US20010045541A1 - Manganese-zinc base ferrite - Google Patents
Manganese-zinc base ferrite Download PDFInfo
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- US20010045541A1 US20010045541A1 US09/855,646 US85564601A US2001045541A1 US 20010045541 A1 US20010045541 A1 US 20010045541A1 US 85564601 A US85564601 A US 85564601A US 2001045541 A1 US2001045541 A1 US 2001045541A1
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- oxide
- manganese
- zinc base
- calculated
- ferrite
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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 60
- WJZHMLNIAZSFDO-UHFFFAOYSA-N manganese zinc Chemical compound [Mn].[Zn] WJZHMLNIAZSFDO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 230000035699 permeability Effects 0.000 claims abstract description 55
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011787 zinc oxide Substances 0.000 claims abstract description 20
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011574 phosphorus Substances 0.000 claims abstract description 8
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims abstract description 3
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 32
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 30
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 22
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 22
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 13
- 239000000292 calcium oxide Substances 0.000 claims description 12
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 11
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 11
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 11
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 11
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims description 11
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 6
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 6
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 5
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 5
- -1 respectively Inorganic materials 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 17
- 239000000203 mixture Substances 0.000 description 15
- 239000013078 crystal Substances 0.000 description 13
- 238000010304 firing Methods 0.000 description 12
- 238000001816 cooling Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 238000005245 sintering Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 239000000696 magnetic material Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 230000007423 decrease Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000004615 ingredient Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 101150012579 ADSL gene Proteins 0.000 description 1
- 102100020775 Adenylosuccinate lyase Human genes 0.000 description 1
- 108700040193 Adenylosuccinate lyases Proteins 0.000 description 1
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 description 1
- 229910015227 MoCl3 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- ZSSVQAGPXAAOPV-UHFFFAOYSA-K molybdenum trichloride Chemical compound Cl[Mo](Cl)Cl ZSSVQAGPXAAOPV-UHFFFAOYSA-K 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000005549 size reduction Methods 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
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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
-
- 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
- This invention relates to manganese-zinc base ferrite, and more particularly, to high permeability manganese-zinc base ferrite suitable as cores in broad-band transformers.
- the electromagnetic properties such as permeability and loss of manganese-zinc base ferrite have structure sensitivity and are largely affected by its micro-structure.
- the permeability of such ferrite is increased by selecting a composition giving a low crystal magnetic anisotropy constant and a low magnetostriction constant, increasing the grain size, reducing vacancy, and increasing the sintered density. This is because the above choice facilitates magnetic wall migration. It is believed that permeability is governed by magnetic wall migration.
- auxiliary components have a substantial influence on the magnetic properties. Unless the contents of auxiliary components are controlled, the auxiliary components can prevent smooth migration of magnetic walls due to precipitation on grain boundaries, promoted abnormal grain growth and promoted void formation, leading to a decline of permeability.
- JP-B 5-55463 discloses a sintering type oxide magnetic material comprising ferric oxide, manganese oxide and zinc oxide as main components, and up to 0.01 wt % of silicon dioxide and up to 0.02 wt % of calcium oxide as auxiliary components, characterized in that the material further contains 0.02 to 0.05 wt % of bismuth oxide and 0.005 to 0.05 wt % of aluminum oxide as auxiliary components, and has an initial permeability ⁇ 0 of at least 18,000 and a relative loss factor tan ⁇ / ⁇ of up to 2.0 ⁇ 10 ⁇ 6 ; an oxide magnetic material in the form of a sintered body produced by sintering the above material at 1300 to 1370° C.; and an oxide magnetic material in which the temperature coefficient of ⁇ 0 is always kept positive due to addition of aluminum oxide.
- the magnetic material described in this patent is allegedly suitable for use as communication transformer cores, it fails to provide the high permeability character required to be commensurate with higher transmission speeds.
- JP-B 52-29439 discloses a method of preparing a polycrystalline manganese-zinc ferrite body by shaping a fine ferrite-forming mixture into an article of desired shape, followed by compression and sintering, characterized in that a grain growth promoting substance selected from among SrF 2 , oxides of B, Bi, Ca, Cu, Mg, Pb, Si and V, and Fe 3 (PO 4 ) 2 and mixtures of any is added in an amount of 0.005 to 1 wt % based on the ferrite at any preparation stage prior to the sintering step, and the sintering is conducted at a temperature of 1350 to 1400° C.
- a grain growth promoting substance selected from among SrF 2 , oxides of B, Bi, Ca, Cu, Mg, Pb, Si and V, and Fe 3 (PO 4 ) 2 and mixtures of any is added in an amount of 0.005 to 1 wt % based on the ferrite at any preparation stage prior to the s
- this ferrite is limited to heads. Its object is to provide a head having improved anti-decay and long lifetime characteristics by virtue of irregularly conjugated crystals having a large grain size, unlike the object of the present invention to provide a high permeability by making use of very large crystal grains, and the high permeability characteristics required for pulse transformers in transmitters are not available. Additionally, this ferrite, intended to be applied to heads, does not have a high permeability as required in pulse transformers in transmitters.
- JP-A 6-204025 a manganese-zinc base ferrite having a high permeability over a broad band and especially throughout the band of 10 to 500 kHz.
- a manganese-zinc base ferrite comprising 50 to 56 mol % calculated as Fe 2 O 3 of iron oxide, 22 to 39 mol % calculated as MnO of manganese oxide, and 8 to 25 mol % calculated as ZnO of zinc oxide, which is sintered after addition of up to 800 ppm calculated as Bi 2 O 3 of bismuth oxide and up to 1200 ppm calculated as MoO 3 of molybdenum oxide.
- the manganese-zinc base ferrite disclosed in this patent exhibits a high initial permeability over a broad band as demonstrated by an initial permeability of at least 9000, at least 9000 and at least 3000 at 10 kHz, 100 kHz and 500 kHz and 25° C., respectively.
- JP-A 6-204025 of the present applicant proposes a manganese-zinc base ferrite comprising 50 to 56 mol % calculated as Fe 2 O 3 of iron oxide, 22 to 39 mol % calculated as MnO of manganese oxide, and 8 to 25 mol % calculated as ZnO of zinc oxide, which is sintered after addition of up to 800 ppm calculated as Bi 2 O 3 of bismuth oxide and up to 1200 ppm calculated as MoO 3 of molybdenum oxide.
- This ferrite fails to provide the necessary high permeability characteristics.
- An object of the invention is to provide a manganese-zinc base ferrite having a high permeability over a broad band and especially, a high permeability in a frequency region in proximity to 10 to 100 kHz.
- a manganese-zinc base ferrite comprising iron oxide, manganese oxide and zinc oxide as main components in amounts calculated as Fe 2 O 3 , MnO and ZnO, respectively, Fe 2 O 3 50 to 56 mol %, MnO 21 to 27 mol %, and ZnO 20 to 26 mol %,
- the manganese-zinc base ferrite of (1) further comprising more than 0% to 0.08% by weight of bismuth oxide as an auxiliary component, based on the main components and calculated as Bi 2 O 3 .
- FIG. 1 is a drawing-substituting photograph showing a cross section of an inventive sample.
- FIG. 2 is a drawing-substituting photograph showing a cross section of a comparative sample.
- the resulting manganese-zinc base ferrite has a permeability of at least 15,000 at 10 kHz.
- the manganese-zinc base ferrite of the invention has a high permeability at 100 kHz which is 15,000 or greater.
- this enables to reduce the number of windings and the size of transformers.
- transformers can be manufactured which exhibit high performance in digital transmission systems such as ISDN and ADSL.
- the manganese-zinc base ferrite of the invention is defined as comprising 50 to 56 mol % calculated as Fe 2 O 3 of iron oxide, 21 to 27 mol % calculated as MnO of manganese oxide, and 20 to 26 mol % calculated as ZnO of zinc oxide as main components, and 0.0003 to 0.003% by weight calculated as P of phosphorus as an auxiliary component, and having a mean grain size from more than 50 ⁇ m to 200 ⁇ m.
- the content of iron oxide be 50 to 56 mol %, especially 52 to 54 mol %, calculated as Fe 2 O 3
- the content of manganese oxide be 21 to 27 mol %, especially 23 to 25 mol %, calculated as MnO
- the content of zinc oxide be 20 to 26 mol %, especially 22 to 24 mol %, calculated as ZnO. Outside the range, a decline of permeability at 10 kHz is likely to occur.
- the manganese-zinc base ferrite of the invention may contain calcium oxide and silicon oxide as auxiliary components.
- the contents of these auxiliary components are 0.005 to 0.05% by weight, especially 0.01 to 0.03% by weight, calculated as CaO, and 0.005 to 0.015% by weight calculated as SiO 2 . It is noted that CaO and SiO 2 are generally present at grain boundaries.
- the inventive ferrite contains bismuth oxide and molybdenum oxide, especially in the form of Bi 2 O 3 and MoO 3 , respectively.
- the oxide components of bismuth and molybdenum added especially the molybdenum oxide component, will partially evaporate off or sublimate during firing, the contents of bismuth oxide and molybdenum oxide in the ferrite are sometimes not coincident with the addition amounts.
- the content of bismuth oxide is preferably about 50 to 100% by weight, calculated as Bi 2 O 3 , of the addition amount and the content of molybdenum oxide is preferably about 10 to 60% by weight, especially about 10 to 30% by weight, calculated as MoO 3 , of the addition amount.
- the ferrite of the invention contains 0.0003 to 0.003% by weight, and preferably 0.0005 to 0.002% by weight, calculated as P of phosphorus as an auxiliary component.
- P of phosphorus as an auxiliary component.
- the inclusion of phosphorus permits larger crystal grains to form at a lower sintering temperature.
- a lowering of the sintering temperature allows for a margin to the operating conditions of the furnace.
- the ferrite of the invention preferably contains at least one oxide of niobium oxide, tantalum oxide and zirconium oxide in amounts calculated as Nb 2 O 5 , Ta 2 O 5 and ZrO 2 , respectively, Nb 2 O 5 more than 0 to 0.03 wt %, more preferably 0.003 to 0.02 wt %, and especially 0.005 to 0.01 wt %, Ta 2 O 5 more than 0 to 0.06 wt %, more preferably 0.01 to 0.04 wt %, and especially 0.015 to 0.03 wt %, and ZrO 2 more than 0 to 0.06 wt %. more preferably 0.01 to 0.04 wt %, and especially 0.015 to 0.03 wt %.
- auxiliary components leads to an outstanding increase of permeability especially on the high frequency side.
- zirconium is especially preferred.
- a combination of zirconium oxide and tantalum oxide is preferred.
- their mixing ratio is not critical.
- the ferrite of the invention containing the above-mentioned components has a mean crystal grain size from more than 50 ⁇ m to 200 ⁇ m. Too small a mean grain size leads to a decline of permeability at 10 kHz, probably failing to achieve a permeability of at least 15,000 at 10 kHz. Too large a mean grain size, though being able to achieve a permeability of at least 15,000 at 10 kHz, leads to a decline of permeability at 100 kHz. It is noted that the mean grain size is determined by etching a mirror polished surface with acid, observing the surface under an optical microscope, measuring the diameters of equivalent circles of polycrystalline grains, and computing an average therefrom.
- the manganese-zinc base ferrite of the invention has a mean crystal grain size from more than 50 ⁇ m to 180 ⁇ m, more preferably 60 to 150 ⁇ m, and most preferably 70 to 130 ⁇ m.
- those grains having a grain size from more than 50 ⁇ m to 140 ⁇ m preferably account for at least 50% by volume, more preferably at least 70% by volume and most preferably at least 80% by volume.
- the permeability at 10 kHz of the inventive manganese-zinc base ferrite is preferably at least 20,000, and especially at least 25,000.
- the permeability at 10 kHz of the inventive manganese-zinc base ferrite that has been achieved so far is about 35,000 at maximum. The higher the permeability, the better becomes the performance.
- a large mean crystal grain size and a narrow distribution of grain size as mentioned above enable to achieve a permeability at 10 kHz and 25° C. of at least 15,000, especially at least 20,000, further at least 25,000, for example, 15,000 to 35,000; a permeability at 100 kHz of at least 10,000, especially at least 12,000, further at least 15,000, for example, about 10,000 to 22,000; and a permeability at 500 kHz of at least 2,000, especially at least 3,000, further at least 3,500, for example, about 3,500 to 6,000, which are comparable to or greater than those available in the prior art.
- the manganese-zinc base ferrite of the invention is prepared by first furnishing a mixture of customary iron oxide, manganese oxide and zinc oxide ingredients to serve as the main components. These ingredients used as starting materials for the main components are mixed in such amounts as to provide the above-defined ratio in the final composition of ferrite. If necessary, calcium oxide or a compound capable of converting to calcium oxide upon firing such as calcium carbonate, silicon oxide or a compound capable of converting to silicon oxide upon firing, and the like are added as starting materials for auxiliary components. The starting materials for auxiliary components are added in such amounts as to provide the above-defined ratio in the final composition of magnetic material.
- bismuth oxide and molybdenum oxide components are added as auxiliary components.
- the bismuth oxide component used herein may be Bi 2 O 3 , Bi 2 (SO 4 ) 3 , etc., with Bi 2 O 3 being preferred.
- the bismuth oxide component added is up to 0.08% by weight, preferably up to 0.06% by weight, and more preferably 0.005 to 0.04% by weight, calculated as Bi 2 O 3 . Addition amounts beyond the range rather lead to a permeability decline.
- the molybdenum oxide component used herein may be MoO 3 , MoCl 3 , etc., with MoO 3 being preferred.
- the molybdenum oxide component added is up to 0.12% by weight, preferably up to 0.1% by weight, and more preferably 0.003 to 0.05% by weight, calculated as MoO 3 . Addition amounts beyond the range rather lead to a permeability decline.
- Phosphorus is added as an auxiliary component in an amount of 0.0003 to 0.003% by weight calculated as P.
- at least one oxide of niobium oxide, tantalum oxide and zirconium oxide is added to the starting mixture if necessary. It is preferred to use Nb 2 O 5 as niobium oxide, Ta 2 O 5 as tantalum oxide and ZrO 2 as zirconium oxide. The addition amounts of these oxides are from more than 0 to 0.03 wt % of Nb 2 O 5 , from more than 0 to 0.06 wt % of Ta 2 O 5 , and from more than 0 to 0.06 wt % of ZrO 2 .
- a small amount, for example, 0.1 to 1.0% by weight of a suitable binder such as polyvinyl alcohol is added to the mixture, which is atomized into granules having a diameter of about 80 to 200 ⁇ m through a spray dryer or the like, which are shaped into a compact.
- the temperature holding step during firing of the compact of ferrite material following calcination sets a holding temperature in the range of 1,200 to 1,450° C., especially 1,350 to 1,450° C.
- the temperature holding step may be preceded by a temperature lowering step during firing which sets a lowest temperature in the range of 1,000 to 1,400° C. and a lowering temperature of at least 30° C., especially at least 50° C.
- the holding temperature in the temperature holding step is set in the range of 1,200 to 1,450° C. because it is effective for promoting ferrite formation and controlling the crystal grain size. Within this temperature range, an improvement in permeability, especially at 10 kHz, is achievable.
- the holding time of the temperature holding step is preferably about 1 ⁇ 2 to 10 hours.
- the heating step, temperature holding step and subsequent cooling step used in the firing process according to the invention may follow a temperature profile as in the prior art firing process.
- the heating rate of the heating step is preferably 20 to 500° C./hr.
- the heating rate may be varied in two or more stages. In this case, the heating rate is higher in the initial stage, and gradually lowered in the later stages. In the event of two stage heating, for example, it is preferred to set the heating rate of the first stage to about 200 to 500° C./hr and the heating rate of the second stage to about 20 to 200° C./hr.
- the cooling rate of the cooling step is preferably set to 20 to 500° C./hr.
- the cooling rate may also be varied in two or more stages. In the event of two stage cooling, it is preferred that the cooling rate of the first stage be about 20 to 200° C./hr and the cooling rate of the second stage be about 200 to 500° C./hr.
- the furnace used for firing according to the invention may be either a continuous one or a batchwise one.
- the atmosphere during firing may be adjusted in accordance with the theory of equilibrium oxygen partial pressure. Firing is preferably conducted in a nitrogen atmosphere having a controlled oxygen partial pressure (inclusive of an atmosphere consisting solely of oxygen).
- Samples were obtained by using 24 mol % of MnO, 23 mol % of ZnO, and 53 mol % of Fe 2 O 3 as main components, 0.02 wt % (calculated as CaO and based on the final composition of magnetic material) of CaCO 3 , 0.01 wt % (based on the final composition of magnetic material) of SiO 2 , 0.02 wt % of Bi 2 O 3 and 0.02 wt % of MoO 3 as auxiliary components, and adding 0.0008 wt % of P as an additive.
- a binder was added to the mixture, which was granulated to a mean particle diameter of 150 ⁇ m by means of a spray dryer.
- the granules were shaped into 100 compacts.
- the compacts were heated in a nitrogen atmosphere having PO 2 of 0.5%, held in an atmosphere having an oxygen concentration of at least 20% at a constant temperature of 1,380 to 1,450° C. for 1 to 10 hours for sintering, then cooled in an atmosphere having a controlled oxygen partial pressure, yielding toroidal cores having a mean grain size from more than 50 ⁇ m to 200 ⁇ m, an outer diameter of 6 mm, an inner diameter of 3 mm and a height of 1.5 mm.
- Cooling rate from 1000° C. to room temperature is
- the toroidal cores thus obtained were measured for permeability at 10 kHz and 100 kHz and 25° C. and mean grain size.
- an impedance analyzer was used for the permeability measurement. The results are shown in Table 1.
- TABLE 1 Sample Mean grain size Permeability No. ( ⁇ m) 10 kHz 100 kHz 1 64 22800 16200 2 75 26100 15200 3 81 29700 13800 4 107 36300 15000 5 131 33600 14600 6 154 30200 13200 7 189 24800 11800 8* 14 10300 10300 9* 27 12100 12000 10* 47 18200 13900
- FIGS. 1 and 2 are photographs on polished cross-sectional surfaces of inventive and comparative samples rough an optical microscope.
- the manganese-zinc base ferrite of the invention exhibits a very high permeability in a band near the frequency of 10 kHz, and yet in a high frequency region at or beyond the frequency 100 kHz, a permeability at least comparable to the prior art.
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Abstract
Description
- This application claims priority to International Application No. PCT/JP00/06218 filed Sep. 12, 2000 and Japanese Application No. 11-264061 filed Sep. 17, 1999, and the entire content of both applications is hereby incorporated by reference.
- This invention relates to manganese-zinc base ferrite, and more particularly, to high permeability manganese-zinc base ferrite suitable as cores in broad-band transformers.
- For broad-band transformers such as pulse transformers, a core-forming manganese-zinc base ferrite having a high magnetic permeability over a broad band, and especially throughout the band of 10 to 500 kHz is needed in order to enable accurate digital communication.
- The electromagnetic properties such as permeability and loss of manganese-zinc base ferrite have structure sensitivity and are largely affected by its micro-structure. In general, the permeability of such ferrite is increased by selecting a composition giving a low crystal magnetic anisotropy constant and a low magnetostriction constant, increasing the grain size, reducing vacancy, and increasing the sintered density. This is because the above choice facilitates magnetic wall migration. It is believed that permeability is governed by magnetic wall migration. Also auxiliary components have a substantial influence on the magnetic properties. Unless the contents of auxiliary components are controlled, the auxiliary components can prevent smooth migration of magnetic walls due to precipitation on grain boundaries, promoted abnormal grain growth and promoted void formation, leading to a decline of permeability.
- JP-B 5-55463 discloses a sintering type oxide magnetic material comprising ferric oxide, manganese oxide and zinc oxide as main components, and up to 0.01 wt % of silicon dioxide and up to 0.02 wt % of calcium oxide as auxiliary components, characterized in that the material further contains 0.02 to 0.05 wt % of bismuth oxide and 0.005 to 0.05 wt % of aluminum oxide as auxiliary components, and has an initial permeability μ0 of at least 18,000 and a relative loss factor tanδ/μ of up to 2.0×10−6; an oxide magnetic material in the form of a sintered body produced by sintering the above material at 1300 to 1370° C.; and an oxide magnetic material in which the temperature coefficient of μ0 is always kept positive due to addition of aluminum oxide. Although the magnetic material described in this patent is allegedly suitable for use as communication transformer cores, it fails to provide the high permeability character required to be commensurate with higher transmission speeds.
- As the technique relating to large grain sizes, JP-B 52-29439 discloses a method of preparing a polycrystalline manganese-zinc ferrite body by shaping a fine ferrite-forming mixture into an article of desired shape, followed by compression and sintering, characterized in that a grain growth promoting substance selected from among SrF2, oxides of B, Bi, Ca, Cu, Mg, Pb, Si and V, and Fe3(PO4)2 and mixtures of any is added in an amount of 0.005 to 1 wt % based on the ferrite at any preparation stage prior to the sintering step, and the sintering is conducted at a temperature of 1350 to 1400° C. until conjugated crystals having a mean grain size of at least 50 μm are formed. However, the application of this ferrite is limited to heads. Its object is to provide a head having improved anti-decay and long lifetime characteristics by virtue of irregularly conjugated crystals having a large grain size, unlike the object of the present invention to provide a high permeability by making use of very large crystal grains, and the high permeability characteristics required for pulse transformers in transmitters are not available. Additionally, this ferrite, intended to be applied to heads, does not have a high permeability as required in pulse transformers in transmitters.
- Under the circumstances, the present applicant proposed in JP-A 6-204025 a manganese-zinc base ferrite having a high permeability over a broad band and especially throughout the band of 10 to 500 kHz. Disclosed in this patent is a manganese-zinc base ferrite comprising 50 to 56 mol % calculated as Fe2O3 of iron oxide, 22 to 39 mol % calculated as MnO of manganese oxide, and 8 to 25 mol % calculated as ZnO of zinc oxide, which is sintered after addition of up to 800 ppm calculated as Bi2O3 of bismuth oxide and up to 1200 ppm calculated as MoO3 of molybdenum oxide.
- The manganese-zinc base ferrite disclosed in this patent exhibits a high initial permeability over a broad band as demonstrated by an initial permeability of at least 9000, at least 9000 and at least 3000 at 10 kHz, 100 kHz and 500 kHz and 25° C., respectively.
- In order to accomplish size reduction and higher transmission speed for pulse transformers, it is crucial for ferrite to have a higher permeability especially in a frequency region near 10 kHz. The provision of a high permeability permits a smaller number of windings to provide a higher inductance and a lower distributed capacity and enables passage of signals in a broad band.
- Meanwhile, aiming to provide a manganese-zinc base ferrite having a high permeability over a broad band (typically a permeability of at least 9000 in a frequency region of 10 to 100 kHz) and especially, a high permeability throughout a frequency region of 10 to 500 kHz, JP-A 6-204025 of the present applicant proposes a manganese-zinc base ferrite comprising 50 to 56 mol % calculated as Fe2O3 of iron oxide, 22 to 39 mol % calculated as MnO of manganese oxide, and 8 to 25 mol % calculated as ZnO of zinc oxide, which is sintered after addition of up to 800 ppm calculated as Bi2O3 of bismuth oxide and up to 1200 ppm calculated as MoO3 of molybdenum oxide. This ferrite, however, fails to provide the necessary high permeability characteristics.
- An object of the invention is to provide a manganese-zinc base ferrite having a high permeability over a broad band and especially, a high permeability in a frequency region in proximity to 10 to 100 kHz.
- This and other objects are achieved by any of the following constructions (1) to (7).
- (1) A manganese-zinc base ferrite comprising iron oxide, manganese oxide and zinc oxide as main components in amounts calculated as Fe2O3, MnO and ZnO, respectively,
Fe2O3 50 to 56 mol %, MnO 21 to 27 mol %, and ZnO 20 to 26 mol %, - and 0.0003 to 0.003% by weight calculated as P of phosphorus as an auxiliary component, and having a mean grain size from more than 50 μm to 200 μm.
- (2) The manganese-zinc base ferrite of (1) further comprising more than 0% to 0.08% by weight of bismuth oxide as an auxiliary component, based on the main components and calculated as Bi2O3.
- (3) The manganese-zinc base ferrite of (1) or (2) further comprising more than 0% to 0.12% by weight of molybdenum oxide as an auxiliary component, based on the main components and calculated as MoO3.
- (4) The manganese-zinc base ferrite of any one of (1) to (3) further comprising at least one oxide of niobium oxide, tantalum oxide and zirconium oxide as an auxiliary component in amounts calculated as Nb2O5, Ta2O5 and ZrO2, respectively,
Nb2O5 more than 0 to 0.03 wt %, Ta2O5 more than 0 to 0.06 wt %, and ZrO2 more than 0 to 0.06 wt %. - (5) The manganese-zinc base ferrite of any one of (1) to (4) further comprising 0.005 to 0.05% by weight, calculated as CaO, of calcium oxide.
- (6) The manganese-zinc base ferrite of any one of (1) to (5), having a permeability of at least 15,000 at 10 kHz.
- (7) The manganese-zinc base ferrite of any one of (1) to (6), having a permeability of at least 15,000 at 100 kHz.
- FIG. 1 is a drawing-substituting photograph showing a cross section of an inventive sample.
- FIG. 2 is a drawing-substituting photograph showing a cross section of a comparative sample.
- According to the invention, by controlling the temperature condition and the atmosphere during firing of phosphorus-containing manganese-zinc base ferrite, a sintered body having a mean crystal grain size from more than 50 μm to 200 μm is obtained without abnormal crystal growth. Due to the synergistic effects of such a crystal grain size combined with a trace amount of additive element, the resulting manganese-zinc base ferrite has a permeability of at least 15,000 at 10 kHz. This leads to the advantage that when a core formed of the inventive manganese-zinc base ferrite is incorporated in a pulse transformer, for example, the high permeability the ferrite has acquired permits a smaller number of windings to provide a higher inductance and a lower distributed capacity and enables passage of signals in a broad band.
- As compared with prior art manganese-zinc base ferrites, the manganese-zinc base ferrite of the invention has a high permeability at 100 kHz which is 15,000 or greater. When transformers are manufactured, this enables to reduce the number of windings and the size of transformers. Especially transformers can be manufactured which exhibit high performance in digital transmission systems such as ISDN and ADSL.
- Now the illustrative construction of the invention is described in detail.
- The manganese-zinc base ferrite of the invention is defined as comprising 50 to 56 mol % calculated as Fe2O3 of iron oxide, 21 to 27 mol % calculated as MnO of manganese oxide, and 20 to 26 mol % calculated as ZnO of zinc oxide as main components, and 0.0003 to 0.003% by weight calculated as P of phosphorus as an auxiliary component, and having a mean grain size from more than 50 μm to 200 μm.
- With respect to the main components, it is preferred that the content of iron oxide be 50 to 56 mol %, especially 52 to 54 mol %, calculated as Fe2O3, the content of manganese oxide be 21 to 27 mol %, especially 23 to 25 mol %, calculated as MnO, and the content of zinc oxide be 20 to 26 mol %, especially 22 to 24 mol %, calculated as ZnO. Outside the range, a decline of permeability at 10 kHz is likely to occur.
- Also the manganese-zinc base ferrite of the invention may contain calcium oxide and silicon oxide as auxiliary components. The contents of these auxiliary components are 0.005 to 0.05% by weight, especially 0.01 to 0.03% by weight, calculated as CaO, and 0.005 to 0.015% by weight calculated as SiO2. It is noted that CaO and SiO2 are generally present at grain boundaries.
- Preferably, the inventive ferrite contains bismuth oxide and molybdenum oxide, especially in the form of Bi2O3 and MoO3, respectively. In this regard, since the oxide components of bismuth and molybdenum added, especially the molybdenum oxide component, will partially evaporate off or sublimate during firing, the contents of bismuth oxide and molybdenum oxide in the ferrite are sometimes not coincident with the addition amounts. This suggests that the content of bismuth oxide is preferably about 50 to 100% by weight, calculated as Bi2O3, of the addition amount and the content of molybdenum oxide is preferably about 10 to 60% by weight, especially about 10 to 30% by weight, calculated as MoO3, of the addition amount.
- The ferrite of the invention contains 0.0003 to 0.003% by weight, and preferably 0.0005 to 0.002% by weight, calculated as P of phosphorus as an auxiliary component. The inclusion of phosphorus permits larger crystal grains to form at a lower sintering temperature. In particular, since high permeability ferrite is often processed in a sintering furnace near its performance limit, a lowering of the sintering temperature allows for a margin to the operating conditions of the furnace.
- As a further auxiliary component, the ferrite of the invention preferably contains at least one oxide of niobium oxide, tantalum oxide and zirconium oxide in amounts calculated as Nb2O5, Ta2O5 and ZrO2, respectively,
Nb2O5 more than 0 to 0.03 wt %, more preferably 0.003 to 0.02 wt %, and especially 0.005 to 0.01 wt %, Ta2O5 more than 0 to 0.06 wt %, more preferably 0.01 to 0.04 wt %, and especially 0.015 to 0.03 wt %, and ZrO2 more than 0 to 0.06 wt %. more preferably 0.01 to 0.04 wt %, and especially 0.015 to 0.03 wt %. - The inclusion of these auxiliary components leads to an outstanding increase of permeability especially on the high frequency side. Of these elements, zirconium is especially preferred. When two or more elements are added together, a combination of zirconium oxide and tantalum oxide is preferred. When two or more elements are used, their mixing ratio is not critical.
- The ferrite of the invention containing the above-mentioned components has a mean crystal grain size from more than 50 μm to 200 μm. Too small a mean grain size leads to a decline of permeability at 10 kHz, probably failing to achieve a permeability of at least 15,000 at 10 kHz. Too large a mean grain size, though being able to achieve a permeability of at least 15,000 at 10 kHz, leads to a decline of permeability at 100 kHz. It is noted that the mean grain size is determined by etching a mirror polished surface with acid, observing the surface under an optical microscope, measuring the diameters of equivalent circles of polycrystalline grains, and computing an average therefrom.
- Preferably the manganese-zinc base ferrite of the invention has a mean crystal grain size from more than 50 μm to 180 μm, more preferably 60 to 150 μm, and most preferably 70 to 130 μm. In the manganese-zinc base ferrite of the invention, those grains having a grain size from more than 50 μm to 140 μm preferably account for at least 50% by volume, more preferably at least 70% by volume and most preferably at least 80% by volume. The permeability at 10 kHz of the inventive manganese-zinc base ferrite is preferably at least 20,000, and especially at least 25,000. The permeability at 10 kHz of the inventive manganese-zinc base ferrite that has been achieved so far is about 35,000 at maximum. The higher the permeability, the better becomes the performance.
- A large mean crystal grain size and a narrow distribution of grain size as mentioned above enable to achieve a permeability at 10 kHz and 25° C. of at least 15,000, especially at least 20,000, further at least 25,000, for example, 15,000 to 35,000; a permeability at 100 kHz of at least 10,000, especially at least 12,000, further at least 15,000, for example, about 10,000 to 22,000; and a permeability at 500 kHz of at least 2,000, especially at least 3,000, further at least 3,500, for example, about 3,500 to 6,000, which are comparable to or greater than those available in the prior art.
- The manganese-zinc base ferrite of the invention is prepared by first furnishing a mixture of customary iron oxide, manganese oxide and zinc oxide ingredients to serve as the main components. These ingredients used as starting materials for the main components are mixed in such amounts as to provide the above-defined ratio in the final composition of ferrite. If necessary, calcium oxide or a compound capable of converting to calcium oxide upon firing such as calcium carbonate, silicon oxide or a compound capable of converting to silicon oxide upon firing, and the like are added as starting materials for auxiliary components. The starting materials for auxiliary components are added in such amounts as to provide the above-defined ratio in the final composition of magnetic material.
- Also if necessary, bismuth oxide and molybdenum oxide components are added as auxiliary components. The bismuth oxide component used herein may be Bi2O3, Bi2(SO4)3, etc., with Bi2O3 being preferred. The bismuth oxide component added is up to 0.08% by weight, preferably up to 0.06% by weight, and more preferably 0.005 to 0.04% by weight, calculated as Bi2O3. Addition amounts beyond the range rather lead to a permeability decline.
- The molybdenum oxide component used herein may be MoO3, MoCl3, etc., with MoO3 being preferred. The molybdenum oxide component added is up to 0.12% by weight, preferably up to 0.1% by weight, and more preferably 0.003 to 0.05% by weight, calculated as MoO3. Addition amounts beyond the range rather lead to a permeability decline.
- Phosphorus is added as an auxiliary component in an amount of 0.0003 to 0.003% by weight calculated as P. Also, at least one oxide of niobium oxide, tantalum oxide and zirconium oxide is added to the starting mixture if necessary. It is preferred to use Nb2O5 as niobium oxide, Ta2O5 as tantalum oxide and ZrO2 as zirconium oxide. The addition amounts of these oxides are from more than 0 to 0.03 wt % of Nb2O5, from more than 0 to 0.06 wt % of Ta2O5, and from more than 0 to 0.06 wt % of ZrO2.
- Once the main components and trace additive components are mixed, a small amount, for example, 0.1 to 1.0% by weight of a suitable binder such as polyvinyl alcohol is added to the mixture, which is atomized into granules having a diameter of about 80 to 200 μm through a spray dryer or the like, which are shaped into a compact.
- Next, the compact is fired. The firing should comply with the following conditions.
- In the method of preparing the manganese-zinc base ferrite according to the invention, the temperature holding step during firing of the compact of ferrite material following calcination sets a holding temperature in the range of 1,200 to 1,450° C., especially 1,350 to 1,450° C. The temperature holding step may be preceded by a temperature lowering step during firing which sets a lowest temperature in the range of 1,000 to 1,400° C. and a lowering temperature of at least 30° C., especially at least 50° C.
- The holding temperature in the temperature holding step is set in the range of 1,200 to 1,450° C. because it is effective for promoting ferrite formation and controlling the crystal grain size. Within this temperature range, an improvement in permeability, especially at 10 kHz, is achievable. The holding time of the temperature holding step is preferably about ½ to 10 hours.
- The heating step, temperature holding step and subsequent cooling step used in the firing process according to the invention may follow a temperature profile as in the prior art firing process. Specifically, the heating rate of the heating step is preferably 20 to 500° C./hr. The heating rate may be varied in two or more stages. In this case, the heating rate is higher in the initial stage, and gradually lowered in the later stages. In the event of two stage heating, for example, it is preferred to set the heating rate of the first stage to about 200 to 500° C./hr and the heating rate of the second stage to about 20 to 200° C./hr. On the other hand, the cooling rate of the cooling step is preferably set to 20 to 500° C./hr. In the cooling step, the cooling rate may also be varied in two or more stages. In the event of two stage cooling, it is preferred that the cooling rate of the first stage be about 20 to 200° C./hr and the cooling rate of the second stage be about 200 to 500° C./hr.
- The furnace used for firing according to the invention may be either a continuous one or a batchwise one. The atmosphere during firing may be adjusted in accordance with the theory of equilibrium oxygen partial pressure. Firing is preferably conducted in a nitrogen atmosphere having a controlled oxygen partial pressure (inclusive of an atmosphere consisting solely of oxygen).
- In this way, the manganese-zinc base ferrite of the invention is obtained.
- Examples of the invention are given below for further illustrating the invention.
- Samples were obtained by using 24 mol % of MnO, 23 mol % of ZnO, and 53 mol % of Fe2O3 as main components, 0.02 wt % (calculated as CaO and based on the final composition of magnetic material) of CaCO3, 0.01 wt % (based on the final composition of magnetic material) of SiO2, 0.02 wt % of Bi2O3 and 0.02 wt % of MoO3 as auxiliary components, and adding 0.0008 wt % of P as an additive.
- After the ingredients were mixed, a binder was added to the mixture, which was granulated to a mean particle diameter of 150 μm by means of a spray dryer. The granules were shaped into 100 compacts. The compacts were heated in a nitrogen atmosphere having PO2 of 0.5%, held in an atmosphere having an oxygen concentration of at least 20% at a constant temperature of 1,380 to 1,450° C. for 1 to 10 hours for sintering, then cooled in an atmosphere having a controlled oxygen partial pressure, yielding toroidal cores having a mean grain size from more than 50 μm to 200 μm, an outer diameter of 6 mm, an inner diameter of 3 mm and a height of 1.5 mm.
- One typical temperature profile used in the above process is described below.
- Temperature profile in Example
- Heating step
- Heating rate to 1200° C.: 300° C./hr
- Heating rate from 1200° C. to 1420° C.: 100° C./hr
- Holding step
- Holding at 1420° C. for 3.0 hours
- Cooling step
- Cooling rate from 1420° C. to 1000° C.: 100° C./hr
- Cooling rate from 1000° C. to room temperature:
- 250° C./hr
- The final composition of the samples of Examples and Comparative Examples was measured by fluorescent x-ray spectroscopy, finding that the main components, CaO, SiO2, Nb2O5, ZrO2 and Ta2O5 substantially corresponded to the raw material composition, while Bi2O3 and MoO3 corresponded to 10 to 80 wt % of the addition amounts.
- The toroidal cores thus obtained were measured for permeability at 10 kHz and 100 kHz and 25° C. and mean grain size. For the permeability measurement, an impedance analyzer was used. The results are shown in Table 1.
TABLE 1 Sample Mean grain size Permeability No. (μm) 10 kHz 100 kHz 1 64 22800 16200 2 75 26100 15200 3 81 29700 13800 4 107 36300 15000 5 131 33600 14600 6 154 30200 13200 7 189 24800 11800 8* 14 10300 10300 9* 27 12100 12000 10* 47 18200 13900 - The effectiveness of the invention is evident from the results shown in Table 1. Specifically, those samples in which the mean grain size is adjusted to 64 to 189 μm according to the invention (Sample Nos. 1 to 7 in Table 1) have a very high permeability at 10 kHz as compared with prior art samples (Sample Nos. 8 to 10 in Table 1), and a permeability at 100 kHz at least comparable to the prior art samples. In the samples of Examples, those crystal grains having a size from more than 50 μm to 140 μm accounted for more than 80% by volume.
- FIGS.1 and 2 are photographs on polished cross-sectional surfaces of inventive and comparative samples rough an optical microscope.
- While changing the composition of manganese-zinc base ferrite from Example 1, there were obtained Sample Nos. 11 to 16 containing Bi2O3, MoO3 and P, Sample Nos. 17 and 18 containing Bi2O3 and P, and Sample No. 19 containing only P, all in addition to CaCO3 and SiO2 as auxiliary components. Also prepared were Comparative Sample Nos. 20 to 22 in which the amounts of Bi2O3, MoO3 and P added were outside the above-described ranges.
- The samples were examined as in Example 1. The results are shown in Table 2.
TABLE 2 Auxiliary component content Sample (wt %) Permeability No. Bi2O3 MoO3 P 10 kHz 100 kHz 11 0.01 0.01 0.0008 31000 13900 12 0.02 0.02 0.0008 36300 15000 13 0.02 0.02 0.0020 33100 14800 14 0.04 0.02 0.0008 35800 16200 15 0.02 0.04 0.0008 34900 16800 16 0.05 0.05 0.0008 28600 14700 17 0.02 0 0.0008 32100 13200 18 0.04 0 0.0008 30100 12100 19 0 0 0.0008 24300 12500 20* 0 0 0.0050 18900 12300 21* 0.02 0.02 0.0050 26200 15400 22* 0.10 0.10 0.0008 16200 11400 - While changing the composition of manganese-zinc base ferrite from Example 1, there were obtained Sample Nos. 31 to 34 containing ZrO2, Sample Nos. 35 to 37 containing Ta2O5, and Sample Nos. 38 to 39 containing Nb2O5, all in addition to CaCO3, SiO2, Bi2O3, MoO3 and P, as auxiliary components. Also prepared was Comparative Sample No. 40 to which none of the above additives were added.
- The samples were examined as in Example 1. The results are shown in Table 3.
TABLE 3 Auxiliary component content Sample (wt %) Permeability No. ZrO2 Ta2O5 Nb2O5 10 kHz 100 kHz 31 0.01 0 0 33900 16600 32 0.02 0 0 32800 18500 33 0.03 0 0 33500 19300 34 0.04 0 0 28800 20100 35 0 0.01 0 31900 17800 36 0 0.02 0 29800 19400 37 0 0.03 0 27900 21800 38 0 0 0.005 32500 18300 39 0 0 0.01 29900 19200 40* 0 0 0 36300 15000 - The manganese-zinc base ferrite of the invention exhibits a very high permeability in a band near the frequency of 10 kHz, and yet in a high frequency region at or beyond the frequency 100 kHz, a permeability at least comparable to the prior art.
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JP6085228B2 (en) * | 2012-11-20 | 2017-02-22 | Jfeケミカル株式会社 | MnZn ferrite and method for producing the same |
CN107216139A (en) * | 2017-05-08 | 2017-09-29 | 中国计量大学 | High saturated flux density MnZn ferrite |
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DE2148554A1 (en) | 1970-10-07 | 1972-04-13 | Philips Nv | Process for the production of a polycrystalline ferrite body |
JPH0350124A (en) * | 1989-07-19 | 1991-03-04 | Hitachi Ferrite Ltd | Mn-Zn ferrite core |
JPH0555463A (en) | 1991-08-29 | 1993-03-05 | Mitsubishi Electric Corp | Manufacture of semiconductor device |
JP3233420B2 (en) * | 1991-08-30 | 2001-11-26 | ティーディーケイ株式会社 | Manganese-zinc ferrite and magnetic core |
JP3635410B2 (en) | 1992-12-28 | 2005-04-06 | Tdk株式会社 | Method for producing manganese-zinc based ferrite |
JP2735790B2 (en) * | 1994-06-29 | 1998-04-02 | ケミライト工業株式会社 | Mn-Zn ferrite |
KR0144224B1 (en) * | 1995-08-22 | 1998-07-15 | 미노루 다나까 | Soft ferrite powder, its sintered body, manufacturing method and apparatus |
EP0763507B1 (en) * | 1995-09-15 | 1999-03-31 | SIEMENS MATSUSHITA COMPONENTS GmbH & CO. KG | Manganese-zinc-ferrite |
JPH10256026A (en) * | 1997-03-14 | 1998-09-25 | Tdk Corp | Manganese-zinc ferrite |
JP3743795B2 (en) | 1999-09-17 | 2006-02-08 | Tdk株式会社 | Method for producing manganese-zinc based ferrite |
-
1999
- 1999-09-17 JP JP26406199A patent/JP3743795B2/en not_active Expired - Fee Related
-
2000
- 2000-09-12 DE DE10083302T patent/DE10083302T1/en not_active Ceased
- 2000-09-12 WO PCT/JP2000/006218 patent/WO2001022440A1/en active IP Right Grant
- 2000-09-12 CN CNB008019932A patent/CN1226757C/en not_active Expired - Fee Related
- 2000-09-12 KR KR10-2001-7006091A patent/KR100392505B1/en not_active IP Right Cessation
- 2000-09-15 TW TW089118985A patent/TW516048B/en active
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2001
- 2001-05-16 US US09/855,646 patent/US6423243B2/en not_active Expired - Fee Related
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2005048276A2 (en) * | 2003-11-12 | 2005-05-26 | Kanto Denka Kogyo Co., Ltd. | An mg-based ferrite, an electrophotographic development carrier containing the ferrite, and developer containing the carrier |
US20070087282A1 (en) * | 2003-11-12 | 2007-04-19 | Kanto Denka Kogyo Co. Ltd. | Mg-based ferrite, an electrophotographic development carrier containing the ferrite, and developer containing the carrier |
WO2005048276A3 (en) * | 2003-11-12 | 2008-01-10 | Kanto Denka Kogyo Kk | An mg-based ferrite, an electrophotographic development carrier containing the ferrite, and developer containing the carrier |
US7476482B2 (en) | 2003-11-12 | 2009-01-13 | Kanto Denka Kogyo Co., Ltd. | Mg-based ferrite, an electrophotographic development carrier containing the ferrite, and developer containing the carrier |
CN100557726C (en) * | 2003-11-12 | 2009-11-04 | 关东电化工业株式会社 | Magnesium-based ferrite, electrophotographic developing carrier containing the ferrite, and developer containing the carrier |
CN104072119A (en) * | 2014-06-12 | 2014-10-01 | 天长市中德电子有限公司 | Low-loss ferrite material |
Also Published As
Publication number | Publication date |
---|---|
KR100392505B1 (en) | 2003-07-23 |
KR20010102948A (en) | 2001-11-17 |
JP3743795B2 (en) | 2006-02-08 |
TW516048B (en) | 2003-01-01 |
CN1322364A (en) | 2001-11-14 |
WO2001022440A1 (en) | 2001-03-29 |
DE10083302T1 (en) | 2002-03-21 |
JP2001085217A (en) | 2001-03-30 |
US6423243B2 (en) | 2002-07-23 |
CN1226757C (en) | 2005-11-09 |
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