KR20010040436A - Soft magnetic nickel iron alloy with low coercive field strength, high permeability and improved resistance to corrosion - Google Patents
Soft magnetic nickel iron alloy with low coercive field strength, high permeability and improved resistance to corrosion Download PDFInfo
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- KR20010040436A KR20010040436A KR1020007008231A KR20007008231A KR20010040436A KR 20010040436 A KR20010040436 A KR 20010040436A KR 1020007008231 A KR1020007008231 A KR 1020007008231A KR 20007008231 A KR20007008231 A KR 20007008231A KR 20010040436 A KR20010040436 A KR 20010040436A
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- 229910001030 Iron–nickel alloy Inorganic materials 0.000 title claims abstract description 14
- 238000005260 corrosion Methods 0.000 title description 13
- 230000007797 corrosion Effects 0.000 title description 13
- 230000035699 permeability Effects 0.000 title description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 16
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 8
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 8
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 8
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims description 21
- 229910045601 alloy Inorganic materials 0.000 claims description 19
- 239000000956 alloy Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- 238000006477 desulfuration reaction Methods 0.000 claims description 9
- 230000023556 desulfurization Effects 0.000 claims description 9
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 238000007872 degassing Methods 0.000 claims description 3
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 238000005272 metallurgy Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910001004 magnetic alloy Inorganic materials 0.000 claims 4
- 239000013598 vector Substances 0.000 claims 1
- 238000003723 Smelting Methods 0.000 abstract 1
- 239000000945 filler Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000696 magnetic material Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000000137 annealing Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910000640 Fe alloy Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000010953 base metal Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- MMXSKTNPRXHINM-UHFFFAOYSA-N cerium(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Ce+3].[Ce+3] MMXSKTNPRXHINM-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000005261 decarburization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000033764 rhythmic process Effects 0.000 description 1
- 238000000550 scanning electron microscopy energy dispersive X-ray spectroscopy Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
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
- H01F1/14—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 metals or alloys
- H01F1/147—Alloys characterised by their composition
-
- 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
- H01F1/14—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 metals or alloys
- H01F1/147—Alloys characterised by their composition
- H01F1/14708—Fe-Ni based alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H50/00—Details of electromagnetic relays
- H01H50/16—Magnetic circuit arrangements
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- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Soft Magnetic Materials (AREA)
- Hard Magnetic Materials (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Treatment Of Steel In Its Molten State (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Conductive Materials (AREA)
- Powder Metallurgy (AREA)
Abstract
본 발명은 35-65 질량%의 니켈, 하나 또는 몇개의 희토류 세륨, 란타늄, 프라세오디뮴 또는 네오디뮴(희토류 합은 0.003-0.05 질량%임) 및 제련시 도입되는 불순물을 포함하는 소프트 자성 니켈-아이언 합금에 관한다.The present invention relates to a soft magnetic nickel-iron alloy comprising 35-65 mass% nickel, one or several rare earth cerium, lanthanum, praseodymium or neodymium (the sum of rare earths is 0.003-0.05 mass%) and impurities introduced during smelting To
Description
본 발명은 소프트 자성 니켈 아이언 합금에 관한다.The present invention relates to a soft magnetic nickel iron alloy.
Carl Heck, Huetig Verlag, Heidelberg 1975의 "Magnetische Werkstoffe und ihre technische Anwendung"(자성 재료 및 이의 기술적 용도), p.349 및 속편으로부터 소프트 자성 재료를 계전기의 접극자 및 요크 재료로 사용하는 것이 공지되어 있다.Carl Heck, Huetig Verlag, Heidelberg 1975 "Magnetische Werkstoffe und ihre technische Anwendung" (magnetic materials and their technical uses), p. 349 and the sequel are known to use soft magnetic materials as relay contacts and yoke materials. .
이러한 재료의 주요 요구사항은 적은 에너지로 높은 자성 보유력 및 높은 침투성을 얻을 수 있도록 포화 플럭스 밀도가 높아서 에어 갭내에 낮은 자기장력, 즉 낮은 자극 전류 및 높은 플럭스 밀도가 생성될 수 있어 접극자 상에 높은 인력이 작용하는 것이다. 낮은 고압 장력은 자극 전류가 감소할 경우 계전기가 용이하게 열릴 수 있게 한다.The main requirement for these materials is that the high saturation flux density allows high magnetic retention and high permeability with low energy, resulting in low magnetic tension in the air gap, i.e. low stimulation current and high flux density, resulting in high Manpower is at work. Low high tension allows the relay to open easily when the stimulus current decreases.
자성 조건 외에, 계전기 재료는 어떤 기후 조건에서도 계전기가 적절히 작동해야 하므로 대체 기후 테스트에서 내식성일 것이 요구된다. 내식성이 충분치 않은 재료에 대하여 이러한 조건은 마무리된 부품을 내식층으로 추가 피복함으로써만 충족될 수 있다.In addition to magnetic conditions, the relay material is required to be corrosion resistant in alternative climate tests as the relay must operate properly under any climatic conditions. For materials that do not have sufficient corrosion resistance, these conditions can only be met by further coating the finished part with a corrosion resistant layer.
접극자 및 요크의 접촉면은 요크 및 접극자의 자성 서클의 투과성이 높드록 가능한 작은 갭을 포함하여야 한다. 이것은 계전기의 방출 전류가 변하지 않을 것이므로 계전기를 작동시키는 것에 의하여 손상되지 않을 수 있을 것이다.The contact surface of the pole and the yoke shall comprise a small gap capable of high permeability of the magnetic circle of the yoke and the pole. This will not be damaged by operating the relay since the emission current of the relay will not change.
소프트 자성 재료의 다른 성형 및 압형 부품에 대하여도 조건은 유사하다.The conditions are similar for other molded and pressed parts of the soft magnetic material.
계전기 재료의 자성 조건은 DIN 17405 "Weichmagnetische Werkstoffe fuer Gleichstromrelais"(직렬 계전기용 소프트 자성 재료")에 기술되어 있다. 다음은 DIN 17405에서 발췌한 것이다.The magnetic conditions of the relay material are described in DIN 17405 "Weichmagnetische Werkstoffe fuer Gleichstromrelais" (soft magnetic material for series relays) The following is taken from DIN 17405.
DIN 17745 "Knetlegierungen aus Nickel und Eisen"("니켈 및 아이언의 가공 합금")은 RNi12 및 RNi8(표2를 참조하시오)류의 기본 재료로서 합금 Ni 48(재료 번호 1.3926 및 1.3927)에 대하여 기술한다. 합금 Ni 36(재료 번호 1.3911)은 RNi 24류의 기본 재료이다.DIN 17745 "Knetlegierungen aus Nickel und Eisen" ("working alloys of nickel and iron") describes alloy Ni 48 (material numbers 1.3926 and 1.3927) as the base material of the class RNi12 and RNi8 (see Table 2). Alloy Ni 36 (material number 1.3911) is the base material of the RNi 24 class.
니켈 아이언 합금의 용융시 의도하는 합금 원소외에 망가네즈, 실리슘 및 알루미늄과 같은 탈산화 및/또는 탈황화 원소가 필요하다. 또한, 비용이 적게 들므로 통상적인 스틸 밀 기법을 사용하여 이들 합금을 제조하는 것이 바람직할 경우 산소, 황, 질소, 탄소, 칼슘, 마그네슘, 크롬, 몰리브데넘, 구리 및 코발트의 최소 혼합물을 피할 수 있다. 본원에서 이것은 탈산, 탈황 및 탈기를 위한 진공 산화 탈탄 처리 및/또는 순차 레들 야금술로 오픈 아크 노에서 합금들을 용융시키는 통상적인 스틸 밀 기법에 의하여 이해된다. 이후 블록 각각 연속 캐스팅 슬랩은 1 또는 2단계로 두께 약 4mm로 고온 생성된 다음 필요할 경우 중간 어닐링으로 최종 두께로 저온 생성된다. 자성 특성은 예를들어 독일 제19612556 A1호에 기술된 바와 같이 탄소, 질소, 산소, 황 및 고체 비금속 혼합물로 인하여 악화된다. 비금속 불순물은 캐스팅 전 필요한 용융된 매스의 탈산 및/또는 탈황 처리에 의하여 야기된다. 탈산 및/또는 탈황제에 따라 이들은 칼슘, 마그네슘 또는 알루미늄 산화물이다.In addition to the intended alloying elements in the melting of nickel iron alloys, deoxidation and / or desulfurization elements such as manganese, silicon and aluminum are required. In addition, because of the low cost, it is desirable to avoid the minimal mixture of oxygen, sulfur, nitrogen, carbon, calcium, magnesium, chromium, molybdenum, copper and cobalt when it is desirable to manufacture these alloys using conventional steel mill techniques. Can be. This is understood here by conventional steel mill techniques for melting alloys in open arc furnaces by vacuum oxidative decarburization and / or sequential ladle metallurgy for deoxidation, desulfurization and degassing. Each subsequent cast slab of the block is then hot produced to a thickness of about 4 mm in one or two steps and then cold to the final thickness with intermediate annealing if necessary. Magnetic properties deteriorate due to mixtures of carbon, nitrogen, oxygen, sulfur and solid base metals, as described, for example, in German 1942 556 A1. Nonmetallic impurities are caused by the deoxidation and / or desulfurization treatment of the molten mass required before casting. Depending on the deoxidation and / or desulfurization agents they are calcium, magnesium or aluminum oxides.
이러한 어려움을 피하기 위하여 소프트 자성 재료는 실제로 제DE-A 3910147호 및 제DE-C 1259367호에 명백히 기술되어 있는 바와 같이 현행 기술의 최고 조건을 따르는 진공 기법을 이용하고 선택된 순수한 원재료를 사용하여 제조한다. 문헌에 공지된 또다른 가능성은 매우 고가인 진공 또는 블록의 보호 기체하 일랙트로슬래그 재용해법인데 이는 제DE-A 4105507호에 기술한 바와 같이 진공 또는 보호 기체하 용해가 선행된다.To avoid this difficulty, the soft magnetic material is actually manufactured using selected pure raw materials using vacuum techniques that follow the highest conditions of current technology, as clearly described in DE-A 3910147 and DE-C 1259367. . Another possibility known in the literature is the very expensive vacuum or block of gas under protective gas electroslag remelting, which is preceded by dissolution under vacuum or protective gas as described in DE-A 4105507.
본 발명의 목적은 전술한 자성 및 내부식성 및 내마모성 조건을 만족시키고 소프트 자성 부품에 일련의 바람직한 용도로 사용되는 소프트 자성 아이언 니켈 합금을 용해시키는 것으로 이루어진다.The object of the present invention consists in dissolving the soft magnetic iron nickel alloys which meet the above mentioned magnetic and corrosion and wear resistance conditions and are used in a series of preferred applications in soft magnetic parts.
이 목적은 35-65 질량%의 니켈 및 하나 이상의 희토류, 세륨, 란타늄, 프라세오디뮴 또는 네오디뮴 및 용해 의존 불순물로 이루어지는 소프트 자성 아이언 니켈 합금으로 이루어지는데 이때 희토류 총합은 0.003-0.05 질량%를 구성하고 희토류인 세륨, 란타늄, 프라세오디뮴 또는 네오디뮴의 총분율(질량%)은 황(질량%)보다 4.4 펙터 이상 높다.The objective consists of a soft magnetic iron nickel alloy consisting of 35-65 mass% nickel and one or more rare earths, cerium, lanthanum, praseodymium or neodymium and dissolution dependent impurities in which the total rare earth constitutes 0.003-0.05 mass% and is rare earth. The total fraction (mass%) of cerium, lanthanum, praseodymium or neodymium is at least 4.4 factor higher than sulfur (mass%).
본 발명 목적의 유리한 개발은 종속항들에서 기술한다.Advantageous developments of the object of the invention are described in the dependent claims.
본 발명 합금은 바람직하게는 스틸 밀 기법을 이용하여, 즉 탈산, 탈황 및 탈기를 위한 VOD 처리(진공 산화 탈탄화) 및/또는 순차 레들 야금술로 오픈 아크 노에서 용융시켜 제조한다. 이후 블록 각각 연속 캐스팅 슬랩은 1 또는 2단계로 두께 약 4mm로 고온 생성된 다음 필요할 경우 스트립으로부터 부품을 제조하는데 필요한 경도를 조절하기 위한 중간 어닐링으로 최종 두께로 저온 생성된다.The alloy of the invention is preferably prepared by melting in an open arc furnace using a steel mill technique, ie VOD treatment (vacuum oxidative decarbonization) and / or sequential ladle metallurgy for deoxidation, desulfurization and degassing. Each block of continuous casting slab is then hot produced to a thickness of about 4 mm in one or two stages and then cold to final thickness with intermediate annealing to adjust the hardness required to manufacture the part from the strip, if necessary.
이러한 합금으로 제조한 부품의 제조 및 이들 부품을 800-1150℃의 온도에서 어닐링시킨후 이들 부품으로 8A/m 미만의 보자력마당 세기를 얻는 것이 가능하다.It is possible to obtain coercive field strengths of less than 8 A / m with these parts after the manufacture of parts made of such alloys and after annealing these parts at temperatures of 800-1150 ° C.
본 발명 합금의 바람직한 용도는 특히 접극자 및 요크와 같은 계전기 부품이다.Preferred uses of the alloy of the invention are in particular relay components such as poles and yokes.
또한 아이언 니켈 합금은 다음 용도로 사용할 수 있다:Iron nickel alloys can also be used for:
- 솔레노이드 밸브의 밸브 보넷 및 밸브 포트-Valve bonnet and valve port of solenoid valve
- 각각의 요크, 각각의 극편, 각각의 자극편, 극시트 금속 및 미가공 자석 및 전기자석의 접극자-Poles of each yoke, each pole piece, each pole piece, pole sheet metal and raw magnet and electromagnet
- 전기모터의 로터 및 스테이터 및 펄스 모터의 인덕터 코어 및 스테이터Rotor and stator of electric motor and inductor core and stator of pulse motor
- 센서의 성형 및 압형 부품, 위치 전송기 및 리시버-Molded and pressed parts of sensors, position transmitters and receivers
- 마그네트 헤드 및 헤드 스크린-Magnet head and head screen
- 예를들어 모터 스크린과 스크리닝, 지시기용 스크리닝 캔 및 음극선관용 스크린.Motor screens and screening, screening cans for indicators and screens for cathode ray tubes, for example.
스틸 밀 기법을 이용하여 제조한 두께 1.2mm의 스트립으로부터 평평한 샘플을 잘라내어 세척하고 수소하에 4시간동안 1080℃에서 어닐링 처리한 다음 노에서 300℃로 냉각하였다. 이들 샘플을 DIN 50017에 기술한 바와 같이 55℃/공기 습도 90-96%에서 8시간 및 25℃에서 공기 습도 95-99%에서 16시간동안 28회 기후 테스트 하였다. 36-81 질량%의 니켈을 포함하는 합금 및 크롬, 구리 및/또는 몰리브데늄과 같은 부분적 부가물을 조사하였다(표3을 참조하시오). 55 질량% 이하의 니켈을 포함하는 모든 합금은 75% 이상의 니켈을 함유하는 합금보다 대체 기후 테스트후 표면 부식이 더 큼이 명백하므로(B. Gehrmann, H. Hattendorf, A. Kolb-Telieps, W.Kramer, W. Moettgen의 Material and Corrosion 48, 535-541(1997)) 내부식성을 개선시키기 위한 추가적 조치 없이는 계전기 재료의 내부식성 조건에 부합하지 않는다. 다른 한편, 제DIN 17405호에 의하여 요구되는 자성은 표3의 실시예(현행 기술)에 의하여 기술한 보자력마당 세기 Hc에 의하여 보여지는 바와 같이 부합하였다.Flat samples were cut from the 1.2 mm thick strip prepared using the steel mill technique, washed, annealed at 1080 ° C. for 4 hours under hydrogen and then cooled to 300 ° C. in a furnace. These samples were subjected to 28 climate tests for 8 hours at 55 ° C / air humidity 90-96% and 16 hours at 25 ° C air humidity 95-99% as described in DIN 50017. Alloys containing 36-81 mass% nickel and partial adducts such as chromium, copper and / or molybdenum were investigated (see Table 3). All alloys containing less than 55 mass% nickel are apparently more susceptible to surface corrosion after alternative climate tests than alloys containing more than 75% nickel (B. Gehrmann, H. Hattendorf, A. Kolb-Telieps, W. Kramer, W. Moettgen's Material and Corrosion 48, 535-541 (1997)) do not meet the corrosion resistance requirements of the relay material without further measures to improve the corrosion resistance. On the other hand, the magnetism required by DIN 17405 was met as shown by the coercive field strength Hc described by the example of Table 3 (current technology).
대체 기후 테스트후 SEM/EDX를 이용하여 이들 샘플의 부식 지점에서 황을 발견하였다.After an alternate climate test, SEM / EDX was used to find sulfur at the corrosion point of these samples.
놀랍게도 세륨을 사용하여 35-65 질량%의 니켈을 함유하는 부식성이 더 큰 아이언 니켈 합금을 탈황시킴으로써 본 발명 부식 작용 개선이 이루어진다. 이것은 바람직하게는 그 화학적 행동이 매우 유사한 희토류 세륨 및/또는 란타늄 및/또는 프라세오디뮴 및/또는 네오디뮴으로 이루어지는 조성 금속을 사용하여 실행한다. 황을 전부 안전하게 결합시키기 위하여 충분한 희토류 원자가 존재하여야 한다. 예를들어 세륨 분율이 높은 CeS를 사용하여 세륨 설파이드를 제조할 것을 가정하면 이 경우 황 원자보다 더 많은 세륨 원자가 합금내에 존재한다.Surprisingly, the inventive corrosive improvement is achieved by desulfurizing the more corrosive iron nickel alloy containing 35-65 mass% nickel with cerium. This is preferably done using a composition metal consisting of rare earth cerium and / or lanthanum and / or praseodymium and / or neodymium with very similar chemical behavior. Sufficient rare earth atoms must be present to safely bind all the sulfur. For example, assuming that cerium sulfide is prepared using CeS having a high cerium fraction, in this case more cerium atoms are present in the alloy than sulfur atoms.
따라서, 세륨에 의한 황의 완전한 결합을 위하여 세륨 함량(질량%)은 황 함량(질량%)보다 4.4 펙터 높아야 한다. 해당하는 룰은 다른 희토류 란타늄, 프라세오디뮴 및/또는 네오디뮴 및 전체 희토류에 적용되는 것이다.Therefore, the cerium content (mass%) must be 4.4 factor higher than the sulfur content (mass%) for complete bonding of sulfur by cerium. Applicable rules apply to other rare earth lanthanum, praseodymium and / or neodymium and the entire rare earth.
앞서 이미 언급한 바와 같이 예를들어 세륨과 같은 이러한 강력한 탈산 및 탈황제를 가하여 재료내 잔류하는 반응 생성물로 인한 자성을 부여할 수 있다(A. Hoffmann, Ueber den Einfluss von verschiedenen Desoxidationselementen auf die Verformung und Anfangspermeabilitaet von Ni-Fe-Legierungen(Ni-Fe합금의 분해 및 초기 투과성에 미치는 상이한 탈산화 요소의 영향에 대하여), Z. angew, Physik 32, p236-241). 놀랍게도 희토류의 부가는 보자력마당 세기 및 침투성의 자기값이 현행 기술에 따른 용융 충전물의 통상적인 변형내에 있을 수 있도록 정량적이 될 수 있다.As already mentioned above, such strong deoxidation and desulfurization agents such as cerium can be added to impart magnetism due to the reaction products remaining in the material (A. Hoffmann, Ueber den Einfluss von verschiedenen Desoxidationselementen auf die Verformung und Anfangspermeabilitaet von Ni-Fe-Legierungen (on the effect of different deoxidation factors on the decomposition and initial permeability of Ni-Fe alloys), Z. angew, Physik 32, p236-241). Surprisingly, the addition of rare earths can be quantitative so that the magnetic values of coercive field strength and permeability can be within the conventional deformation of the melt charge according to the current technology.
계전기의 접촉면 밖으로 나온 탈산 잔기가 이들 표면 사이에 남아있어 최종적으로 광택처리한 접촉면을 파괴할 수 있음은 공지되어 있다. 그러나 계전기 재료는 DIN 50602(방법 M)에 따른 소량의 고체 비금속 포함물을 함유하도록만 허용된다. 세륨 또는 희토류 세륨, 란타늄, 프라세오디뮴, 네오디뮴으로 이루어지는 조성 금속을 이용한 탈산화에서 DIN 50602에 따른 라인 형태 SS에서 황화된 포함물의 최대값은 0.1, 1.1 이하, 용해된 형태 OA(알루미늄 옥사이드)내 산성 포함물의 DIN 50602에 따른 최대값은 2.2, 3.2, 4.2이하, 라인 형태 OS(실리케이트)내 산성 포함물의 DIN 50602에 따른 최대값은 5.2, 6.2, 7.2이하, 공모양의 OG(알루미늄 옥사이드)내 산성 포함물의 DIN 50602에 따른 최대값은 8.2, 9.2이하이다.It is known that deoxidized residues which exit the contact surface of the relay can remain between these surfaces and destroy the finally polished contact surface. However, the relay material is only allowed to contain small amounts of solid nonmetallic inclusions according to DIN 50602 (Method M). In deoxidation with a composition metal consisting of cerium or rare earth cerium, lanthanum, praseodymium and neodymium, the maximum value of sulfided inclusions in line form SS according to DIN 50602 is 0.1, 1.1 or less, including acid in dissolved form OA Maximum values of water according to DIN 50602 up to 2.2, 3.2 and 4.2, acid inclusions in line form OS (silicate) Maximum values according to DIN 50602 up to 5.2, 6.2 and 7.2, including acid in ball OG (aluminum oxide) The maximum value according to DIN 50602 for water is 8.2 and below 9.2.
약 48%의 니켈 및 소량의 망간 및 실리슘을 포함하는 니켈 아이언 합금을 스틸 밀 기법을 이용하여 30톤 아크 노에서 용융시켜 현행 기술에 해당하는 희토류를 가하지 않은 매우 유사한 조성물(T4392, T5405 및 T5406)과 비교하였다. 표4에 정확한 조성을 나타내었다.Very similar compositions (T4392, T5405, and T5406) containing about 48% nickel and a small amount of manganese and silicium nickel iron alloys melted in a 30 ton arc furnace using a steel mill technique to add the rare earth equivalent of current technology. ). Table 4 shows the correct composition.
T4392, T5405 및 T5406에 행한 바와 같이, 펀칭 특성을 개선시키기 위하여 최소량의 보론을 가할 수 있다. 본 발명 충전물 E5407 및 E0545내 세륨의 함량(질량%)은 황 함량(질량%)보다 4.4 펙터 이상 높다.As in T4392, T5405, and T5406, a minimum amount of boron can be added to improve the punching properties. The content (mass%) of cerium in the fillers E5407 and E0545 of the present invention is at least 4.4 factor higher than the sulfur content (mass%).
용융후, 약 4mm까지 블루밍과 이어서 핫 스트립 롤링을, 이어서 최종 두께 1.0mm까지 저온 리덕션시켰다.After melting, blooming to about 4 mm followed by hot strip rolling followed by cold reduction to a final thickness of 1.0 mm.
이로부터 직경 25.5mm인 둥근 샘플을 펀칭하였다. 이것을 E0545를 제외한 모든 충전물에 가하였다. 약 15mm x 15mm x 5mm의 캐스팅 샘플 조각을 사용하는데 이 표면은 미세하게 광택을 내었다. 샘플을 전부 세척하고 샘플 일부를 수소하에 6시간동안 970℃에서 어닐링시킨 다음 노에서 300℃ 이하로 냉각시켰다. 샘플의 두번째 일부를 수소하에 2시간동안 1030℃에서 어닐링시킨 다음 노에서 300℃ 이하로 냉각시켰다. 샘플을 전부에 25℃, 공기습도 55% 내지 55℃, 공기습도 98%에서 3시간 리듬으로 온도/습도를 변화시켜 2일간 단축된 기후 테스트를 하였다. 이때 샘플은 개별적으로 유리판 위에 평평하게 놓아서 훨씬 더 심한 균열 부식 조건에 노출시켰다. 표5는 결과를 나타낸다.From this a round sample of 25.5 mm diameter was punched out. This was applied to all fillings except E0545. A cast sample piece of about 15 mm x 15 mm x 5 mm was used and the surface was finely polished. The samples were washed thoroughly and some of the samples were annealed at 970 ° C. for 6 hours under hydrogen and then cooled to 300 ° C. or below in a furnace. The second part of the sample was annealed at 1030 ° C. for 2 hours under hydrogen and then cooled to 300 ° C. or below in a furnace. All samples were subjected to a 2-day shortened climate test by varying the temperature / humidity at 25 ° C., air humidity 55% to 55 ° C., air humidity 98% in a 3 hour rhythm. The samples were then individually laid flat on the glass plate to expose them to even more severe crack corrosion conditions. Table 5 shows the results.
본 발명 E5407 및 E0545에 따른 충전물은 부식을 보이지 않는 반면 두 비교 충전물 T5405 및 T5406의 각 시료는 양면에 부식점을 보이지 않았다.The fillers according to the inventions E5407 and E0545 showed no corrosion while the respective samples of the two comparative fillers T5405 and T5406 did not show corrosion points on both sides.
세륨과 같은 강한 탈산 및 탈황제의 부가는 전술한 바와 같이 재료에 잔류하는 반응 생성물로 인하여 자성을 부여할 수 있다. 놀랍게도 본 발명 E5407 및 E0545에 따른 충전물에 의하여 보여지는 보자력마당 세기 및 자성 투과치는 표6에 나타낸 바와 같이 첨단 용융 충전물의 통상적인 변형 범위내이다.Strong deoxidation and the addition of desulfurization agents such as cerium can impart magnetism due to the reaction products remaining in the material as described above. Surprisingly, the coercive field strength and the magnetic permeability seen by the fillers according to the inventions E5407 and E0545 are within the usual range of deformation of the advanced melt fillers as shown in Table 6.
표6은 수소하에 1080℃에서 4시간동안 어닐링시키고 노에서 450℃로 냉각시킨 후의 두께 1mm의 시료에 대하여 현행 기술(T) 및 본 발명(E)에 따른 충전물의 자성치를 측정한 것이다. 표4는 충전물의 조성을 나타내었다.Table 6 measures the magnetic values of the packing according to the current technology (T) and the invention (E) for a sample of 1 mm thickness after annealing at 1080 ° C. for 4 hours under hydrogen and cooling to 450 ° C. in a furnace. Table 4 shows the composition of the filler.
두번째로, 표7에 열거한 현행 두 조성물의 블루밍 및 핫 스트립 롤링시 행동을 관찰하였다.Second, the behavior during blooming and hot strip rolling of the two current compositions listed in Table 7 was observed.
두 충전물은 실질적으로 희토류 함량이 상이하다는 점에서만 차이가 난다.The two charges differ only in that the rare earth content is substantially different.
희토류 총함량 0.054%인 충전물 T0626에 대하여 고온 형성시 균열이 생긴후 블록이 부서졌다. 이러한 고함량 희토류는 더 나쁜 고온 형성 행동을 유발한다. 이와는 대조적으로 충전물 T0624는 블록 및 두께 4mm의 고온 스트립 양쪽으로 롤링시킬 수 있을 것이다. 희토류는 유사한 화학적 행동을 보이므로 희토류 세륨, 란타늄, 프라세오디뮴 및 네오디뮴의 함량은 고온 형성 문제를 피하기 위하여 본 발명에 따라 최대 0.05 질량%로 제한하여야 한다.The block was broken after cracking at high temperature formation for the filler T0626 having a total rare earth content of 0.054%. Such high content rare earths cause worse hot forming behavior. In contrast, the filling T0624 will be able to roll into both the block and the hot strip 4 mm thick. Rare earths exhibit similar chemical behavior, so the content of rare earths cerium, lanthanum, praseodymium and neodymium should be limited to a maximum of 0.05 mass% in accordance with the present invention to avoid high temperature formation problems.
표8은 현행 기술(T)에 따른 상이한 충전물 및 본 발명(E)에 따른 충전물에서 DIN 50602에 따른 고체 비금속 포함물의 함량 분석을 보인다.Table 8 shows the content analysis of the solid base metal inclusions according to DIN 50602 in the different packings according to the current technology (T) and in the packings according to the invention (E).
충전물 T2536은 라인 제조시(방법 M) 산성 포함물에 대하여 최대값 2.7을 보인다. 이 값은 계전기 부품 재료로서 이 충전물을 사용하기에 너무 높다. 이것은 계전기의 접촉면을 마모시켜 계전기의 작동성을 손상시킨다. 따라서 본 발명 고체 비금속 포함물의 함량은 다음과 같이 제한하여야 한다.Fill T2536 shows a maximum value of 2.7 for acid inclusions in line preparation (method M). This value is too high to use this filling as relay component material. This wears off the contact surface of the relay and impairs its operability. Therefore, the content of the solid nonmetallic inclusion of the present invention should be limited as follows.
DIN 50602에 따른 라인 형태 SS에서 황화된 포함물의 최대값은 0.1, 1.1 이하, 용해된 형태 OA(알루미늄 옥사이드)내 산성 포함물의 DIN 50602에 따른 최대값은 2.2, 3.2, 4.2이하, 라인 형태 OS(실리케이트)내 산성 포함물의 DIN 50602에 따른 최대값은 5.2, 6.2, 7.2이하, 공모양의 OG(알루미늄 옥사이드)내 산성 포함물의 DIN 50602에 따른 최대값은 8.2, 9.2이하이다. 표8에 열거된 모든 다른 충전물은 고체 비금속 포함물의 함량 요구조건을 부합시킨다.The maximum value of sulfided inclusions in line form SS according to DIN 50602 is 0.1, 1.1 or less, the maximum values according to DIN 50602 of acid inclusions in dissolved form OA (aluminum oxide) are 2.2, 3.2, 4.2 or less, and the line form OS ( The maximum values according to DIN 50602 of acidic inclusions in silicates) are 5.2, 6.2 and 7.2 or less and the maximum values according to DIN 50602 of acidic inclusions in ball-shaped OG (aluminum oxide) are 8.2 and 9.2 or less. All other fillers listed in Table 8 meet the content requirements for solid base metal inclusions.
Claims (15)
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803598A DE19803598C1 (en) | 1998-01-30 | 1998-01-30 | Soft magnetic iron-nickel alloy for relay armatures and yokes |
| DE19803598.5 | 1998-01-30 |
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| KR20010040436A true KR20010040436A (en) | 2001-05-15 |
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| CN102306528B (en) * | 2011-05-23 | 2012-11-28 | 浙江科达磁电有限公司 | Fe-Ni alloy soft magnetic material with magnetic permeability mu of 125 and manufacturing method for Fe-Ni alloy soft magnetic material |
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| PT1051714E (en) | 2002-06-28 |
| ES2169597T5 (en) | 2008-11-01 |
| PL341568A1 (en) | 2001-04-23 |
| CZ20002616A3 (en) | 2000-11-15 |
| JP2002502118A (en) | 2002-01-22 |
| EP1051714A1 (en) | 2000-11-15 |
| JP2007314885A (en) | 2007-12-06 |
| HUP0003646A3 (en) | 2001-04-28 |
| ES2169597T3 (en) | 2002-07-01 |
| CZ301345B6 (en) | 2010-01-20 |
| PL192145B1 (en) | 2006-09-29 |
| TW418406B (en) | 2001-01-11 |
| DE59900588D1 (en) | 2002-01-31 |
| EP1051714B1 (en) | 2001-12-19 |
| HUP0003646A2 (en) | 2001-02-28 |
| WO1999039358A1 (en) | 1999-08-05 |
| TR200002190T2 (en) | 2000-11-21 |
| CN1163915C (en) | 2004-08-25 |
| HU222469B1 (en) | 2003-07-28 |
| SK10832000A3 (en) | 2001-03-12 |
| CN1275238A (en) | 2000-11-29 |
| KR100384768B1 (en) | 2003-06-18 |
| ATE211297T1 (en) | 2002-01-15 |
| DE19803598C1 (en) | 1999-04-29 |
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| SK285293B6 (en) | 2006-10-05 |
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