CN1275238A - Soft magnetic nickel-iron aloy with low coercive field strength, high permeability and improved resistance to corrosion - Google Patents
Soft magnetic nickel-iron aloy with low coercive field strength, high permeability and improved resistance to corrosion Download PDFInfo
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- CN1275238A CN1275238A CN99801411A CN99801411A CN1275238A CN 1275238 A CN1275238 A CN 1275238A CN 99801411 A CN99801411 A CN 99801411A CN 99801411 A CN99801411 A CN 99801411A CN 1275238 A CN1275238 A CN 1275238A
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- 230000007797 corrosion Effects 0.000 title description 12
- 238000005260 corrosion Methods 0.000 title description 12
- 230000035699 permeability Effects 0.000 title description 8
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 12
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 7
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 7
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims description 38
- 239000000956 alloy Substances 0.000 claims description 38
- 239000000463 material Substances 0.000 claims description 30
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 20
- 150000002910 rare earth metals Chemical class 0.000 claims description 19
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 230000005389 magnetism Effects 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229910000831 Steel Inorganic materials 0.000 claims description 8
- 239000010959 steel Substances 0.000 claims description 8
- 238000000137 annealing Methods 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 239000011575 calcium Substances 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 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
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-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
- 238000007872 degassing Methods 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 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
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000976 Electrical steel Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 229910000990 Ni alloy Inorganic materials 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 claims 1
- 230000023556 desulfurization Effects 0.000 claims 1
- 238000003723 Smelting Methods 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract 1
- 239000011651 chromium Substances 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 229910052755 nonmetal Inorganic materials 0.000 description 6
- 235000021050 feed intake Nutrition 0.000 description 5
- 239000000696 magnetic material Substances 0.000 description 5
- 229910001021 Ferroalloy Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 3
- 230000008030 elimination Effects 0.000 description 3
- 238000003379 elimination reaction Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 230000000717 retained effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000003763 carbonization 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
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005352 clarification 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
- 238000005262 decarbonization Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 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 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- 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)
- Powder Metallurgy (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to a soft magnetic nickel-iron alloy containing 35-65 mass % nickel, one or several of the rare earths cerium, lanthanum, praseodymium or neodymium and the impurities introduced during smelting, the sum of the rare earths being between 0.003 and 0.05 mass %.
Description
The present invention relates to the soft magnetism nickel-ferro alloy.
By " magnetic material and its commercial Application " of Carl Heck, H tig publishing house, Heidelberg 1975, the 349 pages or leaves such as grade) book is known, and soft magnetic material is as the material of armature and yoke in relay.
Major requirement to this material is to have high saturation flux density, so that under low energy, obtain high magnetic holding force, has high magnetic permeability, and therefore low magnetic field intensity, that is to say, in air gap, can produce low exciting current and high magnetic flux density, on armature, produce big attraction like this.When exciting current reduced, low coercive field strength can make relay disconnect easily.
Except that magnetic requires, when weather replaces, relay material also had corrosion resistant requirement, because the normal function of relay is essential under every kind of climatic condition.When material does not have enough corrosion resistances, only be by additionally applying finished product, making it have corrosion-resistant finishes to satisfy this requirement.
The contact surface of armature and yoke must have as far as possible little gap, so that the magnetic circuit of being made up of yoke and armature has high magnetic permeability.It can not be subjected to the damage of relay status conversion, because the release current of relay will change.
Also there is similar requirement in other mold pressing and the stamping parts of being made by soft magnetic material.
DIN17405 " soft magnetic material that is used for direct current relay " has described the magnetic requirement of relay material.Following table provides the content of being taken passages by DIN17405.
Table 1: according to the relay material of DIN17405
| Material | Coercive field strength | Minimum magnetic flux | The feature of alloy is formed | ||||||
| Be called for short | Material number | Maximum Hc A/m | Under magnetic field intensity H (A/m) | Weight % | |||||
| ??20 | ??50 | ??100 | ??300 | ??500 | ??4000 | ||||
| ??RNi24 | ???1.3911 | ????24 | ??0.20 | ??0.45 | ??0.70 | ??0.90 | ??1.00 | ??1.18 | ????36Ni |
| ??RNi12 | ???1.3926 | ????12 | ??0.50 | ??0.90 | ??1.10 | ??1.25 | ??1.35 | ??1.45 | ????50Ni |
| ??RNi8 | ???1.3927 | ????8 | ??0.50 | ??0.90 | ??1.10 | ??1.25 | ??1.35 | ??1.45 | ????50Ni |
| ??RNi5 | ???2.4596 | ????5 | ??0.50 | ??0.65 | ??0.70 | ??0.75 | 70 to 80Ni, a small amount of Cu, Cr, Mo | ||
| ??RNi2 | ???2.4595 | ????2.5 | ??0.50 | ??0.65 | ??0.70 | ??0.75 | |||
Alloy Ni48 (material sequence number 1.3926 and 1.3927) (referring to table 2) as the basic material of RNi12 and RNi8 class has been described among the DIN17745 " nickel and-iron wrought alloy ".Alloy Ni36 (material sequence number 1.3911) is the basic material of RNi24 class.
Table 2: by the content of DIN17745 extracts
| Be called for short | Material number | Form weight % | |
| Alloy composition | Admissible tramp material | ||
| ????Ni?48 | ????1.3926 ????1.3927 | Ni is minimum 46, and Fe49-53 | ??C?0.05，Mn?0.5， ??????Si?0.3 |
| ????Ni?36 | ????1.3911 | About 36 | |
When melting of nickel-ferro alloy refined, except that required alloying element, also need deoxidation element and/or sulphur removal element such as manganese, silicon and aluminium.In addition, when adopting conventional steel-smelting technology to prepare this alloy owing to cost is low, unavoidably introduce certain minimum flow, oxygen, sulphur, phosphorus, carbon, calcium, magnesium, chromium, molybdenum, copper and cobalt be mingled with.Therefore, under the steel-smelting technology of routine, melting in arc furnace refined these alloys and subsequently steel ladle metallurgy that is used for deoxidation, sulphur removal and the degassing and/or vacuum oxidizability carbonization treatment.Afterwards, the hot forming in one or two step with steel ingot or continuously cast slab (Stranggussbramme) is 4 millimeters until thickness, subsequently-if desired, comprises that also intermediate annealing-cold forming is to final thickness.As describing among the DE19612556A1, be mingled with carbon, nitrogen, oxygen, sulphur and nonmetal inclusion magnetic property is worsened.By the deoxidation of required melt before the casting and/or remove sulphuring treatment and introduce nonmetal inclusion.According to deoxidation and/or sulfur elimination difference, these are mingled with for example is the oxide of calcium, magnesium and aluminium.
Therefore, in order to overcome these difficulties, up to now, the soft magnetic material that has peak demand in the prior art is to prepare by the basic material that the nothing of selecting is mingled with by means of vacuum technique, as offering some clarification among DE-A 3910147 and the DE-C 1259367.Other by possibility known in the open source literature is, in as DE-A 4105507, describe very expensive, in advance under vacuum or protective gas melting the electro-slag re-melting method of steel ingot.
Task of the present invention is a melting soft magnetism Fe-Ni alloy, and this alloy has the magnetic property that meets above-mentioned requirements, corrosion-resistant and resistance to wear, and has a series of preferred application in soft magnetic components.
This task is by having 35 to 65 weight % nickel and one or more rare earth metal ceriums, lanthanum, praseodymium or neodymium and depend on that the soft magnetism Fe-Ni alloy that is mingled with under the melting condition finishes, and wherein the total amount of rare earth metal is 0.003 to 0.05 weight %.
The favourable execution mode of theme of the present invention is described in the appended dependent claims.
Alloy of the present invention is preferably by steel-smelting technology, promptly by fusing in open arc furnace (offenen Lichtbogen), undertaken by steel ladle metallurgy and/or (vacuum oxidation and decarbonization) processing subsequently that deoxidation, sulphur removal and the degassing make.Afterwards, the hot forming in one or two step with steel ingot or continuously cast slab is 4 millimeters until thickness, subsequently-if desired, also adjusts by this band by intermediate annealing-cold forming to final thickness and prepares the required hardness of element.
Preparing element by this alloy and at 800 to 1150 ℃ down after the annealing, the coercive field strength that this element obtains is lower than 8A/m.
The preferred purposes of alloy of the present invention is relay element such as yoke and armature.
In addition, Fe-Ni alloy of the present invention also is suitable for using in below the application:
The bonnet of-magnet valve and valve body
The yoke of-idle magnet and electromagnet or pole piece or pole shoe or the utmost point silicon steel sheet and armature
The rotor of the magnetic bobbin core of-stepping motor and stator and motor and stator
The molding and the stamping parts of-transducer, location transmitter and location recipient
-magnetic head and magnetic head shielding
-shielding, for example motor shielding, the radome of indicating instrument and the shielding of cathode ray tube.
To strike out the plain film sample by the thick 1.2 millimeters band that steel mill's technology makes, clean, under hydrogen, carry out annealing in process, in stove, be cooled to 300 ℃ then with 1080 ℃/4 hours.The weather test of using this sample to carry out describing among the DIN50017: under 55 ℃/90-96% air humidity 8 hours and at 25 ℃, following 16 hours of 95-99% air humidity was carried out this circulation 28 times.The alloy of test is the alloy (referring to table 3) that comprises 36-81 weight % nickel and portions additive such as chromium, copper and/or molybdenum.After the end of anti-alternately climatic test, with nickel content greater than 75% alloy phase ratio, nickel content obviously more serious corrosion phenomenon (B.Gehrmann all occurs smaller or equal to all alloys of 55 weight % on its surface, H.Hattendorf, A.Kolb-Telieps, W.Kramer, W.Mottgen, and do not having the requirement of not satisfying above-mentioned corrosion resistance to relay material under the additional corrosive measure of improvement material and corrosion 48,535-541 (1997)).In contrast, as the coercive field strength Hc explanation shown in the example of passing the imperial examinations at the provincial level at table 3, it satisfies the magnetic property (prior art) that DIN 17405 requires.
Table 3
| Form weight % | ?Hc ?A/m | Maximum Hc is according to DIN17405 | |||||||
| Alloy | ?Fe | ?Ni | ?Mo | ?Cr | ?Cu | ?Mn | ?Si | ||
| ?Fe-36Ni | ?62.90 | ?36.50 | ?0.01 | ?0.03 | ?0.03 | ?0.27 | ?0.18 | ?4.2 | ??24 |
| ?Fe-40Ni | ?58.35 | ?40.75 | ?0.02 | ?0.05 | ?0.04 | ?0.50 | ?0.18 | ?4.7 | |
| ?Fe-41Ni | ?58.50 | ?40.65 | ?0.01 | ＜0.01 | ?0.04 | ?0.47 | ?0.21 | ?3.2 | |
| ?Fe-45Ni | ?54.25 | ?44.70 | ?0.02 | ?0.02 | ?0.02 | ?0.58 | ?0.28 | ?2.5 | |
| ?Fe-47Ni-6Cr | ?45.85 | ?47.30 | ＜0.01 | ?6.04 | ?0.01 | ?0.21 | ?0.26 | ?3.8 | |
| ?Fe-48Ni | ?51.70 | ?47.50 | ?0.04 | ?0.03 | ?0.02 | ?0.41 | ?0.20 | ?2.4 | ??8 |
| ?Fe-50Ni | ?48.85 | ?50.70 | ?0.01 | ?0.04 | ?0.03 | ?0.21 | ?0.05 | ?3.5 | ??8 |
| ?Fe-55Ni | ?43.70 | ?55.45 | ?0.06 | ?0.06 | ?0.05 | ?0.42 | ?0.14 | ?12.5 | |
| ?Fe-76Ni- ?Cr，Cu | ?16.05 | ?75.95 | ?0.10 | ?2.00 | ?4.96 | ?0.60 | ?0.22 | ?0.87 | ??2.5 |
| ?Fe-77Ni- ?Ti，Nb | ?14.80 | ?77.30 | ?0.01 | ?0.10 | ?4.50 | ?0.49 | ?0.24 | ?2.4 | ??2.5 |
| ?Fe-77Ni- ?Mo，Cu | ?13.85 | ?77.15 | ?3.45 | ?0.10 | ?4.47 | ?0.53 | ?0.33 | ?0.85 | ??2.5 |
| ?Fe-80Ni-Mo | ?13.95 | ?80.10 | ?4.75 | ?0.05 | ?0.09 | ?0.50 | ?0.33 | ?0.44 | ??2.5 |
| ?Fe-81Ni-Mo | ?12.45 | ?81.50 | ?5.27 | ?0.03 | ?0.05 | ?0.43 | ?0.13 | ?1.23 | ??2.5 |
After the end of anti-alternately climatic test, find sulphur at the corrosion location of sample by means of REM/EDX.
According to the present invention, the improvement of corrosive nature is astoundingly by adopting cerium that nickel-ferro alloy sulphur removal corrosion-prone, that its nickel content is 35-65 weight % is realized.Therefore, preferably this by chemical property very similarly rare earth metal cerium and/or lanthanum and/or praseodymium and/or the neodymium hybrid metal formed carry out.In order to ensure fixed all sulphur, must there be enough rare earth.If from forming the cerium sulphide CeS that for example has high cerium content, the cerium atom that exists in alloy so comes to this for a long time than sulphur atom.
For by the whole fixed sulphur of cerium, cerium content (weight %) must be 4.4 times of sulfur content (weight %) at least so.To other rare earth lanthanum, praseodymium and/or neodymium with the total content of rare earth metal is required also is same.
As mentioned above, be retained in the material owing to adding the product that strong like this deoxidier and sulfur elimination such as cerium form, thereby influenced magnetic property (A.Hoffmann, " about different deoxidant elements to the distortion of Ni-Fe alloy and the influence of initial permeability ", Z.angew. physics is 32, the 236 to 241 pages).Astoundingly, should add rare earth metal, even the magnetic values of magnetic permeability and coercive field strength is in the conventional fluctuation range according to the furnace charge of prior art melting with such amount.
Known, but go out dexidizing slag from the contact surface explosion of relay, and it is retained in the middle of the contact surface, and has destroyed the contact surface of smart throwing when further connection of relay owing to its high hardness (for example under the situation at oxidation residua).Therefore, according to DIN 50602 (method M), relay material must only have low-down nonmetal inclusion content.Therefore, in the time of when the hybrid metal deoxidation of using cerium or being made up of rare earth metal cerium, lanthanum, praseodymium, neodymium, at linear SS, the greatest measure of sulphide inculsion is less than 0.1 or 1.1; In the fusing form, the greatest measure of oxide inclusions OA (aluminium oxide) is less than 2.2 or 3.2 or 4.2; In wire-form, the greatest measure of oxide inclusions OS (silicate) is less than 5.2 or 6.2 or 7.2, and in balled form, the greatest measure of oxide inclusions OG is less than 8.2 or 9.2.
The nickel-ferro alloy (furnace charge E5407 and E0545) that for example has about 48% nickel and inappreciable manganese and silicon by means of the melting in 30 tons arc furnace of steel mill's technology, and with form very similarly, but the furnace charge (furnace charge T4392, T5405 and T5406) (prior art) that does not add the prior art of rare earth compares.List in the table 4 accurate the composition.
Table 4: charge composition of the prior art (T) and charge composition of the present invention (E),
Unit: weight %.
| Element | Prior art | By composition of the present invention | The limit | ||||||
| Feed intake | ?T2536 | ?T5477 | ?T5488 | ?T4392 | ?T4505 | ??T5406 | ?E5407 | ?E0545 | |
| ?Ni | ?47.45 | ?47.5 | ?47.85 | ?47.7 | ?47.45 | ??47.9 | ?47.65 | ?47.65 | |
| ?Mn | ?0.40 | ?0.40 | ?0.36 | ?0.38 | ?0.40 | ??0.38 | ?0.39 | ?0.41 | Maximum 0.5 |
| ?Si | ?0.19 | ?0.19 | ?0.22 | ?0.20 | ?0.14 | ??0.15 | ?0.14 | ?0.22 | Maximum 0.3 |
| ?Al | ?0.005 | ?0.005 | ?0.007 | ?0.009 | ?0.007 | ??0.008 | ?0.005 | ?0.005 | Maximum 0.010 |
| ?Mg | ?0.001 | ?0.0003 | ?0.0008 | ?0.0001 | ?0.0001 | ??0.0002 | ?0.0006 | ?0.0008 | Maximum 0.002 |
| ?Ca | ?0.0004 | ?0.0004 | ?0.0003 | ?0.0001 | ??0.0002 | ?0.0002 | ?0.0003 | Maximum 0.002 | |
| ?Cer | ?- | ?- | ?- | ?- | ?- | ??- | ?0.014 | ?0.011 | |
| ?La | ?- | ?- | ?- | ?- | ?- | ??- | ?0.008 | ?0.005 | |
| ?Pr | ?- | ?- | ?- | ?- | ?- | ??- | ?0.001 | ?0.001 | |
| ?Nd | ?- | ?- | ?- | ?- | ?- | ??- | ?0.003 | ?0.003 | |
| The total rare earth (TRE) amount | ?- | ?- | ?- | ?- | ?- | ??- | ?0.026 | ?0.020 | Maximum 0.050 |
| ?S | ?0.0020 | ?0.0012 | ?0.0007 | ?0.0012 | ?0.0008 | ??0.0010 | ?0.0010 | ?0.0022 | Maximum 0.0040 |
| ?4.4 *S | ?0.0044 | ?0.0088 | |||||||
| ?O | ?0.0020 | ?0.0010 | ??0.0015 | ?0.0020 | ??0.0020 | ?0.0020 | ?0.0025 | Maximum 0.0040 | |
| ?N | ??0.0010 | ?0.0010 | ??0.001 | ?0.0010 | ?0.0010 | ||||
| ?C | ?0.011 | ?0.009 | ?0.004 | ??0.013 | ?0.012 | ??0.009 | ?0.007 | ?0.016 | Maximum 0.05 |
| ?P | ?0.002 | ?0.002 | ?0.002 | ??0.002 | ?0.002 | ??0.002 | ?0.002 | ?0.003 | |
| ?Cr | ?0.03 | ?0.03 | ?0.03 | ??0.04 | ?0.04 | ??0.04 | ?0.05 | ?0.02 | |
| ?Mo | ?0.05 | ?0.09 | ?0.13 | ??0.10 | ?0.14 | ??0.05 | ?0.04 | ?0.08 | |
| ?Cu | ?0.06 | ?0.06 | ?0.04 | ??0.10 | ?0.05 | ??0.05 | ?0.05 | ?0.15 | |
| ?Co | ?0.04 | ?0.02 | ?0.01 | ??0.04 | ?0.02 | ??0.02 | ?0.02 | ?0.03 | |
| ?B | ?- | ?- | ?- | ??0.001 | ?0.001 | ??0.001 | ?0.001 | ||
As furnace charge T4392, T5405, T5406 and furnace charge E5407, add small amount of boron and can improve stampability.The content (weight %) of cerium is more than 4.4 times of sulfur content (weight %) in the furnace charge of the present invention (E5407 and E5405).
After fusing, carry out breaking down, hot rolling subsequently is into about 4 millimeters hot-rolled band, and through the final thickness of cold deformation to 1.0 subsequently millimeter.
In addition, the punching press diameter is 25.5 millimeters a round specimen.Use is until all furnace charges of E0545.Here use about 15 millimeters * 15 millimeters * 5 millimeters foundry goods, finish grind its surface by the founding specimen preparation.Clean all samples, a part of sample carries out annealing in process with 970 ℃/hour under hydrogen, be cooled in stove below 300 ℃ then.The second portion sample under hydrogen to carry out annealing in process in 1030 ℃/2 hours.In stove, be cooled to below 300 ℃ afterwards.All samples are carried out in short-term (2 days) weather test, wherein the temperature/humidity alternate cycles be 3 hours from 25 ℃ and 55% air humidity to 55 ℃ and 98% air humidity.In the glass dish that the single face of sample is placed, the bottom surface is shrouded under the crevice corrosion condition of aggravating like this.The results are shown in Table 5.
Table 5: weather result of the test
| Feed intake | Behind the weather resistance test that shortens: the sample/confession of the band hot spot piece sample sum of having a try | Explanation | |
| 970 ℃/6 hours | 1030 ℃/2 hours | ||
| T5405 | ????10/10 | ?????10/10 | There are a plurality of tangible points on the two sides of each sample |
| T5406 | ????10/10 | ?????10/10 | There are a plurality of tangible points on the two sides of each sample |
| E5407 | ????0/10 | ?????0/10 | |
| E0545 | ????0/1 | ||
In furnace charge E5407 of the present invention and E0545, do not find corrosion, and in two contrast furnace charge T5405 and T5406, find hot spot on two positions at each sample.
As mentioned above, the adding of strong like this deoxidier and sulfur elimination such as cerium since its product be retained in and influence magnetic property in the material.Astoundingly, the magnetic permeability that furnace charge E5407 of the present invention and E0545 demonstrate and the magnetic values of coercive field strength are in the conventional fluctuation range of the furnace charge that melts according to prior art, and be as shown in table 6.
Table 6: the magnetic values of furnace charge of the prior art (T) and furnace charge of the present invention (E), its under hydrogen with 1080 ℃/4 hours annealing in process with in stove, be cooled to and after 450 ℃, on the sample of 1 millimeters thick, measure.The composition of furnace charge sees Table 4.
| Workpiece material | Coercive field strength | Minimum magnetic permeability, T | Statistical value | |||||||
| Be called for short | Worker's piece number | ???Hc， ???A/m | When field intensity is H, A/m | ????μ4 | The μ maximum | |||||
| ???20 | ???50 | ???100 | ???300 | ???500 | ??4000 | |||||
| ??RNi?24 | ??1.3911 | ??＜24 | ???0.20 | ???0.45 | ???0.70 | ???0.90 | ???100 | ??1.18 | ||
| ??RNi?12 | ??1.3926 | ??＜12 | ???0.50 | ???0.90 | ???1.10 | ???1.25 | ???1.35 | ??1.45 | ||
| ??RNi?8 | ??1.3927 | ??＜8 | ???0.50 | ???0.90 | ???1.10 | ???1.25 | ???1.35 | ??1.45 | ||
| Feed intake | ||||||||||
| ??E5407 | ??4.2 | ???1.02 | ???1.12 | ???1.18 | ???1.31 | ???1.50 | ??1.56 | ??10200 | ??97800 | |
| ??E0545 | ??2.6 | ??11690 | ??133770 | |||||||
| ??T2536 | ??1.9 | ??8000 | ??179600 | |||||||
| ??T4392 | ??3.8 | ???1.07 | ???1.16 | ???1.22 | ???1.36 | ???1.44 | ??1.54 | ??5000 | ??154700 | |
| ??T5405 | ??2.5 | ???1.06 | ???1.14 | ???1.20 | ???1.32 | ???1.41 | ??1.57 | ??9200 | ??142100 | |
| ??T5406 | ??2.1 | ???1.06 | ???1.14 | ???1.20 | ???1.33 | ???1.42 | ??1.53 | ??10000 | ??158900 | |
| ??T5477 | ??2.76 | ???1.08 | ???1.17 | ???1.21 | ???1.34 | ???1.42 | ??1.53 | ??8200 | ??135100 | |
| ??T5488 | ??5.21 | ???1.09 | ???1.20 | ???1.35 | ???1.40 | ???1.46 | ??1.54 | ??2600 | ??99850 | |
Second embodiment is that observation has the performance of two kinds of furnace charges of the prior art when breaking down and hot rolling of the composition that provides in the table 7.
The main difference of these two kinds of furnace charges is content differences of rare earth metal.
Table 7
| Element | The limit | ||
| Feed intake | ?T0626 | ??T0624 | |
| ?Ni | ?36.2 | ??36.45 | |
| ?Mn | ?0.25 | ??0.26 | Maximum 0.5 |
| ?Si | ?0.20 | ??0.19 | Maximum 0.3 |
| ?Al | ?0.009 | ??0.009 | Maximum 0.010 |
| ?Mg | ?0.0030 | ??0.003 | Maximum 0.002 |
| ?Ca | Maximum 0.002 | ||
| ?Cer | ?0.029 | ??0.001 | |
| ?La | ?0.017 | ||
| ?Pr | ?0.002 | ||
| ?Nd | ?0.006 | ||
| The total rare earth (TRE) amount | ?0.054 | ??0.002 | Maximum 0.050 |
| ?S | ?0.002 | ??0.002 | Maximum 0.0040 |
| ?O | ?0.0050 | ??0.0020 | Maximum 0.0040 |
| ?N | ?0.0025 | ??0.0020 | |
| ?C | ?0.004 | ??0.009 | Maximum 0.05 |
| ?P | ?0.002 | ??0.002 | |
| ?Cr | ?0.04 | ??0.01 | |
| ?Mo | ?0.06 | ??0.06 | |
| ?Cu | ?0.05 | ??0.09 | |
| ?Co | ?0.05 | ??0.03 | |
| ?B | ?- | ??- |
The rare earth metal total content is that 0.054% furnace charge T0626 produces the crack when hot forming, and rolls ingot afterwards and become waste material.High like this rare earth metal content causes the thermal deformation deterioration.On the contrary, furnace charge T0624 can be rolled into billet and thickness is about 4 millimeters hot-rolled band.Because the chemical property of rare earth metal is similar, so among the present invention the total amount of rare earth metal cerium, lanthanum, praseodymium, neodymium is defined as maximum 0.05 weight %, to avoid the heat processing and forming problem.
Table 8 expression is according to the test of DIN50602 to the nonmetal inclusion content of different furnace charges among prior art (T) and the present invention (E).
Table 8
| Material | Press the percent purity of DIN 50602: maximum (technology M) | |||
| Feed intake | SS | ?OA | OS | ?OG |
| The limit | 0.1 or 1.1 | 2.2 or 3.2 or 4.2 | 5.2 or 6.2 or 7.2 | 8.2 or 9.2 |
| ?E5407 | Do not survey | ?2.1 | Do not survey | ?8.0 |
| ?E0545 | The same | ?2.2 | Do not survey | ?8.1 |
| ?T4392 | The same | ?2.2 | Do not survey | ?8.0 |
| ?T5405 | The same | ?2.0 | Do not survey | ?8.0 |
| ?T5406 | The same | ?2.2 | Do not survey | ?8.0 |
| ?T5477 | The same | ?2.1 | Do not survey | ?8.1 |
| ?T5488 | The same | ?2.0 | Do not survey | ?8.0 |
| ?T2536 | The same | ?2.7 | Do not survey | Do not survey |
The greatest measure of the oxide inclusions of furnace charge T2536 in wire-form is 2.7 (method M).This numerical value is too high when this furnace charge is used as the material of relay element.It will cause the wearing and tearing of relay contact surface, consequently cause the relay function loss.Therefore, the content of following restriction nonmetal inclusion according to the present invention:
According to DIN50602, form among the SS at wire rod, the greatest measure of sulphide inculsion is to be less than or equal to 0.1 or 1.1, according to DIN50602, in the fusing form, the greatest measure of oxide inclusions OA (aluminium oxide) is less than 2.2 or 3.2 or 4.2, according to DIN50602, in wire-form, the greatest measure of oxide inclusions OS (silicate) is less than 5.2 or 6.2 or 7.2, and according to DIN50602, in balled form, the greatest measure of oxide inclusions OG is less than 8.2 or 9.2.All other furnace charges of enumerating in table 8 all satisfy the content condition of nonmetal inclusion.
Claims (15)
1. soft magnet-nickel-alloy, it has the nickel of 35 to 65 weight % and one or more rare earth metal ceriums, lanthanum, praseodymium, neodymium and by being mingled with that melting is introduced, wherein, the total amount of rare earth metal is 0.003 to 0.05 weight %.
2. the magnetically soft alloy of claim 1 is characterized in that, this alloy comprises the cerium of the highest 0.05 weight %.
3. claim 1 or 2 magnetically soft alloy, it is characterized in that, this alloy comprises as manganese deoxidation and/or sulfur-removing additives, the highest 0.5 weight %, silicon and the blend of the highest 0.5 weight %, blend is the magnesium of the highest 0.002 weight %, the calcium of the highest 0.002 weight %, the aluminium of the highest 0.010 weight %, the sulphur of the highest 0.004 weight %, the oxygen of the highest 0.004 weight %, and other trace is mingled with under the melting condition.
4. the magnetically soft alloy of one of claim 1 to 3 is characterized in that, when representing with weight %, the total content of rare earth metal is 4.4 times of sulfur content at least.
5. the magnetically soft alloy of one of claim 1 to 4 is characterized in that, alloy comprises the boron that is at most 0.002 weight %.
6. the method for the soft magnetism Fe-Ni alloy of a melting claim 1 to 5 is characterized in that, this alloy of fusing in the arc furnace that opens wide is handled by steel ladle metallurgy and/or VOD-subsequently, carries out deoxidation, desulfurization and the degassing.
7. the method for claim 6 is characterized in that, adjusts following parameter in the alloy of fusing:
-in wire rod, the greatest measure of sulphide inculsion is less than 0.1 or 1.1,
-in the fusing form, the greatest measure of oxide inclusions OA (aluminium oxide) is less than 2.2
Or 3.2 or 4.2
-in wire rod, the greatest measure of oxide inclusions OS (silicate) is less than 5.2
Or 6.2 or 7.2,
-in balled form, the greatest measure of oxide inclusions OG be less than 8.2 or
9.2。
8. claim 6 or 7 method is characterized in that, are being prepared element by this alloy and at 800 to 1150 ℃ down after the annealing, the coercive field strength that this element obtains is lower than 8A/m.
9. the purposes of the soft magnetism Fe-Ni alloy of one of claim 1 to 8, it is as the relay element material.
10. the purposes of the soft magnetism Fe-Ni alloy of one of claim 1 to 8, it is as the bonnet of magnet valve and the material of valve body.
11. the purposes of the soft magnetism Fe-Ni alloy of one of claim 1 to 8, it is as the yoke of idle magnet and electromagnet or the material of pole piece or pole shoe or utmost point usefulness silicon steel sheet and armature.
12. the purposes of the soft magnetism Fe-Ni alloy of one of claim 1 to 8, it is as magnetic bobbin core and the rotor of stator and motor and the material of stator of stepping motor.
13. the purposes of the soft magnetism Fe-Ni alloy of one of claim 1 to 8, it is as transducer, location transmitter and the molding of location recipient and the material of stamping parts.
14. the purposes of the soft magnetism Fe-Ni alloy of one of claim 1 to 8, it is as magnetic head and magnetic head shielding material.
15. the purposes of the soft magnetism Fe-Ni alloy of one of claim 1 to 8, it is as shielding material.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19803598.5 | 1998-01-30 | ||
| DE19803598A DE19803598C1 (en) | 1998-01-30 | 1998-01-30 | Soft magnetic iron-nickel alloy for relay armatures and yokes |
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| Publication Number | Publication Date |
|---|---|
| CN1275238A true CN1275238A (en) | 2000-11-29 |
| CN1163915C CN1163915C (en) | 2004-08-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB998014117A Expired - Lifetime CN1163915C (en) | 1998-01-30 | 1999-01-08 | Soft magnetic nickel-iron aloy with low coercive field strength, high permeability and improved resistance to corrosion |
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| Country | Link |
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| EP (1) | EP1051714B2 (en) |
| JP (2) | JP2002502118A (en) |
| KR (1) | KR100384768B1 (en) |
| CN (1) | CN1163915C (en) |
| AT (1) | ATE211297T1 (en) |
| CZ (1) | CZ301345B6 (en) |
| DE (2) | DE19803598C1 (en) |
| ES (1) | ES2169597T5 (en) |
| HU (1) | HU222469B1 (en) |
| PL (1) | PL192145B1 (en) |
| PT (1) | PT1051714E (en) |
| SK (1) | SK285293B6 (en) |
| TR (1) | TR200002190T2 (en) |
| TW (1) | TW418406B (en) |
| WO (1) | WO1999039358A1 (en) |
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| CN112176222A (en) * | 2020-10-30 | 2021-01-05 | 东北大学 | Ce-containing Fe-Ni permalloy material and preparation method thereof |
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| CN116377284A (en) * | 2023-03-08 | 2023-07-04 | 北京北冶功能材料有限公司 | Iron-nickel-based soft magnetic alloy foil and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| PL341568A1 (en) | 2001-04-23 |
| SK10832000A3 (en) | 2001-03-12 |
| KR20010040436A (en) | 2001-05-15 |
| CZ301345B6 (en) | 2010-01-20 |
| JP2002502118A (en) | 2002-01-22 |
| HUP0003646A3 (en) | 2001-04-28 |
| ATE211297T1 (en) | 2002-01-15 |
| SK285293B6 (en) | 2006-10-05 |
| DE59900588D1 (en) | 2002-01-31 |
| KR100384768B1 (en) | 2003-06-18 |
| TR200002190T2 (en) | 2000-11-21 |
| EP1051714B1 (en) | 2001-12-19 |
| JP2007314885A (en) | 2007-12-06 |
| CN1163915C (en) | 2004-08-25 |
| TW418406B (en) | 2001-01-11 |
| HUP0003646A2 (en) | 2001-02-28 |
| PT1051714E (en) | 2002-06-28 |
| PL192145B1 (en) | 2006-09-29 |
| CZ20002616A3 (en) | 2000-11-15 |
| HU222469B1 (en) | 2003-07-28 |
| ES2169597T5 (en) | 2008-11-01 |
| DE19803598C1 (en) | 1999-04-29 |
| ES2169597T3 (en) | 2002-07-01 |
| EP1051714B2 (en) | 2008-04-30 |
| WO1999039358A1 (en) | 1999-08-05 |
| EP1051714A1 (en) | 2000-11-15 |
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