CN1321938C - Low-temperature burnt ferrite material and ferrite parts using the same - Google Patents

Low-temperature burnt ferrite material and ferrite parts using the same Download PDF

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CN1321938C
CN1321938C CNB2005100687359A CN200510068735A CN1321938C CN 1321938 C CN1321938 C CN 1321938C CN B2005100687359 A CNB2005100687359 A CN B2005100687359A CN 200510068735 A CN200510068735 A CN 200510068735A CN 1321938 C CN1321938 C CN 1321938C
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CN1721365A (en
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川崎邦彦
桃井博
铃木孝志
佐藤高弘
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TDK Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
    • H01F1/342—Oxides
    • H01F1/344—Ferrites, e.g. having a cubic spinel structure (X2+O)(Y23+O3), e.g. magnetite Fe3O4

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Abstract

A nickel-basis ferrite material, a sulfur content of ferrite powder in a raw material stage is in a range of from 300 ppm to 900 ppm on S basis and a chlorine content of the ferrite powder is not higher than 100 ppm on Cl basis, while a sulfur content of a ferrite sinter after burning is not higher than 100 ppm on S basis and a chlorine content of the ferrite sinter is not higher than 25 ppm on Cl basis. Furthermore, a ferrite material is constituted by an Ni ferrite material using a nickel compound as a raw material, the nickel compound having a specific surface area in a range of from 1.0 m<2>/g to 10 m<2>/g and a sulfur content in a range of from 100 ppm to 1,000 ppm on S basis.

Description

The ferrite part that the Ferrite Material of low-temperature burning and this material are made
The application is dividing an application of the same patent application of application number 01143384.1, the December 21 calendar year 2001 applying date, denomination of invention.
Invention field
The present invention relates to the Ferrite Material that the ceramic electrical sensor is used, be specifically related to stable and the fabulous Ferrite Material of temperature profile, and relate to ferrite sintered thing as the application of various magneticsubstances, this material can be at low-temperature burning, also relate to the ferrite part that uses this Ferrite Material to make, for example chip inducer, sheet pearl part, composite multi-layer part, ferrite core etc.
Background technology
For example, the multilayer chiop member manufacturing method of chip inducer or sheet pearl part and so on is as follows.Promptly magnetic substance layer creme and inner conductor creme are overlapped together with thick film technology, burning then, and adopt the outer electrode creme to form outer electrode, again with whole laminated piece burning, produce the multilayer chiop parts thus.
Under this situation, this can be in not being higher than agglomerating Ni-Cu-Zn ferrite under the low temperature of the contained Ag fusing point of electrode, generally be used as magnetospheric magneticsubstance.
When using Ni-Cu-Zn ferrite or Ni-Zn ferrite, adopt hydrochloric acid acid etching waste liquid, carry out the Fe that thermolysis obtains with iron(ic) chloride as raw material 2O 3, or carry out the Fe that thermolysis obtains by the ferric sulfate that sulfuric acid acid etching steel obtain 2O 3, as the ferric oxide of producing one of this ferrite raw material.The result exists a small amount of S or Cl inevitably in ferrite raw material.Therefore, according to S or Cl content, people know that this ferrite can influence electromagnetic performance, i.e. inductance performance, or influence sintering character, i.e. density (JP-B 2867196 or JP-A-11-144934).
In addition, also the someone proposes additives (sintering auxiliary material) such as glass, bismuth oxide, vanadium oxide are added, and obtains the production method (seeing JP-B-7-24242 or JP-A-1-179402) of ferrite of high density sinter.If but add examples of such additives, crystal size can occur and disperse the destruction that causes μ, Q and temperature profile.
In the conventional Ferrite Material, the high-density sintered body that lattice vacancy is few can not promptly obtain under the temperature that is not higher than the used Ag fusing point of inner wire under sintering temperature and low.Therefore, in moisture-resistant loading experiment etc., magnetic property is damaged.
Therefore,, but also there is side effect as described below, inner wire disconnected or disappearance, perhaps because Ag diffusion or Cu segregation produce destruction mutually at the crystal grain edge even use additive to make Ferrite Material can at high temperature burn or make density to increase.Therefore inductance, Q or temperature profile all are damaged, and perhaps cause transport phenomena by diffusion Ag.Insulation resistance is damaged as a result, or causes inefficacy by short circuit.
Ferrite Material generally is that iron cpd is got with other ferrite component compound, and with the temporary burning of mixture.In this temporary combustion processes, known to ferrite mixed powder contained S or Cl content difference, and the solid state reaction ratio difference (seeing JP-A-11-144934) of formation spinel type crystal.Because this reaction ratio difference, raw material or midbody product are residual, perhaps because raw material segregation or thermal dissociation intermediate product produce destruction mutually.As a result, it is inhomogeneous that powder composition becomes, and sintered density or magnetic property are all had detrimentally affect.
After the known temporary transient burning, by S residual in the powder that this powder obtained that atomizes or Cl content influence magnetic property (seeing JP-B-2867196), this S or Cl are contained in ferrite and constitute in the element compound.
Disclosure of an invention
The object of the invention provides Fe-Ni-Cu-Zn-Mg Ferrite Material or Fe-Ni-Cu-Zn Ferrite Material, wherein contained S and Cl content are regulated, under the situation of not using any additives, provide high-density and the low Ferrite Material of temperature profile value like this when producing multilayer chiop parts and magnetic core.
In order to reach aforementioned purpose, as described in following (A1)-(A3) section, the inventor finds by regulating the S and the Cl content of the ferrite powder in the Ferrite Material, what no any additives can be provided can reach highdensity Ferrite Material, although and the density height, still have low temperature profile value, thereby use this Ferrite Material that the high performance ferrite parts can be provided, for example chip inducer, sheet pearl part, composite multi-layer part, ferrite core etc. are as described in following (A4)-(A6) section.
(A1) in the Fe-Ni-Cu-Zn-Mg Ferrite Material, sulphur content in the feed stage ferrite powder is counted 300ppm-900ppm with the S element, and the cl content of ferrite powder is in the no more than 100ppm of Cl element, yet the sulphur content of ferrite cemented body is in the no more than 100ppm of S element after the burning, and the cl content of ferrite cemented body is in the no more than 25ppm of Cl element.
(A2) in the Fe-Ni-Cu-Zn Ferrite Material, sulphur content is counted 300ppm-900ppm with the S element in the feed stage ferrite powder, and the cl content of ferrite powder is in the no more than 100ppm of Cl element, but sulphur content is in the no more than 100ppm of S element in the ferrite cemented body after the burning, and the cl content of ferrite cemented body is lower than 10ppm in the Cl element.
(A3) (A1) section defined Ferrite Material in, described ferrite consists of and contains 25-52mol%Fe 2O 3, 40mol% or be lower than 40mol%ZnO, 20mol% be lower than 20mol%CuO, 65mol% or be lower than 65mol%NiO, all the other are for MgO.
(A4) chip part is formed by laminating chip inducer or the sheet pearl part that ferrimagnetism layer and inner wire constituted, and wherein said ferrimagnetism layer is made up of defined any Ferrite Material of (A1)-(A3) section.
(A5) the composite multi-layer parts are grouped into by laminating at least one inductor portion that ferrimagnetism layer and inner wire constitute, and wherein said ferrimagnetism layer is made up of any Ferrite Material of (A1)-(A3) section definition.
(A6) ferrite core is made up of any Ferrite Material of (A1)-(A3) section definition.
Therefore another purpose of the present invention provide that the manufacturing multilayer chiop parts that do not use any additives and magnetic core are used, can provide high-density and the temperature profile value is low, the Ferrite Material that is made of the Ni Ferrite Material.
For reaching aforementioned purpose, the inventor finds as following (B1) and (B2) can provide the Ferrite Material of realizing this purpose as described in the section, and press (B3)-(B5) described ferrite part that realization the object of the invention is provided.
(B1) Ferrite Material that constituted of the Ni Ferrite Material that uses nickel compound to make raw material, described nickel compound specific surface area is 1.0-10m 2/ g, and sulphur content is counted 100ppm-1000ppm with the S element.
(B2) according to the Ferrite Material of (B1) section, wherein consisting of of Ni Ferrite Material contains 25-52mol%Fe 2O 3, 0-40mol%ZnO, 0-20mol%CuO, 1-65mol%NiO, all the other are MgO.
(B3) by laminating the chip part that chip inducer that ferrimagnetism layer and inner wire constitute or sheet pearl part are formed, wherein the ferrimagnetism layer is composed as follows: use the Ni compound to make the Ni Ferrite Material of raw material, its specific surface area of described nickel compound is 1.0m 2/ g-10m 2/ g, its sulphur content are counted 100ppm-1000ppm with the S element; Or use specific surface area 1.0-10m 2/ g, sulphur content is counted the nickel compound of 100ppm-1000ppm with pure S element and is consisted of and contain 25-52mol%Fe as Ni Ferrite Material, this Ni Ferrite Material of nickel compound raw material 2O 3, 0-40mol%ZnO, 0-20mol%CuO, 1-65mol%NiO, all the other are MgO.
(B4) by laminating the composite multi-layer parts that at least one inductor portion branch that ferrimagnetism layer and inner wire constitute is formed, wherein the ferrimagnetism layer is composed as follows: use the Ni compound to make the Ni Ferrite Material of raw material, its specific surface area of described nickel compound is 1.0m 2/ g-10m 2/ g, its sulphur content are counted 100ppm-1000ppm with the S element; Or use specific surface area 1.0-10m 2/ g, Ni Ferrite Material, consisting of of this Ni Ferrite Material that the nickel compound that sulphur content is counted 100ppm-1000ppm with the S element is made the Ni compound of raw material contain 25-52mol%Fe 2O 3, 0-40mol%ZnO, 0-20mol%CuO, 1-65mol%NiO, all the other are MgO.
(B5) ferrite core is constructed as follows: use the Ni compound to make the Ni Ferrite Material of raw material, its specific surface area of described nickel compound is 1.0m 2/ g-10m 2/ g, its sulphur content are counted 100ppm-1000ppm with the S element; Or use specific surface area 1.0-10m 2/ g, Ni Ferrite Material, consisting of of this Ni Ferrite Material that the nickel compound that sulphur content is counted 100ppm-1000ppm with the S element is made the Ni compound of raw material contain 25-52mol%Fe 2O 3, 0-40mol%ZnO, 0-20mol%CuO, 1-65mol%NiO, all the other are MgO.
The accompanying drawing summary
Fig. 1 is to use the view of the composite multi-layer parts that low-temperature sintering of the present invention, high performance ferrite material make.
Detailed description with reference to embodiment
First embodiment
Now more details are as follows for Ferrite Material of the present invention.At first ferrite is constituted element compound, for example Fe 2O 3, the preparation of weighing of NiO, CuO, ZnO and the MgO composition after by burning, close with the pure water wet mixing with ball mill etc.Make wet blended mixture drying with spray-dryer etc., temporarily burn then.Should pulverize by temporary incendiary mixture, and then, obtain ferrite powder thus with dryings such as spray-dryers.
Pulverized and dried this ferrite powder, set its sulphur content and count 300ppm-900ppm with the S element, its cl content is counted 100ppm or lower with the Cl element.
Count 300ppm when following when being in ferrite raw material stage sulphur content with the S element, the sintered density value is lower than the sintered density value 4.85g/cm that can guarantee its moisture resistance 3On the contrary, when sulphur content surpassed 900ppm, sintered density uprised, but the raising of the segregation of the diffusion of Ag or Cu, this is damaged inductance and temperature profile.Here, the inductance of 25 ℃ of measurements of temperature profile value representation and the inductance of 85 ℃ of mensuration, with 25 ℃ inductance be with reference to the time the two between the variation ratio.
The temperature profile value preferably is limited to ± 3%, more preferably be limited to ± 2% within.Therefore, more preferably ferrite raw material stage sulphur content is counted 300ppm-700ppm with the S element.
Even ferrite raw material stage sulphur content in the S element in the 300ppm-900ppm scope, if cl content in the Cl element above 100ppm, sintered density also can suffer damage.
When ferrite raw material stage S and Cl content are divided equally when being limited in the above-mentioned scope in addition, after the burning in the ferrite cemented body sulphur content can not be higher than 100ppm in the S element, and the ferrite sintered in-vivo content of chlorine can not be higher than 25ppm in the chlorine element.Be used as for Ag under the situation of product inner wire, if in the ferrite cemented body sulphur content in the S element above 100ppm, the Ag that then diffuses in the magnetic substance increases, its inductance and temperature profile are all impaired like this.If above 25ppm, then sintered density and temperature profile also can be impaired in the Cl element for cl content.
By the SO that adopts the infrared detector analysis under oxygen atmosphere, combustion of sulfur to be become with oxidation conversion 2Then can measure sulphur content.On the other hand, by extracting Cl, and measure the specific absorption of extracting solution, can measure cl content with vapor distillation method.
During the temporary burning of mixed powder, measure some parts of powder of temporary incendiary under the differing temps, can select spinel type to synthesize the highest temporary temperature of combustion of ratio like this with X-ray diffractometer.Here, the synthetic ratio of spinel type means with powder x-ray diffraction to be measured, with spinel type ferrite (311) planar peak strength (Isp311), α-Fe 2O 3(104) value that formula is obtained below planar peak strength (IFe104), CuO (111) planar peak strength (ICu111) substitution.X-ray diffraction is to measure under all conditions of Cu source, 40kV voltage, 40mA electric current and 2 ° of/minute sweep velocitys in addition.
Figure C20051006873500071
If the synthetic ratio of spinel type is lower than 96%, then residual a lot of ferrites constitute element compound, and sintered density is lower like this.Therefore, the synthetic ratio of preferred spinel type is not less than 96%, more preferably is not less than 99%.
The scope of ferrite composition composition will be limited in the present invention, and its reason is as follows: if main component Fe 2O 3Beyond the scope of 25-52mol%, then the sintered density step-down causes more impaired than perviousness Q, IR (insulation resistance) etc.If ZnO surpasses 40mol%, then Q reduces, and Curie temperature (magnetic transition temperature) becomes and is not higher than 100 ℃ thus, and this situation is inadvisable.
If CuO surpasses 20mol%, then Q reduces.In addition, if surpass the Ferrite Material system composite multi-layer parts of 20mol% with CuO content, then CuO or ZnO are deposited on the mating surface of itself and capacitor material and so on differing materials, just IR reduces like this.If NiO surpasses 65mol%, then this Ferrite Material can not be at the sintering temperature that is not higher than the Ag fusing point.If substitute part NiO with MgO, then temperature profile is improved, and sintered density or remain unchanged than perviousness.But, if MgO surpasses 15mol%, sintered density or all more impaired then than perviousness, therefore, MgO content preferably is not higher than 15mol%.In addition, the oxide compound of other Co, Mn etc. can account for about 2wt% of whole material or still less.
Above-mentioned Fe 2O 3, NiO, CuO, ZnO and MgO composition can measure for the x-ray fluorescence analysis on basis in order to glass bead method.
Therefore, do not use any additives can obtain to provide highdensity Ferrite Material, although and this material density height has low temperature profile value.In addition, by ferrite core and the multilayer chiop parts that this Ferrite Material is formed, fabulous aspect moisture resistance and temperature profile.And the dissipation of sintered density or inductance can reduce.
The embodiment of first embodiment
Embodiments of the invention are described below.The preparation burning of respectively raw material being weighed contains 49.0mol%Fe afterwards 2O 3, 25.0mol%NiO, 12.0mol%CuO and 14.0mol%ZnO composition.Embodiment 1 and 2 and comparative example 3 in, with MgO partial Ni O, each raw material of weighing respectively, preparation contains 49.0mol%Fe 2O 3, 20.0mol%NiO, 5mol%MgO, 12.0mol%CuO and 14.0mol% ZnO composition.Adopt ball mill, each raw material and pure water wet mixing are closed, and use the spray-dryer drying.Then, this mix powder 700 ℃ to 800 ℃ interim burnings 10 hours, should be eluriated grinding with pure water by temporary incendiary powder with ball mill afterwards, use the spray-dryer drying again.
The polyvinyl alcohol of 10 weight parts is joined in the thus obtained porphyrize powder of 100 weight parts, and make particle.Then this particle is molded into annular.This mold pressing object in 880 ℃ of burnings 2 hours, is obtained sintered compact thus.Weight and size by sintered compact calculate its density.It is as follows than perviousness μ i and Q pH-value determination pH.That is, the copper metal wire is around on the annular element, around 20 circles.Under survey frequency 10MHz and measurement electric current 0.5mA condition, use the LCR instrument to measure inductance and Q value.Draw i by following formula than perviousness μ:
(than perviousness μ i)=(le * L)/(μ o * Ae * N 2)
Le: magnet passage length, L: the inductance of sample,
μ o: very aerial perviousness, Ae: sample in cross section is long-pending,
N: wire circle.
Then, make the multilayer chiop inducer.The ethyl cellulose of 4 weight parts and the terpinol of 78 weight parts are joined in the porphyrize powder of 100 weight parts, it is mediated, so that preparation magnetic substance layer creme by triple-roller mill.On the other hand, the terpinol of the ethyl cellulose of 2.5 weight parts and 40 weight parts is added among the Ag of mean particle size 0.6 μ m of 100 weight parts, with triple-roller mill it is kneaded, so that electrode creme in the preparation, thus obtained magnetosphere creme and interior electrode creme are alternately printed, make it to laminate mutually, and in 850 ℃ of burnings 2 hours, so obtain the multilayer chiop inducer.
This 3216 type (3.2mm is long, and 1.6mm is wide) its size of multilayer chiop inducer is 3.2mm * 1.6mm * 1.2mm, and the number of turns is set at 9.5.Then, in 600 ℃ of burnings, form outer electrode in the end of this multilayer chiop inducer.Adopt LCR instrument method, under survey frequency 10MHz and measurement electric current 0.1mA condition, measure inductance L and Q value.
When measuring frequency 1MHz, measure 25 ℃ inductance and 85 ℃ inductance, with 25 ℃ of variation ratios that inductance is measured as a reference, as the inductance temperature profile value that is equipped with annular element and each multilayer chiop inducer.
Point out in passing,, can obtain desirable S and Cl content by selecting to have the raw material of different S content and different Cl content.
The results are shown in Table 1 for this.
[table 1]
The S in ferrite raw material stage and Cl content S in the ferrite cemented body and Cl content Annular element is in 880 ℃ of burnings The multilayer chiop inducer is in 850 ℃ of burnings
S (ppm) Cl (ppm) S (ppm) Cl (ppm) Sintered density (g/cm 3) Than seeing through property Q Temperature profile value (%) Sintered density (g/cm 3) Inductance (μ H) Q Temperature profile value (%)
Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 300 300 400 550 580 620 700 900 70 100 0 8 5 40 5 5 60 60 62 78 70 90 98 100 15 25 0 0 0 9 0 0 4.91 4.90 4.91 4.90 4.90 4.90 4.91 4 93 81.4 80.5 80.6 81.2 80.7 81.2 81.5 81.8 133 130 131 122 130 133 125 125 0.98 1.20 1.11 0.62 1.05 1.22 1.93 2.59 5.24 5.25 5.25 5.26 5.24 5.25 5.25 5.25 4.32 4.32 4.33 4.38 4.34 4.39 4.30 4.25 62 57 57 57 60 58 67 56 56 1.92 1.80 1.65 1.79 1.24 1.50 1.70 2.25
Comparative example 1 comparative example 2 comparative examples 3 comparative examples 4 150 180 330 950 400 2 125 6 40 54 64 133 120 0 30 0 4.40 4.66 4.69 5.00 49.3 60.9 60.0 86.5 141 138 130 112 4.25 -1.56 -1.10 4.15 4.43 5.09 4.99 5.30 4.00 4.05 4.00 4.02 50 54 51 55 6.98 -0.98 3.88 4.28
Find out obviously that from table 1 when the sulphur content of feed stage was lower than 300ppm in the S element, shown in comparative example 1 and 2, the sintered density of annular element was low to moderate and is not higher than 4.85g/cm 3, and the sintered density of multilayer chiop inducer is not higher than 5.15g/em 3, therefore, this sintered density does not reach the value that can guarantee moisture resistance.
When its sulphur content of feed stage in the S element during above 900ppm, shown in comparative example 4, its temperature profile value increases, the two all is not less than 4% annular element and multilayer chiop inducer.
When the feed stage cl content in the Cl element during above 100ppm, shown in comparative example 1 and 3, the sintered density of annular element is low to moderate and is not higher than 4.85g/cm 3, and the multilayer chiop inducer is not higher than 5.15g/cm 3Therefore, this sintered density does not reach the value that can guarantee its moisture resistance.
On the other hand, when sulphur content in the ferrite cemented body in the S element during above 100ppm, shown in comparative example 4, its temperature profile value increases, the two all is not less than 4% annular element and multilayer chiop inducer.
When cl content in the sintered compact that contains MgO in the Cl element during above 25ppm, shown in comparative example 3, the sintered density of annular element is low to moderate and is not higher than 4.85g/cm 3, and the multilayer chiop inducer is not higher than 5.15g/cm 3Therefore, this sintered density does not reach the value that can guarantee its moisture resistance.
When cl content in the sintered compact that does not contain MgO was lower than 10ppm in the Cl element, shown in embodiment 6, its sintered density satisfied the value that guarantees moisture resistance.Therefore, annular element still is that the multilayer chiop inducer all has fabulous electromagnetic performance and temperature profile.
Therefore, should be clear and definite, if Ferrite Material meets the framework of the present definition, then for annular element, sintered density is not less than 4.85g/cm 3, for the multilayer chiop inducer, be not less than 5.15g/cm 3, the simultaneous temperature characteristic is limited to ± 3% within.
Below with reference to Fig. 1, illustrate that relevant the present invention uses by 49mol%Fe 2O 3, the prepared LC composite multi-layer of the ferrite parts formed of 17mol%NiO, 9mol%CuO and 25mol%ZnO describe.
LC composite component 1 shown in Figure 1 laminates the capacitor part 2 that constitutes mutually by ceramic dielectric layers 21 and inner electrode layer 25, and ceramic magnetic material layer 31 and inner wire 35 inductor portion portions 3 that laminates formation mutually combines and makes.Outer electrode 51 is formed on the surface of LC composite component 1.
Point out that in passing capacitor part 2 and inductor portion portions 3 can have conventional known structure.Capacitor part 2 and inductor portion portions 3 roughly form rectangle separately.The size of this LC composite component 1 is not specifically limited, but can set according to using suitably.The size of this LC composite component 1 can be about 1.6-10.0mm * 0.8-15.0mm * 1.0-5.0mm.
The ceramic magnetic material layer 31 that constitutes inductor portion portions 3 is made up of Ferrite Material of the present invention.That is to say, tackiness agent such as Ferrite Material of the present invention and ethyl cellulose and terpinol or diethylene glycol monobutyl ether equal solvent are mediated the creme of making magnetic substance layer, again itself and interior electrode creme are alternately printed and overlap together, form inductor portion portions 3 thus.Tackiness agent and solvent and unrestricted in this magnetic substance layer creme, for example can set binder content is 1wt%-5wt%, and setting solvent content is roughly 10wt%-50wt%.
In addition, inductor portion portions 3 can use ceramic magnetic material layer sheet material to make.In other words, with Ferrite Material of the present invention with contain polyvinyl butyral acetal or acrylic resin and in ball mill, mediate the slurry of formation as the tackiness agent of main component and toluene or dimethylbenzene equal solvent, be applied on polyester film and so on doctor method etc., make it the dry magnetic substance layer sheet material that obtains.
Binder content and unrestricted in this magnetic substance layer sheet material, for example binder content can be set in about 1-5wt% scope.
The electro-conductive material that is contained in the interior electrode 35 of inductor portion portions 3 there is no concrete restriction.But preferably should make by the electro-conductive material that mainly contains low resistance Ag by interior electrode 35, to obtain the suitable Q value of inducer.Usually use Ag, Ag alloy, Cu, Cu alloy etc.Interior electrode 35 each layers are oval, between electrode 35 adjacent layerss volution electric action are arranged in guaranteeing.Therefore, electrode 35 forms sealing magnetic flux coil (being wound in figure) in this.Outer electrode 51 is connected on the opposite end of sealing magnetic flux coil.
In this case, be wound in figure, that is to say that the sealing magnet passage shape of inner wire 35 can be made various figures.Its number of turns can suitably be selected according to application.In addition, the size of each part etc. and unrestricted in the inductor portion portions 3, but can suitably select according to its application.
In addition, to design inner wire 35 usually, make its thickness be about 3 μ m-50 μ m, the about 10 μ m-400 μ m of coiling pitch, and the about 1.5-50.5 of the number of turns.On the other hand, magnetosphere 31 is also designed, make the about 100 μ m-500 μ m of its basic thickness, and the about 10 μ m-100 μ m of the magnetic layer thickness between each inner wire 35 and 35.
The material that is used for capacitor part 2 ceramic dielectric layers 21 is unrestricted.Though various dielectric materialss all can utilize, preferably use the titanium dioxide dielectric materials, because of its temperature of combustion low.In addition, titanate composite oxides, zirconate composite oxides, or its mixture also can be so that use.In addition, in order to reduce the glass that temperature of combustion also can contain borosilicate glass and so on.
Specifically, contain NiO, CuO, Mn 3O 4, Al 2O 3, MgO, SiO 2Deng, particularly contain the titanium dioxide etc. of CuO, as required, also can be used as the titanium oxide dielectric materials; BaTiO 3, SrTiO 3, CaTiO 3, MgTiO 3Or its mixture can be used as the titanate composite oxides; And BaZrO 3, SrZrO 3, CaZrO 3, MgZrO 3Or its mixture can be used as the zirconate composite oxides.
In addition, if do not use mixing material, for example can use nonmagnetic Zn ferrite etc.
Mediate the creme of gained by the used material of the ceramic dielectric layers 21 of capacitor part 2 and various tackiness agent and solvent, can alternately print with interior electrode creme and be superimposed together.Be contained in the content of tackiness agent in this dielectric layer creme and solvent and unrestricted.For example, binder content can be set at 1-5wt%, and solvent can be set at about 10-50wt%.
In addition, capacitor part 2 can be made by the dielectric layer sheet material.That is to say, dielectric materials and various tackiness agent and solvent are mediated the slurries that the back forms with ball mill, coat in modes such as doctors on the material such as polyester film, make it the dry dielectric layer sheet material that forms.This dielectric layer sheet material and interior electrode creme are alternately overlapped together, form capacitor part 2 thus.Binder content and unrestricted in this dielectric layer sheet material, for example binder content can be set at about 1-5wt%.
The inner electrode layer 25 used electro-conductive materials of forming capacitor part 2 also do not have concrete restriction.This electro-conductive material can be selected from Ag, Pt, Pd, Au, Cu, Ni, contain the alloy of at least a these described metals, for example Ag-Pd alloy etc.Preferred especially Ag, Ag alloy, for example Ag-Pd alloy etc.
The size of each part there is no concrete restriction in the capacitor part 2, but can be according to suitably selections such as its Application Areass.Get on very well in passing, the number of plies of dielectric layer 21 is 1-100, and each medium thickness is 10-150 μ m, and inner electrode layer 25 every layer thickness are 3-30 μ m.
Outer electrode 51 used electro-conductive materials be there is no concrete restriction, and this electro-conductive material can be selected from Ag, Pt, Pd, Au, Cu, Ni, contain the alloy of at least a these described metals, for example Ag-Pd alloy etc.The shape of this outer electrode 51, size etc. are not also had concrete restriction, but can suitably determine according to its purpose and Application Areas.Thickness is about 3-200 μ m usually.
Inner wire creme, interior electrode creme and outer electrode creme, be by with above-mentioned various conducting metals or alloy, perhaps mediate with above-mentioned various tackiness agents and solvent respectively and make by the various oxide compounds that form above-mentioned electro-conductive material after the burning, organometallic compound, resinate etc.
When making LC composite component 1, for example, form inductor portion portions at first with magnetic substance layer creme and inner wire creme printing and superimposed on (polyethylene terephthalate) substrates such as PET.With dielectric layer creme and interior electrode creme printing and superimposed on this inductor portion portions, form capacitor part again.In addition, can form capacitor part earlier and form inductor portion portions then thereon.In addition, can make the not chip of sintering (green chip) as described below.In other words, form not sintered sheets with magnetic substance layer creme and dielectric layer creme, at this not on the sintered sheets after the printing, these cremes can be built up not sintering chip with inner wire creme and inner electrode layer creme.In this case, can directly print with the magnetic substance layer adjacent dielectric layers.
Then, can or be transferred to this not on the sintering chip with the printing of outer electrode creme.Magnetic substance layer creme, inner wire creme, dielectric layer creme, inner electrode layer creme and outer electrode creme are burnt together simultaneously.
In addition, electrode creme printing outside or be needed on not on the sintering chip and before the burning, with this not sintering chip burning.
The preferred burn temperature is set in 800 ℃-930 ℃, especially 850 ℃-900 ℃.If temperature of combustion is lower than 800 ℃, incomplete combustion then, on the contrary, if temperature of combustion surpasses 930 ℃, then inner electrode can diffuse in the Ferrite Material, just electromagnetic performance significantly reduces like this.In addition, the preferred burn time set is 0.05-5 hour, especially 0.1-3 hour.Burn in oxygen partial pressure PO 2Carry out under=1%-100% the condition.
In addition, for the burning outer electrode temperature of combustion be about 500-700 ℃ usually, be generally about 10 minutes to 3 hours combustion time.Burning is carried out in air usually.
According to the present invention, preferably have in when burning or burning back more to many and heat-treat under the atmosphere of excess oxygen than atmosphere.
Since heat-treat containing under the excess oxygen atmosphere, the material that is deposited, or with metallic forms such as Cu, Zn, or with Cu 2O, Zn 2The material of low resistance oxide form deposits such as O can be with high resistance and in fact harmless oxide form deposits such as CuO, ZnO.For this reason, the circuit resistance of part obtains bigger improvement.
Carry out when in addition, preferred thermal treatment is in the end burnt or behind the final combustion.
For example, when sintering chip and outer electrode did not burn simultaneously, predetermined thermal treatment or was carried out after such burning preferably when such burning.On the other hand, when outer electrode during at the burning of sintering chip not back reignition, predetermined thermal treatment or is carried out after outer electrode burns preferably when outer electrode burn.Point out in passing, burn shown in one situation as the back and carried out that according to circumstances, thermal treatment can be when sintering chip burning not, or carries out after burning at twice o'clock.
The oxygen partial pressure of heat-treating atmosphere is 20.8-100%, more preferably 50-100%, most preferably 100%.
Point out in passing, above-mentioned 20.8% if oxygen partial pressure is lower than, then limit Cu, Zn, Cu 2O, Zn 2The ability of deposits such as O reduces.
The thermal treatment of under excess oxygen atmosphere, carrying out usually simultaneously at sintering chip incendiary not, or the outer electrode incendiary carries out simultaneously.Therefore, this thermal treatment temp, conditions such as time length, with sintering chip combustion conditions not, or the outer electrode combustion conditions is similar.If when only heat-treating separately, preferred thermal treatment temp is set at 550 ℃-900 ℃, especially 650 ℃-800 ℃, and the time length is set at 0.5-2 hour, especially 1-1.5 hour.
Get on very well in passing, the composite multi-layer parts outside the LC composite component also can be made in a manner described.
The welding of outer electrode and printed circuit board (PCB), therefore, the composite multi-layer parts such as LC composite component of Zhi Zaoing are assemblied on the printed circuit board (PCB) thus, are used on the various electronicss etc.
Sulphur content in the magnetic substance layer 31, method is analyzed as described below.Be about to magnetic substance layer and separate, pulverize, oxidizing fire under oxygen atmosphere then, the SO that transforms by the infrared detector analysis 2On the other hand, from the broken sample of fine powder, extract Cl, and measure the specific absorption of extracting solution, thereby measure its cl content with vapor distillation method.In addition, the Fe in the magnetic substance layer 2O 3, NiO, CuO, ZnO and MgO form, can adopt based on the fluorescent x-ary analysis of glass bead method and measure.
According to low-temperature sintering of the present invention and high performance Ferrite Material, constitute by the Fe-Ni-Cu-Zn-Mg Ferrite Material.Wherein the ferritic sulphur content of feed stage is set at 300ppm-900ppm in the S element, be not higher than 100ppm and be set in the Cl element at ferrite raw material stage cl content, and after the burning in the ferrite cemented body sulphur content be set in the S element and be not higher than 100ppm, the cl content in the ferrite cemented body is set in the Cl element and is not higher than 25ppm.Do not use any additives just can obtain highdensity Ferrite Material can be provided thus, although and this material density height, less temperature profile value is arranged.In addition, by ferrite chipware and multilayer chiop parts that this Ferrite Material is made, its moisture resistance and temperature profile are fabulous.And the dissipation of sintered density or inductance all can reduce.
Low-temperature sintering of the present invention and high performance Ferrite Material, constitute by the Fe-Ni-Cu-Zn Ferrite Material, wherein the sulphur content in ferrite raw material stage is set at 300ppm-900ppm in the S element, be not higher than 100ppm and be set in the Cl element at ferrite raw material stage cl content, and after the burning in the ferrite cemented body sulphur content be set in the S element and be not higher than 100ppm, and the cl content in the ferrite cemented body is set in the Cl element and is less than 10ppm.Thus, do not use any additives just can obtain highdensity Ferrite Material can be provided, although the density height, this material has less temperature profile value.In addition, by ferrite chipware and multilayer chiop parts that this Ferrite Material is made, its moisture resistance and temperature profile are fabulous.
In addition, use consists of 25-52mol%Fe 2O 3, following ZnO, the 20mol% of 40mol% or its or its following CuO, 65mol% or its following NiO, all the other are the Ferrite Material of MgO, and do not use any additives, low-temperature burning and high performance Ferrite Material just can be provided, and this density of material height, Q value are high, IR value height, more fabulous and temperature profile is fabulous than perviousness.
If chip inducer or sheet pearl parts are made by above-mentioned Ferrite Material, then the moisture resistance of these parts and temperature profile are all fabulous.
Make by above-mentioned Ferrite Material if having the composite component of inductor portion portions, then can obtain the wherein moisture resistance and all fabulous composite component of temperature profile of inductor portion portions.
If the ferrite chipware is to be made by above-mentioned Ferrite Material, then can obtain all fabulous ferrite chipware of moisture resistance and temperature profile.
Second embodiment
According to the present invention, in the Ferrite Material that the ceramic electrical sensor is used, the specific surface area of nickel compound and S content are set respectively in advance.Therefore, obtain highdensity ferrite can not use any additives, although and the density height, its temperature profile value is lower.The ferrite chipware and the multilayer chiop parts that are made by this Ferrite Material have fabulous moisture resistance and temperature profile.And the dissipation of its sintered density or inductance also can reduce.
Ferrite Material generally mixes by iron cpd and other ferrite are constituted element compound, then it is temporarily burnt and obtains.In this temporary burning process, form as everyone knows spinel type crystal the solid state reaction ratio, change to some extent according to the difference of S in the ferrite powder or Cl content.Because this reaction ratio difference, therefore cause raw material or intermediate product residual, perhaps, raw material segregation or intermediate product thermal dissociation destroy because of causing mutually.This powder composition is inhomogeneous as a result, and sintered density or magnetic property are all had detrimentally affect.
People know that also in the powder that this powder of porphyrize is obtained after the temporary burning, S or Cl residual content can influence magnetic property.Described S or Cl are contained in ferrite and constitute in the element compound.
The inventor detects according to this general knowledge, found that, regulated, even do not use any additives also can provide highdensity Ferrite Material by specific surface area and S content to nickel compound in the Ferrite Material, although this material density height, its temperature profile value is lower.
This Ferrite Material of the present invention specifically describes as follows.At first, with Fe 2O 3, NiO, CuO, ZnO and MgO and so on ferrite constitutes element compound as raw material, it by the preparation of weighing of the composition after the burning, and is closed itself and pure water wet mixing with ball mill etc.
, temporarily burn then this wet mixture drying with spray-dryer etc.With ball mill and so on temporary incendiary mixture and pure water are eluriated porphyrize.The mixture of this porphyrize uses spray-dryer and so in addition dry again, obtains ferrite powder thus.At this moment, with the specific surface area be 1.0-10m 2/ g, sulphur content is counted the raw material of 100ppm-1000ppm as nickel compound with the S element.
If the specific surface area of nickel compound is less than 1.0m 2/ g, even so after its temporary burning, this nickel compound is not the solid solution attitude yet.Therefore, ferrite constitutes element compound can be residual, thereby the sintered density value can be lower than the 4.85g/cm that guarantees its moisture resistance 3Value.On the other hand, when the nickel compound specific surface area greater than 10m 2During/g, this powder is difficult to processing, and because of when this powder mixes with water, this powder is very light can only to float on the surface, so mixing efficiency incurs loss.The result closes the bad dispersion in stage owing to this nickel compound in the powder wet mixing, and makes it to be difficult to be the solid solution attitude after the temporary burning.Ferrite constitutes element compound and left behind, and makes sintered density be lower than 4.85g/cm 3Thereby, can not guarantee its moisture resistance.
Even specific surface area is 1.0m 2/ g-10m 2/ g, but if S content is lower than 100ppm, sintered density also can be low to moderate the degree that can not guarantee moisture resistance.On the contrary, if S content surpasses 1000ppm, it is very high that sintered density becomes, but Ag diffusion or the increase of Cu segregation cause inductance or temperature profile all to be damaged.
Herein, the temperature profile value representation is for referencial use with 25 ℃ inductance value, in 25 ℃ the variation ratio of the inductance value of surveying and 85 ℃ of these values between the inductance value of surveying.Described temperature profile value requires in ± 3% scope, more preferably ± 2% in.Therefore for abundant satisfied temperature characteristic value be limited to ± 2% within, and sintered density is 4.85g/cm 3Condition, more preferably the specific surface area of nickel compound is 2-5m 2/ g, and sulphur content is counted 250ppm-700ppm with the S element.
Point out that in passing described specific surface area can be measured with the BET method.In addition, sulphur content can be analyzed as follows, promptly under oxygen atmosphere, will be as the nickel compound oxidizing fire of raw material, and the SO that transforms with the infrared detector analysis 2
In the temporary burning process of mixed powder, in order to obtain best temporary temperature of combustion, measure some parts of powdered samples after temporary burning under the differing temps with X-ray diffractometer, select the highest temporary temperature of combustion of synthetic spinel type ratio thus.
Herein, described spinel type synthesizes ratio, and expression is with the spinel type ferrite in the powder x-ray diffraction (311) planar peak strength (Isp311), α-Fe 2O 3(104) value that formula is obtained below planar peak strength (IFe104) and CuO (111) planar peak strength (ICu111) substitution.In addition, this X-ray diffraction Cu source, voltage 40kV, electric current 40mA, and 2 ° of/minute conditions of sweep velocity under measure.
Figure C20051006873500181
If the synthetic ratio of spinel type is lower than 96%, it is residual that then a large amount of ferrites constitute element compound, makes the sintered density step-down.The synthetic ratio of therefore preferred spinel type is not less than 96%, more preferably is not less than 99%, determines optimum temps in view of the above.
Among the present invention, in view of following reason, ferrite component content scope will be limited.
If main component Fe 2O 3Content is beyond 25-52mol%, and sintered density does not reach 4.85g/cm 3, and be low to moderate cause more impaired than indexs such as perviousness, Q, insulation resistance IR.
If ZnO surpasses 40mol%, then Q reduces, and causes Curie temperature not to be higher than 100 ℃, and this situation is also inadvisable.
If CuO surpasses 20mol%, then Q reduces.In addition, if Ferrite Material is used for the composite multi-layer parts, CuO or ZnO can be deposited on the mating surface place of differing materials such as capacitor material, so IR reduces.
If NiO surpasses 65mol%, then Ferrite Material can not be at the sintering temperature that is not higher than the Ag fusing point.If NiO is lower than 1%, then insulation resistance IR is impaired.
When MgO replaced NiO a part of, its temperature profile was improved, and keeps sintered density and more constant than perviousness.But, if MgO surpasses 15mol%, sintered density or can be impaired then than perviousness, therefore preferred MgO content is not higher than 15mol%.
In addition, oxide compounds such as other Co, Mn can account for overall about 2wt% or still less.The dvielement of Co and Mn can not improve sintered density, but Co improves the Q value, and Mn improves insulation resistance IR.
The embodiment of second embodiment
The embodiment of the invention is described below.Ferrite is constituted the element compound preparation of weighing, and it is composed as follows: the Fe of 49.0mol% after making its burning 2O 3, the CuO of NiO, 12.0mol% of 25.0mol% and the ZnO of 14.0mol%.By ball mill these compounds and pure water wet mixing are closed, again with the spray-dryer drying.It is to be noted that in passing its specific surface area of nickel oxide of using as raw material is 1-71m in addition 2/ g, and sulphur content is counted 0-1130ppm with the S element.
Then in 700-800 ℃ with the temporary burning of this mixed powder 10 hours, the powder that will temporarily burn with ball mill is eluriated with pure water and is ground afterwards, uses the spray-dryer drying again.The polyvinyl alcohol of 10 weight parts is joined in the porphyrize powder of thus obtained 100 weight parts.Then this powder is made particle, and be molded into annular element.
With this molding in 880 ℃ of burnings 2 hours, to obtain sintered compact.Sintered density can be calculated by sintered compact weight and size.In addition, measure as follows than perviousness μ i and Q.In other words copper cash is around on the annular element around 20 circles.Measure inductance and Q value measuring frequency 10MHz under the mensuration electric current 0.5mA condition with the LCR instrument.Obtain than perviousness with following formula:
(than perviousness μ i)=(le * L)/(μ o * Ae * N 2)
Le: magnet passage length, L: the sample inductance,
μ o: perviousness in the vacuum, Ae: sample in cross section is long-pending,
N: the number of turns of coil
Then make the multilayer chiop inducer.The ethyl cellulose and the 78 weight part terpinols of 4 weight parts are joined in the porphyrize powder of 100 weight parts, and mediate, prepare the magnetic substance layer creme with triple-roller mill.On the other hand, ethyl cellulose with 2.5 weight parts, join among the Ag of 100 weight parts of mean particle size 0.6 μ m with the terpinol of 40 weight parts, and mediate with triple-roller mill, electrode creme in preparing thus alternately prints magnetic substance layer creme and the interior electrode creme that makes thus, is superimposed with each other making it, and, obtain the multilayer chiop inducer thus in 850 ℃ of burnings 2 hours.
It is of a size of 3.2mm * 1.6mm * 1.2mm this 3216 type (3.2mm is long, and 1.6mm is wide) multilayer chiop inducer, and the number of turns is set at 5.5.Then, form outer electrode at the both ends of this multilayer chiop inducer 600 ℃ of burnings.By LCR instrument method, measuring frequency 10MHz and measuring under the electric current 0.1mA condition and measure inductance L and Q value.
Measuring under the frequency 1 MHz condition, measures 25 ℃ of following inductance and 85 ℃ of inductance, as reference, its inductance changes ratio as each annular element and the inductance temperature profile value of multilayer chiop inducer fully with 25 ℃ of inductance down.
This results are shown in table 2.
[table 2]
The nickel compound powder characteristics Annular element is in 880 ℃ of burnings The multilayer chiop inducer is in 850 ℃ of burnings
Specific surface area (m 2/g) S (ppm) Sintered density (g/cm 3) Compare perviousness Q Temperature profile value (%) Sintered density (g/cm 3) Inductance (μ H) Q Temperature profile value (%)
Embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 1.0 1.6 2.7 3.0 3.4 4.0 4.3 5.0 7.2 200 740 240 347 318 100 391 650 350 4.85 4.87 4.86 4.87 4.86 4.85 4.90 4.90 4.90 79.3 80.4 79.8 80.3 79.9 79.0 80.8 81.0 81.0 133 136 132 134 134 133 137 136 135 1.38 2.99 1.69 1.56 1.30 1.26 1.76 1.99 2.00 5.15 5.20 5.16 5.17 5.17 5.15 5.18 5.20 5.19 1.50 1.54 1.55 1.56 1.54 1.54 1.60 1.61 1.55 54 58 57 57 55 56 58 57 56 1.00 2.17 1.17 1.38 1.28 0.75 1.67 1.96 2.00
Comparative example 1 comparative example 2 comparative examples 3 comparative examples 4 comparative examples 5 comparative examples 6 comparative examples 7 0.8 11.9 71.0 4.3 2.4 3.2 1.7 0 0 0 0 30 80 1130 4.59 4.72 4.76 4.67 4.75 4.80 5.14 50.0 60.0 64.0 54.0 60.0 71.0 97.0 137 145 144 139 144 134 130 -1.85 -1.24 -1.96 -1.51 -0.49 0.30 4.17 5.00 5.02 5.01 5.02 5.03 5.09 5.15 1.30 1.32 1.31 1.32 1.35 1.42 1.37 46 50 48 49 49 53 52 -1.44 -0.59 -1.46 -0.90 -0.45 0.50 4.28
Find out obviously that from table 2 preferably the specific surface area of nickel compound is at 1.0-10m 2In/g the scope, and its sulphur content in the S element in the 100ppm-1000ppm scope.If in this scope, 1-6 does not obviously find out from comparative example, for annular element, its sintered density is lower than 4.85g/cm 3, and for chip inducer, be lower than 5.15g/cm 3, its moisture resistance can not guarantee like this.
In addition, shown in comparative example 7, if S content surpasses 1000ppm in the nickel compound, its sintered density can reach the value that guarantees moisture resistance, but the temperature profile value increases above ± 3%.Should be clear and definite, satisfy the Ferrite Material of the present invention's definition, for annular element, can provide to be not less than 4.85g/cm 3, the sintered density value, for chip inducer, can provide to be not less than 5.15g/cm 3The sintered density value, and the temperature profile value all is limited to ± 3% within.
Especially the specific surface area at nickel compound is 2-5m 2/ g, its sulphur content is counted with the S element under the situation of 250ppm-750ppm, can obtain better sintered density and better temperature profile, shown in embodiment 3,4,5,7 and 8.
Below with reference to Fig. 1, introduce the Fe that the relevant the present invention of use contains 49mol% 2O 3, the CuO of ZnO, 9mol% of 25mol% and 17mol% the situation of the LC composite multi-layer parts made of the ferrite of NiO.
LC composite component 1 as shown in Figure 1, form by capacitor part 2 and inductor portion portions 3 set, described capacitor part 2 is overrided to form mutually by ceramic dielectric layers 21 and inner electrode layer 22, and described inductor portion portions 3 is overrided to form mutually by ceramic magnetic material layer 31 and inner wire 32.Outer electrode 41 is formed on the surface of LC composite component 1.
Point out that in passing capacitor part 2 and inductor portion portions 3 can be conventional known structure.Each capacitor part 2 and inducer 3 form rectangle usually substantially.The size of LC composite component 1 there is no concrete restriction, but can suitably set according to its concrete application.The size of this LC composite component 1 is about 1.6-10.0mm * 0.8-15.0mm * 1.0-5.0mm.
The ceramic magnetic material layer 31 of inductor portion portions 3 is made up of Ferrite Material of the present invention.That is to say Ferrite Material of the present invention is mediated with tackiness agent such as ethyl cellulose and terpinol, diethylene glycol monobutyl ether equal solvent, obtain the magnetic substance layer creme, itself and interior electrode creme are alternately printed, and superimposed, can form inductor portion portions 3 thus.Tackiness agent and solvent and unrestricted in this magnetic substance layer creme.For example binder content can be set at 1-5wt%, and solvent can be set at about 10-50wt%.
In addition, inductor portion portions 3 can be made by ceramic magnetic material layer sheet material.That is to say, with Ferrite Material of the present invention with contain tackiness agent that polyvinyl butyral acetal or acrylic resin are main component and toluene or dimethylbenzene equal solvent and in ball mill, mediate the formation slurries, it is coated on polyester film and so on material with doctor method etc., make it the dry magnetic substance layer sheet material that obtains.Binder content in this magnetic substance layer sheet material is also unrestricted, for example can be set at about 1-5wt%.
The conductor material that constitutes the interior electrode 32 of inductor portion portions 3 there is no concrete restriction, but preferably should constitute with the electro-conductive material of mainly being made up of low resistance Ag by interior electrode 32, so that obtain the suitable Q value of inducer.Usually use Ag, Ag alloy, Cu, Cu alloy etc.Interior electrode 32 each layers are ellipse, guarantee to have the spiral electric action between interior electrode 32 adjacent each layers.Therefore electrode 32 forms closed magnetic flux lines circle (curling into figure) in, and 41 of outer electrodes are connected on the relative two ends of closed magnetic flux lines circle.
In this case, be wound in figure, promptly the closed magnet passage shape of inner wire 32 can be made various different graphics.Its number of turns can be selected according to its concrete application suitably.In addition, the size of each part etc. and unrestricted in this inducer 3, but can suitably select according to concrete application.
Point out that in passing this inner wire 32 will design usually especially,, twine pitch and be about 10-400 μ m that the number of turns is about 1.5-50.5 so that its thickness is about 3-50 μ m.On the other hand, magnetosphere 31 also will design especially, and making it basic thickness is 100-500 μ m, and the magnetic layer thickness between each inner wire 32 and 32 is about 10-100 μ m.
The material of the ceramic dielectric layers 21 that capacitor part 2 is used there is no concrete restriction.Though various dielectric materialss are all available, preferably adopt the titanium oxide dielectric materials, because of its temperature of combustion low.In addition, titanate composite oxides, zirconate composite oxides or its mixture are all available.In addition, in order to reduce temperature of combustion, this material can contain the glass material of borosilicate glass and so on.
Specifically, contain NiO, CuO, Mn as required 3O 4, Al 2O 3, MgO, SiO 2Deng TiO 2, particularly contain the TiO of CuO 2Can be used as the titanium dioxide dielectric materials; BaTiO 3, SrTiO 3, CaTiO 3, MgTiO 3Or its mixture can be used as the titanate composite oxides; BaZrO 3, SrZrO 3, CaZrO 3, MgZrO 3Or its mixture can be used as the zirconate composite oxides.In addition, if do not use mixing material, for example can use nonmagnetic Zn ferrite etc.
With ceramic dielectric layers 21 material therefors of capacitor part 2, mediate the dielectric layer creme that is obtained with various tackiness agents and solvent, alternately print also superimposed with interior electrode creme.Contained activator and solvent and unrestricted in this dielectric layer creme.For example binder content can be set at 1-5wt%, and solvent can be set at about 10-50wt%.
In addition, capacitor part 2 can also use the dielectric layer sheet material to make.In other words, in ball mill, make dielectric materials and various tackiness agent and solvent mediate form slurries, its class methods with doctor are coated on the material such as polyester film, and made its dry acquisition dielectric layer sheet material.This dielectric layer sheet material and interior electrode creme are alternately overlapped together, form capacitor part 2 thus.Binder content in this dielectric layer sheet material is also unrestricted, and for example this content can be set at about 1-5wt%.
The electro-conductive material of forming inner electrode layer 22 in the capacitor part 2 there is no concrete restriction.This electro-conductive material can be selected from Ag, Pt, Pd, Au, Cu, Ni, contain the alloy of at least a described metal, for example Ag-Pd alloy etc.Especially preferred Ag, Ag alloy, for example Ag-Pd alloy etc.
Each accessory size in the capacitor part 2 there is no concrete restriction, but can be according to suitably selections such as its concrete application.Point out that in passing the number of plies of dielectric layer 21 is 1-100, its every layer thickness is 10-150 μ m, and every layer thickness of inner electrode layer 22 is about 3-30 μ m.
Outer electrode 41 used electro-conductive materials be there is no concrete restriction, and described electro-conductive material can be selected from Ag, Pt, Pd, Au, Cu, Ni, contain the alloy of at least a described metal, for example Ag-Pd alloy etc.The shape of outer electrode 41, size etc. also do not have concrete restriction, but can maybe should be used for suitably determining according to its specific purposes.Its thickness is about 3-200 μ m usually.
Inner wire creme, interior electrode creme and outer electrode creme, can mediate manufacturing with above-mentioned various tackiness agents and solvent respectively by above-mentioned various conducting metals or alloy, the various oxide compounds, organometallic compound, resinate etc. that can become above-mentioned electro-conductive material after maybe will burning are mediated with it and are made.
When making LC composite component 1, for example can at first magnetic substance layer creme and inner wire creme be printed, and laminate on PET substrates such as (polyethylene terephthalates), form inductor portion portions 3 thus.With dielectric layer creme and the printing of interior electrode creme and laminate on this inductor portion portions 3, form capacitor part 2 again.In addition, capacitor part 2 can form earlier before inductor portion portions 3 forms thereon.
Point out in passing, can as described belowly make not sintering chip, in other words, adopt magnetic substance layer creme and dielectric layer creme to form not sintered sheets, with inner wire creme and inner electrode layer creme be printed in this not on the sintered sheets after, these cremes can laminate and form not sintering chip.In this case, can directly print with the magnetic substance layer adjacent dielectric layers.
Then, with the printing of outer electrode creme or be needed on not on the sintering chip.Magnetic substance layer creme, inner wire creme, dielectric layer creme, inner electrode layer creme and outer electrode layer creme are burnt simultaneously.
In addition, can be earlier it goes up also reignition with sintering chip burning not and then with the printing of outer electrode creme or transfer printing.
The preferred burn temperature is set at 800 ℃-930 ℃, particularly 850 ℃-900 ℃.If temperature of combustion is lower than 800 ℃, incomplete combustion then, on the contrary, if temperature of combustion surpasses 930 ℃, then inner electrode can diffuse in the Ferrite Material, and electromagnetic performance suffers damage inevitably.In addition, the preferred burn time set is 0.05-5 hour, particularly 0.1-3 hour.Burning is at oxygen partial pressure PO 2Carry out under=1%-100% the condition.
In addition, be about usually 500-700 ℃ of the temperature of combustion of burning outer electrode, common about 10 minutes to 3 hours of combustion time.Burning is generally carried out in air.
According to the present invention, preferably after when burning or burning, heat-treat under the atmosphere of excess oxygen containing to have than the oxygen in the atmosphere more to many.
Because heat-treat containing under the atmosphere of excess oxygen, the material of institute's deposit is perhaps with metallic forms such as Cu, Zn, or with Cu 2O, Zn 2The material of the low resistance oxide form deposit of O etc. all can be with high resistance and in fact harmless oxide form deposits such as CuO, ZnO.
In addition, preferably when burning or after the burning, heat-treat.
For example, if sintering chip and outer electrode do not burn simultaneously, predetermined thermal treatment is preferably carried out when such burning is carried out or after the burning.On the other hand, if outer electrode reignition after the sintering chip does not burn, then Yu Ding thermal treatment is carried out in the outer electrode burning or after its burning.Point out that in passing as described in one situation of back, burning will carry out twice, then according to circumstances, thermal treatment can be carried out when the sintering chip does not burn or after its burning.
The preferred 20.8-100% of oxygen partial pressure under the heat-treating atmosphere, more preferably 50-100%, most preferably 100%.
Point out in passing, above-mentioned 20.8% if oxygen partial pressure is lower than, then to restriction deposit Cu, Zn, Cu 2O, Zn 2The ability drop of O etc.
Thermal treatment under this kind excess oxygen atmosphere is not usually in that sintering chip or outer electrode incendiary carry out simultaneously.Therefore, conditions such as thermal treatment temp, time length are with the conditional likelihood of burn sintering chip not or outer electrode.If only heat-treat, preferably this thermal treatment temp is set at 550-900 ℃, and preferred 650-800 ℃, the time length is set at 0.5-2 hour, particularly 1-1.5 hour.
Can also make LC composite component composite multi-layer parts in addition as stated above.
Outer electrode and printed circuit board (PCB) etc. weld together.Composite multi-layer parts such as the LC composite component that produces thus are assemblied in above printed circuit board (PCB) etc., are used for various electronicss or the like.
Fe in the magnetic substance layer 2O 3, NiO, CuO, ZnO and MgO composition, can adopt based on the fluorescent x-ary analysis of bead method and measure.
The invention effect
Can obtain following effect according to the present invention.
Be 1.0-10m by adopting specific area2/ g, sulfur content is counted the Ferrite Material that Ni ferrite material that the nickel compound of 100ppm-1000ppm makes as raw material is consisted of with the S element, then can not use any additive, and can provide highdensity Ferrite Material, although and the density height, its temperature characterisitic value is lower. In addition, because consist of multilayer chiop parts or ferrite chipware by the ferrite of high density material, so can give its good moisture resistance and fabulous temperature characterisitic.
Be 1.0-10m by adopting specific area2/ g, the nickel compound that sulfur content is counted 100ppm-1000ppm with the S element make the Ferrite Material that Ni ferrite material that raw material obtains is consisted of, and wherein the composition of this Ferrite Material is: Fe2O 3For 25-52mol%, ZnO are that 0-40mol%, CuO are that 0-20mol%, NiO are 1-65mol%, all the other are MgO, can provide highdensity Ferrite Material in the situation that does not add any additive, although the density height still has fabulous temperature characterisitic value. In addition, this Ferrite Material can be under the temperature that is not higher than the Ag fusing point sintering. Multilayer chiop parts or the ferrite chipware made by this Ferrite Material have excellent performance equally.
The chip part of making by laminated the chip inducer that consists of or sheet pearl part by ferrimagnetism layer and inner wire, wherein said ferrimagnetism layer is composed as follows: the use specific area is 1.0-10m2The nickel compound that/g, sulfur content are counted 100ppm-1000ppm with the S element is made the Ni Ferrite Material that raw material generates; Or use specific area to be 1.0-10m2/ g, sulfur content are counted the nickel compound of 100ppm-1000ppm and are the Ni Ferrite Material of raw material generation take the S element, and consist of in this Ni Ferrite Material: Fe2O 3Account for 25-52mol%, ZnO and account for that 0-40mol %, CuO account for 0-20mol%, NiO accounts for 1-65mol%, all the other are MgO, and chip inducer or sheet pearl parts can be provided thus, though these goods density height, but its temperature characterisitic value is lower, and can be under the temperature that is not higher than the Ag fusing point sintering.
Laminated by ferrimagnetism layer and inner wire by adopting, the composite multi-layer parts that at least one inductor portion portions of formation is made, wherein said ferrimagnetism layer is composed as follows: use specific area to be 1-10m2/ g, the nickel compound that sulfur content is counted 100-1000ppm with the S element is made the Ni Ferrite Material that raw material generates; Or use specific area to be 1.0-10m2/ g, sulfur content is counted the nickel compound of 100-1000ppm and is the Ni Ferrite Material of raw material generation take the S element, and this Ni Ferrite Material consists of Fe2O 3Account for 25-52mol%, ZnO and account for that 0-40mol %, CuO account for 0-20mol%, NiO accounts for 1-65mol%, all the other are MgO, the littler composite multi-layer parts of temperature characterisitic value although the density height can be provided thus, and these parts can be under the temperature that is not higher than the Ag fusing point sintering.
By using the ferrite core of following material formation: the employing specific area is 1.0-10m2/ g, sulfur content is counted the nickel compound of 100-1000ppm and is the Ni Ferrite Material of raw material generation take the S element; The employing specific area is 1.0-10m2/ g, sulfur content is counted the nickel compound of 100-1000ppm and is the Ni Ferrite Material of raw material generation take the S element, and this Ni Ferrite Material consists of Fe2O 3Accounting for 25-52mol%, ZnO accounts for 0-40mol%, CuO and accounts for 0-20mol %, NiO and account for 1-65mol%, all the other are MgO, although can provide the density height thus, and the lower ferrite core of temperature characterisitic value, and this ferrite core can be under the temperature that is not higher than the Ag fusing point sintering.

Claims (4)

1. Ni-based Ferrite Material, it comprises:
Use nickel compound to make the Ni Ferrite Material of raw material, described nickel compound specific surface area is 1.0-10m 2/ g, and sulphur content is counted 100-1000ppm with the S element;
Consisting of of wherein said Ni Ferrite Material: Fe 2O 3Account for 25-52mol%, ZnO and account for that 0-40mol%, CuO account for 0-20mol%, NiO accounts for 1-65mol%, all the other are MgO.
2. foliated core chip part, it comprises by ferrimagnetism layer and inner wire and laminates chip inducer or the sheet pearl part that constitutes;
Wherein said ferrimagnetism layer is composed as follows:
Use specific surface area to be 1.0-10m 2/ g, sulphur content is counted the Ni Ferrite Material of the nickel compound of 100-1000ppm as raw material with the S element;
Consisting of of wherein said Ni Ferrite Material: Fe 2O 3Account for 25-52mol%, ZnO and account for that 0-40mol%, CuO account for 0-20mol%, NiO accounts for 1-65mol%, all the other are MgO.
3. composite multi-layer parts, it comprises inductor portion portions at least, and described inductor portion portions is laminated by ferrimagnetism layer and inner wire and constitutes,
Wherein said ferrimagnetism layer is composed as follows:
Use the Ni Ferrite Material of nickel compound as raw material, the specific surface area of said nickel compound is 1.0-10m 2/ g, sulphur content is counted 100-1000ppm with the S element;
Wherein said Ni Ferrite Material consists of: Fe 2O 3Account for 25-52mol%, ZnO and account for that 0-40mol%, CuO account for 0-20mol%, NiO accounts for 1-65mol%, all the other are MgO.
4. ferrite core, it comprises:
Use the Ni Ferrite Material of nickel compound as raw material, the specific surface area of said nickel compound is 1.0-10m 2/ g, sulphur content is counted 100-1000ppm with the S element;
Wherein said Ni Ferrite Material consists of: Fe 2O 3Account for 25-52mol%, ZnO and account for that 0-40mol%, CuO account for 0-20mol%, NiO accounts for 1-65mol%, all the other are MgO.
CNB2005100687359A 2000-12-25 2001-12-21 Low-temperature burnt ferrite material and ferrite parts using the same Expired - Lifetime CN1321938C (en)

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