WO1999012173A1 - Ferrite de manganese/zinc - Google Patents
Ferrite de manganese/zinc Download PDFInfo
- Publication number
- WO1999012173A1 WO1999012173A1 PCT/JP1998/003763 JP9803763W WO9912173A1 WO 1999012173 A1 WO1999012173 A1 WO 1999012173A1 JP 9803763 W JP9803763 W JP 9803763W WO 9912173 A1 WO9912173 A1 WO 9912173A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxide
- terms
- manganese
- oppm
- raw material
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
- C04B35/2658—Other ferrites containing manganese or zinc, e.g. Mn-Zn ferrites
-
- 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
Definitions
- the present invention relates to a manganese-zinc based ferrite excellent in DC superposition characteristics, and more particularly to a manganese-zinc based ferrite used in coil transformers of various communication devices, consumer appliances, etc. in which the DC superposition characteristics are considered.
- Manganese-zinc based ferrite is used as a core material for coils and transformers in various communication equipment and consumer equipment. For such applications, especially for ferrite cores for communication equipment, high permeability characteristics are required at a relatively high frequency and in a wide band (about 100 to 500 kHz).
- a manganese-zinc ferrite having a high initial magnetic permeability i in such a frequency band is disclosed, for example, in Japanese Unexamined Patent Publication No. Hei 6-2004 / 25 (Bi and Mo added, 100 kHz and 500 kHz). Initial magnetic permeability i force of 900 or more and 300 or more).
- an object of the present invention is to provide a magnetic recording medium having an initial magnetic permeability / i of 500 or more and a core loss P cv Is to provide a manganese-zinc based ferrite having a manganese-zinc content of 400 kW / m 3 or less.
- Another object of the present invention is to provide a manganese-zinc ferrite having a saturation magnetic flux density Bs of 50 OmT or more and excellent DC superimposition characteristics.
- a manganese-zinc ferrite of (1) whose saturation magnetic flux density Bs at a frequency of 100 kHz and 25 ° C is 50 OmT or more.
- subcomponent material is, S I_ ⁇ 2 and oxide Gay containing starting material 1 10 to 170 Hare m in terms of, C and calcium oxide raw material 100 ⁇ 25 Oppm in A_ ⁇ terms, S N_ ⁇ 2 translated at 50 0 and tin oxide raw material to 400 Oppm, and niobium oxide material of 50 to 35 Oppm in Nb 2 0 5 in terms, zirconium oxide material of 100 to 40 Oppm in Z R_ ⁇ 2 terms,
- (6) subcomponent material is, S I_ ⁇ and 1 1 5 ⁇ 15 Oppm oxide Kei containing starting material with 2 equivalent, and calcium oxide raw material of 130 to 230 Hare m in C A_ ⁇ terms, 10 00 in S nO terms 3000 and tin oxide material of the Rabbit m, Nb, O s converted at 100 to 300 ppm of Niobium oxide raw material, Zr0 converted zirconium oxide raw material of 100 to 30 Oppm, Bi 2 ⁇ : Bismuth oxide raw material of 100 to 20 Oppm converted, ⁇ Mo ⁇ : 50 to 15 Oppm converted to i (5) A manganese-zinc ferrite containing the molybdenum oxide raw material.
- Manganese-zinc ferrite with initial permeability i at frequency 100 kHz, 25, core loss P cv at 100 kHz, 200 mT, 40 ° C, and frequency 100 kHz, 25 Manganese-zinc based ferrite whose saturation magnetic flux density Bs at 25 ° C satisfies 7000 ⁇ i ⁇ Bs ZP cv.
- main component material is, and from 6 to 54.4 mol% of oxide Cheorwon fee 53. 6 2 0 3 basis, and 13. 0-1 3.5 mole% of zinc oxide material in terms of ZnO, oxide Manganese-Zinc-based ferrite of (7) consisting of manganese raw material (remainder).
- (1 0) subcomponent material is, S i 0 2 and 1 10 ⁇ 1 7 Oppm oxide Kei raw material in terms of a 1 00-250 Hare m calcium oxide material in C A_ ⁇ terms, S N_ ⁇ 2 equivalent a tin oxide material of 500 to 4000 ppm in the 50 to 350 ppm of niobium oxide material in Nb 2 0 5 in terms, zirconium oxide raw material 1 00 ⁇ 40 Oppm in Z R_ ⁇ 2 equivalent, B i 2 0; i (7) A manganese-zinc ferrite containing a bismuth oxide raw material of 50 to 20 ppm in conversion and a molybdenum oxide raw material of 50 to 200 ppm in Mo ⁇ : i .
- (1 1) subcomponent material is, S 1 and 1. 5 to 1 50 ppm of oxidized Gay raw materials in I_ ⁇ 2 terms, and calcium oxide raw material 1 30 ⁇ 23 Oppm in C aO-terms, with S N_ ⁇ terms 1000 a tin oxide material of ⁇ 3000 ppm, and niobium oxide material of Nb O s 1 00 ⁇ 300 pp m in terms of a zirconium oxide raw material 1 00 ⁇ 30 Oppm in Z R_ ⁇ terms, with B i 2 0 :) terms Bismuth oxide raw material of 100 ⁇ 20 Oppm, Mo ⁇ : 1 (7) A manganese-zinc ferrite containing 50 to 150 m in conversion of a molybdenum oxide raw material. Action and effect
- the manganese-zinc based ferrite of the present invention can improve the saturation magnetic flux density Bs while maintaining the initial magnetic permeability ⁇ i by defining the amount of the main component within the above range, and furthermore, has a DC superposition characteristic.
- the saturation magnetic flux density B s can be increased to 50 OmT or more, so when used for a transformer core that requires DC superposition characteristics for communication equipment, etc., the number of turns of the transformer coil is reduced.
- the size of the core or the transformer can be reduced.
- the initial permeability / ii is particularly high at a frequency of 100 to 500 kHz, and the core loss P cv is low and saturation magnetic flux density B s is high.
- Manganese-zinc ferrites for power transformers are required to improve core loss PcV in the high-frequency range of about 100 to 500 kHz, and various proposals have been made for this purpose.
- some manganese-zinc based ferrites for power transformers have a saturation magnetic flux density B s of 50 OmT or more and take account of the DC bias characteristics, but the initial permeability / i was at most 2300 or less.
- FIG. 1 is a graph showing DC superposition characteristics of core samples according to an example of the present invention and a comparative example.
- the manganese-zinc-based ferrite of the present invention has magnetic properties such as an initial magnetic permeability ⁇ i at a frequency of 100 kHz and 25 ° C of 5000 or more, a saturation magnetic flux density Bs (25 ° C) of 50 OmT or more, and a frequency of 100 Core loss P c V at 40 ° C when applying a sinusoidal AC magnetic field of kHz and 200 mT is 400 kWZm : i or less.
- the larger the initial magnetic permeability i the better, but the upper limit is currently about 6000.
- the larger the saturation magnetic flux density Bs, the better, but the upper limit is currently about 54 OmT.
- the smaller the core loss P c V is, the better, but at present the lower limit is about 270 kW / m 3 .
- the value of i'Bs / Pcv is 7000 or more, preferably 7200 or more, and particularly preferably 8000 or more.
- the upper limit is around 9500. If this value is 7000 or more, i ⁇ 5000, Bs (25 ° C) ⁇ 50 OmT and P cv ⁇ 400 kwZm : i are not necessarily required as described above.
- the manganese-zinc ferrite of the present invention has improved DC bias characteristics.
- the ratio between the residual magnetic flux density and the saturation magnetic flux density that is, the squareness ratio BrZBs, is preferably 0.1 to 0.3, particularly 0.1 to 0.2. Is preferred.
- Manganese present invention -..
- the main component material of zinc ferrite preferably 53.
- 6-54 4 mol% particularly preferably 53.7 to 54 2 molar% iron oxide
- a raw material preferably a zinc oxide raw material in an amount of 13.0 to 13.5 mol% in terms of Z ⁇ , particularly preferably a 13.1 to 13.4 mol%, and a manganese oxide raw material (remaining main component raw material) )
- the composition of the main component material is out of the above range, it tends to be difficult to obtain a high saturation magnetic flux density Bs mainly.
- the main component raw material ordinary iron oxide raw material, manganese oxide raw material and zinc oxide raw material, that is, oxides or various compounds that become oxides by firing may be used.
- the auxiliary component raw materials include a silicon oxide raw material, a calcium oxide raw material, a tin oxide raw material, a niobium oxide raw material, a zirconium oxide raw material, a bismuth oxide raw material, and a molybdenum oxide raw material.
- an oxide of each metal or a compound which becomes an oxide upon firing may be used.
- a raw material for manganese oxide SiO 2 is preferable, and as a raw material for calcium oxide, CaCO 3 is used.
- S N_ ⁇ 2 as a tin oxide material, preferably Nb 2 ⁇ 5 as niobium oxide material, preferably Z R_ ⁇ 2 as zirconium oxide raw material, as the bismuth oxide material B i ⁇ > O
- the molybdenum oxide raw material is preferably ⁇ 0 : ⁇ .
- the content of the silicon oxide raw material is preferably 110 to 170 ⁇ m in terms of SiO 2, particularly preferably 115 to 15 ppm. If the content is outside the above range, the initial magnetic permeability i tends to decrease and the core loss P c V tends to increase.
- the content of the calcium oxide raw material is preferably from 100 to 250 m in Ca ⁇ , particularly preferably from 130 to 23 Oppm. If the content is outside the above range, the initial magnetic permeability i tends to decrease and the core loss P c V tends to increase.
- the content of tin oxide raw material is preferably S N_ ⁇ 2 terms in 500-400 Oppm, particularly preferably 1000 ⁇ 300 Oppm. If the content is out of the above range, the initial magnetic permeability i tends to be low and the core loss P cv tends to be large, as in the case of the above components.
- the content of niobium oxide raw material is preferably 50 to 350 ppm in N b 2 O 5 in terms of, particularly preferably 100 ⁇ 30 Oppm.
- the core loss P cv tends to increase
- the initial permeability i tends to decrease
- the core loss P c V tends to increase.
- the content of the zirconium oxide material is preferably Z R_ ⁇ 2 terms in 100 to 400 pm, particularly preferably 100 ⁇ 30 Oppm. If the content is out of the above range, the core loss P c V increases.
- the content of molybdenum oxide raw material is preferably 50 to 200 ppm by M O_ ⁇ 3 basis, particularly preferably 50 ⁇ 15 Oppm.
- the initial magnetic permeability ⁇ i decreases. If the content is too small, abnormal grain growth occurs during firing and the initial magnetic permeability i decreases. On the other hand, if the content is too high, the amount of sublimation or evaporation of Mo during sintering increases, so that when many compacts are sintered at the same time, the variation in magnetic properties increases.
- the content of the subcomponent raw material is a ratio to the main component raw material.
- Manganese one zinc ferrite in Bok of the present invention shows the above-mentioned is preferably a force for example Ta 2 0 more other is not possible to contain the secondary components,, V 2 0 5, I n, O: i, such as T i ⁇ 2 One or more may be contained. These contents are converted to Ti 0., 0 to 30 Oppm, Ta., ⁇ , V., ⁇ ",, In., ⁇ :, respectively. The total amount is preferably about 0 to 10 ppm.
- a suitable binder for example, polypinyl alcohol, is added in an appropriate amount, for example, 0.1 to 1.0% by weight, to a mixture of the main component material and the auxiliary component material, and the particle size is about 80 to 200 m using a spray dryer or the like. After forming into granules, it is molded.
- the compact is fired.
- the temperature is gradually increased to a sintering temperature at a rate of about 50 to 300 ° CZhr, usually 1250 ° C or more, especially 1300 ° C or more.
- the sintering is completed by holding at a predetermined temperature in the range of 1400 ° C for about 4 to 5 hours. After completion of sintering, it is preferable to cool at a cooling rate of about 50 to 300 ° C / hr in an atmosphere in which the oxygen concentration is controlled.
- the oxygen partial pressure should be at least 25%, especially at least 30%, at least from the temperature of 1000 ° C or more when the temperature is raised to the temperature holding step, more preferably in the temperature range of 1000 ° C or more. It is preferably 30 to 100%.
- a long holding time may be given at a high firing temperature. However, if the firing is performed at a high temperature for a long time, the life of the firing furnace is shortened or the productivity is reduced.
- the above-described oxygen sintering enables the initial firing at 100 to 500 kHz even at a relatively low temperature and in a short time.
- the magnetic permeability i can be increased.
- sublimation or evaporation of Mo and Bi is suppressed, so that the variation of the initial permeability / ii is further reduced.
- firing is preferably performed in a pusher furnace.
- a pusher furnace a set of loaded multiple compacts is continuously introduced into the furnace, enabling continuous firing.
- the composition after firing is usually as follows.
- Main component is 53.6 to 54.4 mol% in terms of Fe 0 ;! , Preferably 53.7 to It contains 54.2 mol% of iron oxide and 13.0 to 13.5 mol% of zinc oxide in terms of Zn ⁇ , with the balance being manganese oxide.
- Subcomponent material is, S I_ ⁇ 2 terms in S I_ ⁇ 2 terms in 1 10 ⁇ 17 Oppm, preferably 1 15-15 and oxidation gay elements of Oppm, C aO converted at 130 to 230 Rabbit m, favored properly 250 and calcium oxide ⁇ 35 Oppm, S N_ ⁇ 2 converted at 500-400 O pm, preferably a tin oxide 1000 to 3000 ppm, Nb 2 ⁇ 5 terms in 5 0 ⁇ 35 Oppm, preferably 100 to 30 Oppm and niobium oxide, Z R_ ⁇ 2 terms in 100 ⁇ 40 Oppm, preferably a zirconium oxide 100 ⁇ 300 ppm, B i 2 0 3 translated at 50 ⁇ 20 Oppm, preferably oxide bis mass 100 ⁇ 20 Oppm, MO0 3 translated at 50 ⁇ 20 Oppm, preferably 50: it includes a L 50 ppm of molybdenum oxide.
- the amount of the subcomponent in the core may be larger than the amount of the subcomponent raw material added, because the subcomponent constituent element is often included as an impurity in the main component raw material.
- the amount of subcomponents in the manganese-zinc based ferrite may be smaller than the amount of the subcomponent raw material added, because the subcomponent constituent elements may sublimate or evaporate during firing.
- the average crystal grain size of the manganese-zinc ferrite of the present invention is preferably 5 to 50 zm. If the average crystal grain size is too large or too small, the high frequency characteristics of the initial magnetic permeability i will be reduced.
- the average crystal grain size may be determined as an average of diameters of polycrystals observed with an optical microscope after the mirror-polished surface is subjected to acid etching and converted into a circle.
- the manganese-zinc-based ferrite of the present invention produced as described above has, as magnetic properties, an initial magnetic permeability i at a frequency of 100 kHz, 5,000 or more, a saturation magnetic flux density Bs of 50 OmT or more, and a frequency of 100 kHz.
- the core loss P c V at 40 ° C when a sine-wave AC magnetic field of 200 mT is applied can achieve all of 400 kW / m : i or less.
- the value of ⁇ Bs (25 ° C) ZP cv (40 ° C) also achieved 7000 or more. Monkey
- the shape can be a crucible type, a toroidal shape, EI, or the like.
- the impedance can be adjusted by providing an air gap of 50 m or less in cores such as crucibles and EI.
- the main ingredient, Mn ⁇ , 110 ⁇ ? 6 2 ⁇ : i and, S i ⁇ 2 is a subcomponent material, Sn_ ⁇ 2, Nb 2 0 5, Z r 0 2, B i 2 ⁇ : i, Mo_ ⁇ 3 and. a A mixture with CO 3 was prepared at the composition ratio shown in Table 1.
- a binder was added to the mixture, and the mixture was granulated with a spray dryer to an average particle size of 15 ⁇ m and molded.
- the compact was heated in an atmosphere in which the oxygen partial pressure was controlled, and sintered at 1350 ° C for 4 hours. Then, it was cooled in an atmosphere with controlled oxygen partial pressure to obtain a toroidal core sample with 31 outer diameter, 19 inner diameter, and 8 mm height.
- a pusher furnace was used for firing. 343 compacts were loaded per set. The loading pattern is 7 x 7 per row, and the number of levels is 7. Each sample was measured with a fluorescent X-ray analyzer and found to be almost equivalent to the raw material composition. table 1
- the sample whose content is out of the range of the present invention or replaced by another component at least one of the initial magnetic permeability i and the core loss PcV has decreased (as can be seen from Table 2).
- both samples deteriorated in many comparative samples.
- Example No. 2-1 an air gap with a width of about 0.8 mm was provided in the pot-shaped core of the components shown in Table 3 (Sample No. 2-1), and the AL-value was 1 000 ⁇ , / ⁇ ⁇ , A coil of 169 turns was used as the core sample of Example 2 (Sample No. 2-1).
- core samples of comparative examples (sample Nos. 2-2 and 2-3) having the same composition as the above sample No. 2-1 were prepared with the component compositions shown in Table 3.
- Example No. 2-1 The cores of these examples (Sample No. 2-1) and the cores of Comparative Examples (Sample Nos. 2-2 and 2-3) were subjected to a DC superposition characteristic under the condition that an AC magnetic field of 10 kHz was applied. Relationship between L (mH) and I de (mA)] was examined. Figure 1 shows the results. As can be seen from FIG. 1, the relationship between the inductance L and I ⁇ in both the core of the example and the core of the comparative example has a linear flat portion having a constant value from the low current side, and sharply decreases at a certain current value. However, in the core of the example (Sample No. 2-1), the current value improved as DC superposition characteristics (the current value where the inductance decreased by 10% from the linear flat part) Force The core of the comparative example (Sample Compared with Nos. 2-2 and 2-3-3), they improved by 20% and 50%, respectively.
- the core of the above example (Sample No. 2-1) and the core of the comparative example (Sample Nos. 2-2 and 2-3) had a frequency of 100 kHz, an initial magnetic permeability i at 25 ° C, and a frequency of 100 kHz. , 200 mT, core loss P cv at 40 ° C, and saturation magnetic flux density B s at 25 ° C at a frequency of 100 kHz, and i ⁇ BsZP cv were calculated. Table 3 shows the results.
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Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU87505/98A AU8750598A (en) | 1997-08-29 | 1998-08-25 | Manganese-zinc ferrite |
EP98938976A EP0936634A4 (en) | 1997-08-29 | 1998-08-25 | MANGANESE / ZINC FERRITE |
US09/301,573 US5980773A (en) | 1997-08-29 | 1999-04-29 | Manganese-zinc system ferrite |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9/249737 | 1997-08-29 | ||
JP24973797 | 1997-08-29 | ||
JP9/356079 | 1997-12-09 | ||
JP35607997A JP3488375B2 (ja) | 1997-08-29 | 1997-12-09 | マンガン−亜鉛系フェライト |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/301,573 Continuation US5980773A (en) | 1997-08-29 | 1999-04-29 | Manganese-zinc system ferrite |
Publications (1)
Publication Number | Publication Date |
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WO1999012173A1 true WO1999012173A1 (fr) | 1999-03-11 |
Family
ID=26539452
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP1998/003763 WO1999012173A1 (fr) | 1997-08-29 | 1998-08-25 | Ferrite de manganese/zinc |
Country Status (6)
Country | Link |
---|---|
US (1) | US5980773A (ja) |
EP (1) | EP0936634A4 (ja) |
JP (1) | JP3488375B2 (ja) |
AU (1) | AU8750598A (ja) |
TW (1) | TW379339B (ja) |
WO (1) | WO1999012173A1 (ja) |
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1997
- 1997-12-09 JP JP35607997A patent/JP3488375B2/ja not_active Expired - Fee Related
-
1998
- 1998-08-25 WO PCT/JP1998/003763 patent/WO1999012173A1/ja not_active Application Discontinuation
- 1998-08-25 AU AU87505/98A patent/AU8750598A/en not_active Abandoned
- 1998-08-25 EP EP98938976A patent/EP0936634A4/en not_active Withdrawn
- 1998-08-28 TW TW087114286A patent/TW379339B/zh active
-
1999
- 1999-04-29 US US09/301,573 patent/US5980773A/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03141612A (ja) * | 1990-09-27 | 1991-06-17 | Tdk Corp | 高周波電源用トランス磁芯 |
JPH06120022A (ja) * | 1992-10-07 | 1994-04-28 | Matsushita Electric Ind Co Ltd | 酸化物磁性体材料 |
JPH07297020A (ja) * | 1994-04-27 | 1995-11-10 | Tdk Corp | フェライトおよび電源用フェライトコア |
Non-Patent Citations (1)
Title |
---|
See also references of EP0936634A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1722586A1 (en) | 2000-05-10 | 2006-11-15 | Mitsubishi Electric Information Technology Centre Europe B.V. | A mobile telecommunication system and base station for allocating secondary synchronisation codes |
Also Published As
Publication number | Publication date |
---|---|
JP3488375B2 (ja) | 2004-01-19 |
US5980773A (en) | 1999-11-09 |
JPH11135317A (ja) | 1999-05-21 |
TW379339B (en) | 2000-01-11 |
EP0936634A4 (en) | 2001-04-18 |
EP0936634A1 (en) | 1999-08-18 |
AU8750598A (en) | 1999-03-22 |
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