33.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 9 | 0.22 | 0.77 | 0.01 | 10.0 | 5.0 | 33.0 | 2.0 | 50.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 10 | 0.22 | 0.77 | 0.01 | 4.0 | 1.6 | 66.3 | 7.3 | 20.9 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 11 | 0.22 | 0.77 | 0.01 | 18.0 | 1.3 | 56.6 | 6.2 | 17.8 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 12 | 0.22 | 0.77 | 0.01 | 8.1 | 0.1 | 64.4 | 7.1 | 20.3 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 13 | 0.22 | 0.77 | 0.01 | 7.6 | 7.0 | 60.0 | 6.6 | 18.9 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 14 | 0.22 | 0.77 | 0.01 | 11.4 | 2.1 | 48.0 | 10.0 | 28.5 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 15 | 0.22 | 0.77 | 0.01 | 4.4 | 0.8 | 80.0 | 3.8 | 11.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 16 | 0.22 | 0.77 | 0.01 | 8.4 | 1.6 | 66.9 | 2.0 | 21.1 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 17 | 0.22 | 0.77 | 0.01 | 7.6 | 1.4 | 60.1 | 12.0 | 18.9 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 18 | 0.22 | 0.77 | 0.01 | 9.6 | 1.8 | 76.2 | 8.4 | 4.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 19 | 0.22 | 0.77 | 0.01 | 6.5 | 1.2 | 51.6 | 5.7 | 35.0 | 0.0 | 0.0 | 100 | 10 | 1 | |
| 20 | 0.22 | 0.77 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 2 | 1 | |
| 21 | 0.22 | 0.77 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 0.0 | 0.0 | 100 | 40 | 1 | |
[table 2]
| ε r | Q×f(GHz) | τ f(ppm/℃) | Sintering temperature/℃ | ||
| Embodiment | 1 | 20.0 | 10000 | 0 | 900 |
| 2 | 19.3 | 10000 | -5 | 900 | |
| 3 | 18.0 | 9000 | -43 | 900 | |
| 4 | 19.8 | 10000 | -3 | 900 | |
| 5 | 22.1 | 12000 | 15 | 900 | |
| 6 | 24.5 | 13000 | 30 | 900 | |
| 7 | 20.0 | 10000 | 0 | 900 | |
| 8 | 19.0 | 8000 | 10 | 900 | |
| 9 | 17.5 | 6000 | 30 | 900 | |
| 10 | 19.5 | 13000 | -20 | 900 | |
| 11 | 18.0 | 12000 | -5 | 900 | |
| 12 | 16.0 | 8000 | -20 | 900 | |
| 13 | 22.0 | 13000 | 10 | 900 | |
| 14 | 18.0 | 7500 | -10 | 900 | |
| Comparative Examples | 1 | 23.5 | 12000 | 55 | 900 |
| 2 | 17.2 | 7000 | -55 | 900 | |
| 3 | 26.0 | 13000 | 53 | 900 | |
| 4 | 42.0 | 14000 | 80 | 900 | |
| 5 | 24.0 | 1000 | -60 | 900 | |
| 6 | 25.0 | 2000 | -70 | 900 | |
| 7 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 8 | Glass is being equal to or higher than stripping under 800 ℃ the temperature | ||||
| 9 | Glass is being equal to or higher than stripping under 800 ℃ the temperature | ||||
| 10 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 11 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 12 | In 4 weight % sulphuric acid solns, melt | ||||
| 13 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 14 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 15 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 16 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 17 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 18 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 19 | Glass is being equal to or higher than stripping under 800 ℃ the temperature | ||||
| 20 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 21 | Glass is being equal to or higher than stripping under 900 ℃ the temperature | ||||
According to the scraping blade method, in the 100g of base material and glass mixture, add 9g as the polyvinyl butyral acetal of tackiness agent, 6g as the dibutyl phthalate of softening agent and simultaneously as the 60g toluene and the 30g Virahol of solvent, thereby make the raw cook (greensheet) of thickness 100 μ m.Then, by applying 200kg/cm in 65 ℃
2The thermocompression bonded of pressure is legal, and 22 layers of described raw cook are carried out lamination.At this moment, be positioned to and make it be provided to the center of thickness direction being printed with layer as the Ag of interior electrode.At 900 ℃ gained layered product sintering is generated outer electrode after 2 hours, thereby made three ply board type syntonizer.Syntonizer is of a size of wide 4.9mm, high 1.7mm, long 8.4mm.
Estimate the unloaded Q of gained three ply board type syntonizer at 2GHz resonant frequency place.The unloaded Q that its result obtains described three ply board type syntonizer is 210.By adopting dielectric ceramic composition of the present invention, can obtain having the three ply board type syntonizer of good characteristic thus.
[embodiment 2 and 3]
(embodiment that belongs to first embodiment):
(x ' influence)
With with the foregoing description 1 in identical mode, will be with the Zn of mixed shown in the table 1
2TiO
4, ZnTiO
3And TiO
2Mixture as base material.Described base material is mixed with glass with ratio shown in the table 1 equally.Then, under the condition identical, make the sintering bead, and estimate each characteristic with the method identical with embodiment 1 with embodiment 1.It the results are shown in the table 2.
[embodiment 4-6]
(embodiment that belongs to first embodiment):
(y ' influence)
With with the foregoing description 1 in identical mode, will be with the Zn of mixed shown in the table 1
2TiO
4, ZnTiO
3And TiO
2Mixture as base material.Described base material is mixed with glass with ratio shown in the table 1 equally.Then, under the condition identical, make the sintering bead, and estimate each characteristic with the method identical with embodiment 1 with embodiment 1.It the results are shown in the table 2.
[embodiment 7-9]
(embodiment that belongs to first embodiment):
(influence of particle diameter)
With with the foregoing description 1 in identical mode, will be with the Zn of mixed shown in the table 1
2TiO
4, ZnTiO
3And TiO
2Mixture as base material.Described base material is mixed with glass with ratio shown in the table 1 equally, and the gains pulverizing is reached the median size shown in the table 1 until its particle diameter.Then, under the condition identical, make the sintering bead, and estimate each characteristic with the method identical with embodiment 1 with embodiment 1.It the results are shown in the table 2.
[embodiment 10-12]
(embodiment that belongs to first embodiment):
(influence that glass is formed)
With with the foregoing description 1 in identical mode, will be with the Zn of mixed shown in the table 1
2TiO
4, ZnTiO
3And TiO
2Mixture as base material.Described base material is mixed with the glass of each composition with ratio shown in the table 1 equally.Then, under the condition identical, make the sintering bead, and estimate each characteristic with the method identical with embodiment 1 with embodiment 1.It the results are shown in the table 2.
[embodiment 13-14]
(embodiment that belongs to first embodiment)
(influence of glass consumption)
With with the foregoing description 1 in identical mode, will be with the Zn of mixed shown in the table 1
2TiO
4, ZnTiO
3And TiO
2Mixture as base material.Described base material is mixed with glass with ratio shown in the table 1 equally.Then, under the condition identical, make the sintering bead, and estimate each characteristic with the method identical with embodiment 1 with embodiment 1.It the results are shown in the table 2.
[Comparative Examples 1 and 2]
(x ' influence)
With with the foregoing description 1 in identical mode, will be with the Zn of mixed shown in the table 1
2TiO
4, ZnTiO
3And TiO
2Mixture as base material.Described base material is mixed with glass with ratio shown in the table 1 equally.Then, under the condition identical, make the sintering bead with embodiment 1.Yet, work as Zn
2TiO
4Mol ratio x ' less than 0.15 o'clock, the temperature factor τ of resonant frequency
fExceed+50ppm/ ℃.When x ' greater than 0.8 the time, the temperature factor τ of resonant frequency
fLess than-50ppm/ ℃.It the results are shown in the table 2.
[Comparative Examples 3 and 4]
(y ' influence)
With with the foregoing description 1 in identical mode, will be with the Zn of mixed shown in the table 1
2TiO
4, ZnTiO
3And TiO
2Mixture as base material.Described base material is mixed with glass with ratio shown in the table 1 equally.Then, under the condition identical, make the sintering bead with embodiment 1.Yet, work as TiO
2Mol ratio y ' greater than 0.2 o'clock, the temperature factor τ of resonant frequency
fExceed+50ppm/ ℃.It the results are shown in the table 2.
[Comparative Examples 5-19]
(influence that glass is formed)
With with the foregoing description 1 in identical mode, will be with the Zn of mixed shown in the table 1
2TiO
4, ZnTiO
3And TiO
2Mixture as base material.Described base material is mixed with the glass of each composition with ratio shown in the table 1 equally.Then, under the condition identical, make the sintering bead with embodiment 1.Yet, when employing exceeds the glass composition of scope that the present invention adopts, the Q value occurs and reduce the temperature factor τ of resonant frequency
fBe lower than-50ppm/ ℃ (Comparative Examples 5 and 6), glass is by sulphuric acid soln fusing (Comparative Examples 12), and perhaps bead can not be sintered in the temperature that is equal to or less than 1000 ℃, and perhaps glass is being equal to or higher than stripping (Comparative Examples 7-11 or 13-19) under 800 ℃ the temperature.It the results are shown in the table 2.
[Comparative Examples 20 and 21]
(influence of glass consumption)
With with the foregoing description 1 in identical mode, will be with the Zn of mixed shown in the table 1
2TiO
4, ZnTiO
3And TiO
2Mixture as base material.Described base material is mixed with glass with ratio shown in the table 1 equally.Then, under the condition identical, make the sintering bead with embodiment 1.Yet, when the glass consumption is lower than 3 weight parts, can not realize sintering in the temperature that is equal to or less than 1000 ℃.When the glass consumption is higher than 30 weight parts, glass stripping and react when being equal to or higher than 900 ℃ of temperature with hasten-solidifying agent (setter).Its result is as shown in table 2.
[embodiment 15]
(embodiment that belongs to second embodiment of the invention)
With 0.33 mole of titanium dioxide (TiO
2) place ball mill with ethanol and mixed 12 hours with 0.66 mole of zinc oxide (ZnO).From solution, remove and desolvate, then the gained material is pulverized and under air atmosphere in 1000 ℃ of calcinings, thereby obtain Zn
2TiO
4Calcined powder.Then, with 0.5 mole of TiO
2Mix in mode same as described above with 0.5 mole of ZnO and calcine, thereby obtain ZnTiO
3Calcined powder.With the Zn that obtains thus
2TiO
4And ZnTiO
3Calcined powder and TiO
2And Al
2O
3With mixed shown in the table 3, thereby make base material (principal constituent).The glass powder that in the above-mentioned base material of 100 weight parts, adds 10 weight parts, the ZnO that consists of 63.5 weight % of described glass powder, the SiO of 8 weight %
2, the Al of 1.5 weight %
2O
3, the BaO of 7 weight %, and the B of 20 weight %
2O
3, the gained material placed ball mill and mixed 24 hours.Remove from solution and desolvate, then the gained material being pulverized until median size is 1 μ m.In the gained crushed material, add the polyvinyl alcohol solution of appropriate amount, carry out drying afterwards.Subsequently, the gained material is shaped to the bead of diameter 12mm, thickness 4mm, and with the gained bead in air atmosphere in 850 ℃ of sintering 2 hours (embodiment 15a).Fig. 4 shows the X-ray diffraction pattern of obtained sintering bead.As can be seen from Figure 4, Zn
2TiO
4Phase, ZnTiO
3Phase, TiO
2Phase and Al
2O
3Be present in jointly mutually in the sintering bead of dielectric ceramic composition of the present invention.Will be in the same manner another bead of gained at 950 ℃ of sintering 2 hours (embodiment 15b) in the same manner.
The media ceramic of gained thus is processed into the size of diameter 7mm, thickness 3mm.Measure unloaded Q, the relative permittivity ε at resonant frequency 7-11GHz place then according to the dielectric resonance method
rTemperature factor τ with resonant frequency
fTable 4 shows the result.
[table 3]
| Base material is formed (molar fraction) | Glass is formed (weight %) | Base material consumption (weight part) | Glass consumption (weight part) | Median size after the pulverizing (μ m) | |||||||||
| Zn 2TiO 4 x | ZnTiO 3 y | TiO 2 z | Al 2O 3 w | SiO 2 | Al 2O 3 | ZnO | BaO | B 2O 3 | |||||
| Embodiment | 15a，b | 0.22 | 0.76 | 0.01 | 0.01 | 8.0 | l.5 | 63.5 | 7.0 | 20.0 | 100 | 10 | 1 |
| 16a，b | 0.40 | 0.58 | 0.01 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 100 | 10 | 1 | |
| 17a，b | 0.80 | 0.18 | 0.01 | 001 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 100 | 10 | 1 | |
| 18a，b | 0.97 | 0.01 | 0.01 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 100 | 10 | 1 | |
| 19a，b | 0.22 | 0.77 | 0.00 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 100 | 10 | 1 | |
| 20a，b | 0.20 | 0.69 | 0.10 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 100 | 10 | 1 | |
| 21a，b | 0.18 | 0.61 | 0.20 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 100 | 10 | 1 | |
| 22a，b | 0.22 | 0.75 | 0.01 | 0.02 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 100 | 10 | 1 | |
| 23a，b | 0.21 | 0.73 | 0.01 | 0.05 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 100 | 10 | 1 | |
| 24a，b | 0.19 | 0.65 | 0.01 | 0.15 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 100 | 10 | 1 | |
| 25a，b | 0.22 | 0.76 | 0.01 | 0.01 | 7.0 | 3.0 | 75.0 | 10.0 | 5.0 | 100 | 10 | 1 | |
| 26a，b | 0.22 | 0.76 | 0.01 | 0.01 | 6.0 | 1.5 | 72.0 | 2.5 | 18.0 | 100 | 10 | 1 | |
| 27a，b | 0.22 | 0.76 | 0.01 | 0.01 | 8.0 | 5.0 | 50.0 | 10.0 | 27.0 | 100 | 10 | 1 | |
| 28a，b | 0.22 | 0.76 | 0.01 | 0.01 | 10.0 | 5.0 | 50.0 | 5.0 | 30.0 | 100 | 10 | 1 | |
| 29a，b | 0.22 | 0.76 | 0.01 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 100 | 5 | 1 | |
| 30a，b | 0.22 | 0.76 | 0.01 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | l00 | 25 | 1 | |
| Comparative Examples | 22a，b | 0.10 | 0.88 | 0.01 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | l00 | 10 | 1 |
| 23a，b | 0.98 | 0.00 | 0.01 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 100 | 10 | 1 | |
| 24a，b | 0.15 | 0.54 | 0.30 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 100 | 10 | 1 | |
| 25a，b | 0.11 | 0.38 | 0.50 | 0.01 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 100 | 10 | 1 | |
| 26a，b，c | 0.22 | 0.77 | 0.01 | 0 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 100 | 10 | 1 | |
| 27 | 0.16 | 0.58 | 0.01 | 0.25 | 8.0 | 1.5 | 63.5 | 7.0 | 20.0 | 100 | 10 | 1 | |
| 28 | 0.22 | 0.76 | 0.01 | 0.01 | 20.0 | 0.5 | 75.0 | 2.5 | 2.0 | 100 | 10 | 1 | |
| 29 | 0.22 | 0.76 | 0.01 | 0.01 | 17.0 | 7.0 | 42.0 | 1.0 | 33.0 | 100 | 10 | 1 | |
| 30 | 0.22 | 0.76 | 0.01 | 0.01 | 10.0 | 5.0 | 33.0 | 2.0 | 50.0 | 100 | 10 | 1 | |
| 31 | 0.22 | 0.76 | 0.01 | 0.01 | 25.0 | 1.5 | 45.0 | 8.5 | 20.0 | 100 | 10 | 1 | |
| 32 | 0.22 | 0.76 | 0.01 | 0.01 | 6.0 | 1.5 | 80.0 | 7.5 | 5.0 | 100 | 10 | 1 | |
| 33 | 0.22 | 0.76 | 0.01 | 0.01 | 4.0 | 1.6 | 66.3 | 7.3 | 20.9 | 100 | 10 | 1 | |
| 34 | 0.22 | 0.76 | 0.01 | 0.01 | 18.0 | 1.3 | 56.6 | 6.2 | 17.8 | 100 | 10 | 1 | |
| 35 | 0.22 | 0.76 | 0.01 | 0.01 | 8.1 | 0.1 | 64.4 | 7.1 | 20.3 | 100 | 10 | 1 | |
| 36 | 0.22 | 0.76 | 0.01 | 0.01 | 7.6 | 7.0 | 60.0 | 6.6 | 18.9 | 100 | 10 | 1 | |
| 37 | 0.22 | 0.76 | 0.01 | 0.01 | 11.4 | 2.1 | 48.0 | 10.0 | 28.5 | 100 | 10 | 1 | |
| 38 | 0.22 | 0.76 | 0.01 | 0.01 | 4.4 | 0.8 | 80.0 | 3.8 | 11.0 | 100 | 10 | 1 | |
| 39 | 0.22 | 0.76 | 0.01 | 0.01 | 8.4 | 1.6 | 66.9 | 2.0 | 21.1 | 100 | 10 | 1 | |
| 40 | 0.22 | 0.76 | 0.01 | 0.01 | 7.6 | 1.4 | 60.1 | 12.0 | 18.9 | 100 | 10 | 1 | |
| 41 | 0.22 | 0.76 | 0.01 | 0.01 | 9.6 | 1.8 | 76.2 | 8.4 | 4.0 | 100 | 10 | 1 | |
| 42 | 0.22 | 0.76 | 0.01 | 0.01 | 6.5 | 1.2 | 51.6 | 5.7 | 35.0 | 100 | 10 | 1 | |
| 43 | 0.22 | 0.76 | 0.01 | 0.01 | 6.0 | 1.5 | 80.0 | 7.5 | 5.0 | 100 | 2 | 1 | |
| 44 | 0.22 | 0.76 | 0.01 | 0.01 | 6.0 | 1.5 | 80.0 | 7.5 | 5.0 | 100 | 40 | 1 | |
[table 4]
| ε r | Q×f(GHz) | τ f(ppm/℃) | Sintering temperature/℃ | ||
| Embodiment | 15a | 20.0 | 10000 | 0 | 850 |
| 15b | 20.0 | 10000 | 0 | 950 | |
| 16a | 19.3 | 10000 | -5 | 850 | |
| 16b | 19.3 | 10000 | -5 | 950 | |
| 17a | 17.7 | 9000 | -30 | 850 | |
| 17b | 17.7 | 9000 | -30 | 950 | |
| 18a | 17.0 | 9000 | -50 | 850 | |
| 18b | 17.0 | 9000 | -50 | 950 | |
| 19a | 20.0 | 10000 | -1 | 850 | |
| 19b | 20.0 | 10000 | -1 | 950 | |
| 20a | 22.1 | 12000 | 15 | 850 | |
| 20b | 22.1 | 12000 | 15 | 950 | |
| 21a | 24.5 | 13000 | 30 | 850 | |
| 21b | 24.5 | 13000 | 30 | 950 | |
| 22a | 20.0 | 10000 | 0 | 850 | |
| 22b | 20.0 | 10000 | 0 | 950 | |
| 23a | 19.0 | 8000 | 10 | 850 | |
| 23b | 19.0 | 8000 | 10 | 950 | |
| 24a | 17.5 | 6000 | 30 | 850 | |
| 24b | 17.5 | 6000 | 30 | 950 | |
| 25a | 18.5 | 13000 | -15 | 850 | |
| 25b | 18.5 | 13000 | -15 | 950 | |
| 26a | 19.5 | 13000 | -20 | 850 | |
| 26b | 19.5 | 13000 | -20 | 950 | |
| 27a | 18.0 | 12000 | -5 | 850 | |
| 27b | 18.0 | 12000 | -5 | 950 | |
| 28a | 16.0 | 8000 | -20 | 850 | |
| 28b | 16.0 | 8000 | -20 | 950 | |
| 29a | 22.0 | 13000 | 10 | 850 | |
| 29b | 22.0 | 13000 | 10 | 950 | |
| 30a | 18.0 | 7500 | -10 | 850 | |
| 30b | 18.0 | 7500 | -10 | 950 | |
| Comparative Examples | 22a | 23.5 | 12000 | 55 | 850 |
| 22b | 23.5 | 12000 | 55 | 950 | |
| 23a | 16.5 | 6000 | -60 | 850 | |
| 23b | 16.5 | 6000 | -60 | 950 | |
| 24a | 26.0 | 13000 | 53 | 850 | |
| 24b | 26.0 | 13000 | 53 | 950 | |
| 25a | 42.0 | 14000 | 80 | 850 | |
| 25b | 42.0 | 14000 | 80 | 950 | |
| 26a | 20.0 | 10000 | -54 | 850 | |
| 26b | 20.0 | 10000 | 0 | 900 | |
| 26c | 20.0 | 10000 | 20 | 950 | |
| 27 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 28 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 29 | Glass is being equal to or less than stripping under 800 ℃ the temperature | ||||
| 30 | Glass is being equal to or less than stripping under 800 ℃ the temperature | ||||
| 31 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 32 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 33 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 34 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 35 | In 4 weight % sulphuric acid solns, melt | ||||
| 36 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 37 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 38 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 39 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 40 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 41 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 42 | Glass is being equal to or less than stripping under 800 ℃ the temperature | ||||
| 43 | Be equal to or less than under 1000 ℃ the temperature not sintering | ||||
| 44 | Glass is being equal to or less than stripping under 800 ℃ the temperature | ||||
According to the scraping blade method, in the 100g of base material and glass mixture, add 9g as the polyvinyl butyral acetal of tackiness agent, 6g as the dibutyl phthalate of softening agent and simultaneously as the 60g toluene and the 30g Virahol of solvent, thereby make the raw cook of thickness 100 μ m.Then, by applying 200kg/cm in 65 ℃
2The thermocompression bonded of pressure is legal, and 22 layers of described raw cook are carried out lamination.At this moment, be positioned to and make it be provided to the center of thickness direction being printed with layer as the Ag of interior electrode.At 900 ℃ gained layered product sintering is generated outer electrode after 2 hours, thereby made three ply board type syntonizer.Syntonizer is of a size of wide 4.9mm, high 1.7mm, long 8.4mm.
Estimate the unloaded Q of gained three ply board type syntonizer at 2GHz resonant frequency place.The unloaded Q that its result obtains described three ply board type syntonizer is 210.By adopting dielectric ceramic composition of the present invention, can obtain having the three ply board type syntonizer of good characteristic thus.
[embodiment 16-18]
(embodiment that belongs to second embodiment)
(influence of x and y)
With with the foregoing description 15 in identical mode, will be with the Zn of mixed shown in the table 3
2TiO
4, ZnTiO
3, TiO
2And Al
2O
3Mixture as base material.Described base material is mixed with glass with ratio shown in the table 3 equally.Then, under the condition identical, make the sintering bead, and estimate each characteristic with the method identical with embodiment 15 with embodiment 15.It the results are shown in the table 4.
[embodiment 19-21]
(embodiment that belongs to second embodiment):
(influence of z)
With with the foregoing description 15 in identical mode, will be with the Zn of mixed shown in the table 3
2TiO
4, ZnTiO
3, TiO
2And Al
2O
3Mixture as base material.Described base material is mixed with glass with ratio shown in the table 3 equally.Then, under the condition identical, make the sintering bead, and estimate each characteristic with the method identical with embodiment 15 with embodiment 15.It the results are shown in the table 4.
[embodiment 22-24]
(embodiment that belongs to second embodiment):
(influence of w)
With with the foregoing description 15 in identical mode, will be with the Zn of mixed shown in the table 3
2TiO
4, ZnTiO
3, TiO
2And Al
2O
3Mixture as base material.Described base material is mixed with glass with ratio shown in the table 3 equally.Then, under the condition identical, make the sintering bead, and estimate each characteristic with the method identical with embodiment 15 with embodiment 15.It the results are shown in the table 4.As can be seen, contain Al among these embodiment
2O
3Dielectric ceramic composition of the present invention following stabilising characteristic is provided: suitable relative permittivity, less dielectric loss (high Q value), and the temperature factor τ of its resonant frequency when under 850-950 ℃ wide scope sintering temperature, carrying out sintering
fDifference is less.
[embodiment 25-28]
(embodiment that belongs to second embodiment):
(influence that glass is formed)
With with the foregoing description 15 in identical mode, will be with the Zn of mixed shown in the table 3
2TiO
4, ZnTiO
3, TiO
2And Al
2O
3Mixture as base material.Described base material is mixed with the glass of each composition with ratio shown in the table 3 equally, and the pulverizing of gained material is reached median size shown in the table 3 until its particle diameter.Then, under the condition identical, make the sintering bead, and estimate each characteristic with the method identical with embodiment 15 with embodiment 15.It the results are shown in the table 4.
[embodiment 29 and 30]
(embodiment that belongs to second embodiment):
(influence of glass consumption)
With with the foregoing description 15 in identical mode, will be with the Zn of mixed shown in the table 3
2TiO
4, ZnTiO
3, TiO
2And Al
2O
3Mixture as base material.Described base material is mixed with glass with ratio shown in the table 3 equally.Then, under the condition identical, make the sintering bead, and estimate each characteristic with the method identical with embodiment 15 with embodiment 15.It the results are shown in the table 4.
[Comparative Examples 22 and 23]
(influence of x and y)
With with the foregoing description 15 in identical mode, will be with the Zn of mixed shown in the table 3
2TiO
4, ZnTiO
3, TiO
2And Al
2O
3Mixture as base material.Described base material is mixed with glass with ratio shown in the table 3 equally.Then, under the condition identical, make the sintering bead with embodiment 15.Yet, work as Zn
2TiO
4Mol ratio x be equal to or less than 0.15 or ZnTiO
3Mol ratio y be equal to or greater than 0.85, the temperature factor τ of resonant frequency then
fGreater than+50ppm/ ℃.When y equals 0, the temperature factor τ of resonant frequency
fLess than-50ppm/ ℃.It the results are shown in the table 4.
[Comparative Examples 24 and 25]
(influence of z)
With with the foregoing description 15 in identical mode, will be with the Zn of mixed shown in the table 3
2TiO
4, ZnTiO
3, TiO
2And Al
2O
3Mixture as base material.Described base material is mixed with glass with ratio shown in the table 3 equally.Then, under the condition identical, make the sintering bead with embodiment 15.Yet, work as TiO
2Mol ratio z greater than 0.2 o'clock, the temperature factor τ of resonant frequency then
fGreater than+50ppm/ ℃.It the results are shown in the table 4.
[comparison example 26 and 27]
(influence of w)
With with the foregoing description 15 in identical mode, will be with the Zn of mixed shown in the table 3
2TiO
4, ZnTiO
3, TiO
2And Al
2O
3Mixture as base material.Described base material is mixed with glass with ratio shown in the table 3 equally.Then, under the condition (in addition carry out 900 ℃ sintering) identical, make the sintering bead with embodiment 15.Yet, work as Al
2O
3Mol ratio w equal at 0 o'clock, then under the situation of 850 ℃ of sintering temperatures, the temperature factor τ of resonant frequency
fGreater than 50ppm/ ℃, and the temperature factor τ of described resonant frequency
fInstability and variation are bigger in 850-950 ℃ sintering range.When w was equal to or higher than 0.2, then sintering temperature was equal to or higher than 1000 ℃.It the results are shown in the table 4.
[Comparative Examples 28-42]
(influence that glass is formed)
With with the foregoing description 15 in identical mode, will be with the Zn of mixed shown in the table 3
2TiO
4, ZnTiO
3, TiO
2And Al
2O
3Mixture as base material.Described base material is mixed with the glass of each composition with ratio shown in the table 3 equally.Then, under the condition identical, make the sintering bead with embodiment 15.Yet, when employing exceeds the glass composition of adopting scope among the present invention, glass then appears by sulphuric acid soln fusing (Comparative Examples 35), perhaps bead can not be sintered in the temperature that is equal to or less than 1000 ℃, and perhaps glass is in the temperature stripping (Comparative Examples 28-34 or 36-42) that is equal to or higher than 800 ℃.It the results are shown in the table 4.
[Comparative Examples 43 and 44]
(influence of glass consumption)
With with the foregoing description 15 in identical mode, will be with the Zn of mixed shown in the table 3
2TiO
4, ZnTiO
3, TiO
2And Al
2O
3Mixture as base material.Described base material is mixed with glass with ratio shown in the table 3 equally.Then, under the condition identical, make the sintering bead with embodiment 15.Yet,, can not realize sintering in the temperature that is equal to or less than 1000 ℃ when glass consumption during less than 3 weight parts.When glass consumption during greater than 30 weight parts, then glass reacts 900 ℃ of strippings and with hasten-solidifying agent.It the results are shown in the table 4.
Industrial usability
Dielectric ceramic composition of the present invention can be equal to or less than Ag or Cu fusing point or contain Ag or Cu as the temperature of the alloy melting point of principal component under sintering, this is what be difficult to realize in routine techniques. Thereby according to dielectric ceramic composition of the present invention, can be in the manufacturing of electronic unit this metalloid be used as internal conductor material in encapsulation and the multiple stratification within it. The relative dielectric constant that has about 10-40 by the media ceramic of sintering dielectric ceramic composition gained of the present invention, be preferably about 15-25, and have less dielectric loss tan δ (high Q value), and the temperature coefficient τ of 50ppm/ ℃ or lower dielectric frequencyfAbsolute value. According to the present invention, dielectric ceramic composition is provided and has obtained the manufacture method of described media ceramic, particularly changed the characteristic variations that causes by sintering temperature and difference is less and forms variation less dielectric ceramic composition and manufacture method thereof when sintering. In addition, according to the present invention, the laminated ceramic parts with dielectric layer and interior electrode are provided, for example laminated ceramic compacitor or LC wave filter, described dielectric layer is made by above-mentioned dielectric ceramic composition, described interior electrode contain Ag or Cu or contain Ag or Cu as the alloy of principal component.
Claims (8)
1. dielectric ceramic composition, it comprises:
100 weight part general formulas are x ' Zn
2TiO
4-(1-x '-y ') ZnTiO
3-y ' TiO
2Principal constituent, wherein x ' satisfies 0.15＜x '＜0.8, y ' satisfies 0≤y '≤0.2; With
3-30 weight part Unlead low-smelting point glass, described Unlead low-smelting point glass contains the ZnO of 50-75 weight %, the B of 5-30 weight %
2O
3, the SiO of 6-15 weight %
2, the Al of 0.5-5 weight %
2O
3And the BaO of 3-10 weight %.
2. media ceramic, it comprises Zn
2TiO
4, ZnTiO
3And TiO
2Crystallization phases (TiO wherein
2Can save mutually) and glassy phase, described media ceramic obtains by the dielectric ceramic composition of sintering claim 1.
3. make the method for the dielectric ceramic composition of claim 1, it comprises following steps:
With ZnO raw material powder and TiO
2Raw material powder mixes and calcining, obtains containing Zn
2TiO
4, ZnTiO
3And TiO
2Ceramic powder (TiO wherein
2Content can be 0); With
Described ceramic powder is mixed with Unlead low-smelting point glass, and described Unlead low-smelting point glass contains the ZnO of 50-75 weight %, the B of 5-30 weight %
2O
3, the SiO of 6-15 weight %
2, the Al of 0.5-5 weight %
2O
3And the BaO of 3-10 weight %.
4. laminated ceramic parts, it comprises:
A plurality of medium layers;
Be formed at the interior electrode between the medium layer; With
The outer electrode that is electrically connected with interior electrode,
Wherein medium layer is made of the media ceramic that the dielectric ceramic composition by sintering claim 1 obtains, and interior electrode is by element Cu or elements A g or contain Cu or Ag forms as the alloy material of principal constituent.
5. dielectric ceramic composition, it comprises:
100 weight part general formulas are xZn
2TiO
4-yZnTiO
3-zTiO
2-wAl
2O
3Principal constituent, wherein x satisfies 0.15＜x＜1.0, y satisfies 0＜y＜0.85, z satisfies 0≤z≤0.2, w satisfies 0＜w≤0.2, and satisfies x+y+z+w=1; With
3-30 weight part Unlead low-smelting point glass, described Unlead low-smelting point glass contains the ZnO of 50-75 weight %, the B of 5-30 weight %
2O
3, the SiO of 6-15 weight %
2, the Al of 0.5-5 weight %
2O
3And the BaO of 3-10 weight %.
6. media ceramic, it comprises Zn
2TiO
4, ZnTiO
3, TiO
2And Al
2O
3Crystallization phases (TiO wherein
2Can save mutually) and glassy phase, described media ceramic obtains by the dielectric ceramic composition of sintering claim 5.
7. make the method for the dielectric ceramic composition of claim 5, it comprises following steps:
With ZnO raw material powder and TiO
2Raw material powder mixes and calcining, obtains containing Zn
2TiO
4, ZnTiO
3And TiO
2Ceramic powder (TiO wherein
2Content can be 0); With
With described ceramic powder and Al
2O
3Mix with Unlead low-smelting point glass, described Unlead low-smelting point glass contains the ZnO of 50-75 weight %, the B of 5-30 weight %
2O
3, the SiO of 6-15 weight %
2, the Al of 0.5-5 weight %
2O
3And the BaO of 3-10 weight %.
8. laminated ceramic parts, it comprises:
A plurality of medium layers;
Be formed at the interior electrode between the medium layer; With
The outer electrode that is electrically connected with interior electrode,
Wherein medium layer is made of the media ceramic that the dielectric ceramic composition by sintering claim 5 obtains, and interior electrode is by element Cu or elements A g or contain Cu or Ag forms as the alloy material of principal constituent.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP142149/2003 | 2003-05-20 | ||
| JP2003142148A JP4174668B2 (en) | 2003-05-20 | 2003-05-20 | DIELECTRIC CERAMIC COMPOSITION, PROCESS FOR PRODUCING THE SAME, DIELECTRIC CERAMIC USING THE SAME, AND MULTILAYER CERAMIC COMPONENT |
| JP142148/2003 | 2003-05-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1791562A true CN1791562A (en) | 2006-06-21 |
| CN100378030C CN100378030C (en) | 2008-04-02 |
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ID=33530319
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
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Country Status (2)
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|---|---|
| JP (1) | JP4174668B2 (en) |
| CN (1) | CN100378030C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103708537A (en) * | 2013-06-13 | 2014-04-09 | 济南大学 | Method for finely synthesizing ilmenite structure ZnTiO3 nanometer powder by using water-soluble sol-gel process |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107176834B (en) * | 2016-03-11 | 2020-02-14 | 上海卡翱投资管理合伙企业（有限合伙） | LTCC (Low temperature Co-fired ceramic) ceramic material with medium and high dielectric constant and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0731065B1 (en) * | 1995-03-06 | 1999-07-28 | Matsushita Electric Industrial Co., Ltd | Zinc oxide ceramics and method for producing the same |
| JP3406787B2 (en) * | 1996-09-30 | 2003-05-12 | 京セラ株式会社 | Manufacturing method of dielectric porcelain |
| US5916834A (en) * | 1996-12-27 | 1999-06-29 | Kyocera Corporation | Dielectric ceramics |
-
2003
- 2003-05-20 JP JP2003142148A patent/JP4174668B2/en not_active Expired - Fee Related
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2004
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103708537A (en) * | 2013-06-13 | 2014-04-09 | 济南大学 | Method for finely synthesizing ilmenite structure ZnTiO3 nanometer powder by using water-soluble sol-gel process |
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|---|---|
| CN100378030C (en) | 2008-04-02 |
| JP2004345877A (en) | 2004-12-09 |
| JP4174668B2 (en) | 2008-11-05 |
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