TW418406B - Soft magnetic nickel-iron-alloy with less coercive field strength, high permeability and improved corrosion resistance - Google Patents

Abstract

A soft magnetic Iron Nickel alloy with a Nickel content of 35-65 mass % and one or more of Rare Earths Cerium, Lanthanum, Praseodym or Neodym as well as impurities caused by melting is proposed where the sum of Rare Earths lies between 0.003 and 0.05 mass %.

Description

Printed by Shelley Consumer Cooperative, Shaoyang Standard Bureau, Ministry of Economic Affairs A7 ----------- B7 V. Description of Invention (i) '' --- This invention relates to soft magnetic nickel-iron alloys. & Carl Heck, Hutig Verlag, and Heidelberg, "Magnetic Materials and Their Technical Applications," book '1975, p. 349, and it has since been known that soft magnetic materials are used for armature and yoke in relays The most important requirement of a material is a high saturation flux density to achieve, at a lower energy, a large magnetic cohesion, a high magnetic permeability with a small magnetic field, and a high degree of permeability. A low excitation current and a high flux density can be generated in the air gap, and therefore a large attractive force is exerted on the armature. The lower coercive field strength 'allows the relay to reduce the excitation current' It is possible to easily open the system. In addition to the magnetic requirements, 'even in climate change, the requirement for corrosion resistance exists in the material of a relay', because a relay with the correct function is necessary in every climate. This one Requirements for materials that are not sufficiently resistant to corrosion can be accomplished by simply applying an additional corrosion resistant layer to the final product. The contact surfaces of the armature and yoke must have There is the least possible gap to achieve a high permeability of the magnetic current that chokes outside the armature < When the release current of the relay is changed, these should not be damaged by the armature switch β German Industrial Standard DIN 17405 "Soft magnetic materials for DC relays" describes the requirements in a relay material. Table 1 below shows excerpts from the DIN 17405. DIN 17745 "refined alloys from nickel and iron" describes Ni48 alloys (material numbers 1_3926 and 13927) ) As used for RNi 12 and RNi 8 (Table 2) * 4 * This paper size is applicable to China Shipping 1 National Standard (CNS) A4 specification (210X297). Packing-(Please read the note of back gas before filling out This page) Order r 4 18 4 0 6- A7 —_______ B7 V. Description of the starting material of type (2). Ni 35 nickel alloy (material number 13911) is used as the starting material of type Rni 24. In molten nickel -Iron-alloys, closer to the desired alloy composition, and further deoxidizing- and / or desulfurizing elements such as manganese, silicon, and aluminum are needed. In addition, when these alloys are cost-effective, they use general steelmaking technology To be made 'some oxygen, sulfur, squat, The minimum mixture of calcium, calcium, magnesium, chromium, molybdenum, steel, and knots is unavoidable. Table 1: Relay materials according to DIN 17405 · W ^ · 4-head magnetic minimum magnetic value characteristics combined field strength gold component abbreviation material maximum HC field strength H, A / m weight% No. Α / ιη 3

Rni 24 1-3911 24 Rni 12 1-3926 12 Rni 8 1-3927 8 Rni 5 2-4596 5 5 0 0 5 4 9 9 6 ο ο ο ο ο ο ο 2 5 5 5 ο ο ο ο 40 0 8 5 5 5 0 14 4 7 11 1 Λ 0 5 5 0 3 3 1 * 0 5 5 9 2 2 oil ο ο G ο 7 117 • 1 · 1 · 1 · 1 Ν Ν Ν Ν 6 0 0 0 3 5 5 7 Printed by Shellfish Consumer Cooperative, Central Bureau of Standards, Ministry of Economic Affairs

Rni 2 2.4595 2_ 5 0.50 0.65 0.70 0.75

Ca, C l, _ Mo Table 2 taken from DIN 17745 abbreviated material number composition, weight% alloy composition allowable mixture Ni 48 1-3926 Ni minimum 46, Fe 49 to 53 Co.05, Mn 0.5, Si 0.3 Ni 36 1-3911 About 36 Melting in an open electric arc furnace with general steelmaking technology, followed by deoxidation, desulfurization, and degassing in known metallurgical systems. After that, the initial rolling and subsequent hot drawing and rolling to 4mm, and the subsequent cold deformation to the final 'thickness', if necessary, can be accompanied by moderate annealing. According to the example described in DE 1 96125 56 A1, printed with carbon and paper standards (CNS) A4 specification (2 丨 0X297 mm) 418406 Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs Preparation A7 B7 5. Description of the invention (3) Mixture of nitrogen, oxygen, and sulfur 'and mixing with non-metallic inclusions, magnetic properties will be degraded. Non-metallic inclusions are due to the deoxidation and / or desulfurization of the smelt necessary before pouring. Relying on deoxidizing and / or desulfurizing agents, there are oxides such as calcium, manganese or aluminum. Therefore, in order to avoid difficulties, according to the conventional technology, the soft magnetic materials with the highest requirements and the selected clean input materials are manufactured by vacuum technology 'as stated in DE-A 3910147 and DE-c 1259367. . «. Another possibility known from the literature is the extremely expensive method of remelting the electrolyzed slag in a true or shielded atmosphere, as described in DE-A 4105507, in vacuum / shielded gas. L pre-melted. The task existing in the foundation of the present invention is to melt a soft magnetic nickel-iron alloy, which is sufficient to meet the described magnetic properties in terms of resistance to corrosion and wear. This problem is overcome by a soft magnetic iron-nickel-alloy with a nickel content of 35 to 65%. And one or more rare earth metals and impurities produced by melting. The rare earth metal is planed, lanthanum, rhenium or Convergence, and the total content of rare earth metal is between 0.003 and 0.005% by weight. Another advantageous development result of the present invention can be known from the appended items of the scope of the combined patent application. The alloy system according to the invention is advantageously produced by steelmaking technology, that is, by melting in an open electric arc furnace, followed by subsequent deoxidation, desulfurization, and degassing metallurgy. After that, it is lightly rolled to a thickness of about 4mm by an initial rolling and hot drawing, and then cold-deformed to a final slab thickness, and if necessary, moderate annealing is used to adjust the required hardness for use. For making articles from the slats.

The articles are manufactured from the alloy and the article is between 800 ° C and the paper standard is applicable to the National Standard (CNS) M specification (2 丨 〇χ297 mm). Please read the notes on the back first ^ Write this page again] Installation.-Order A7 B7 Printed by the Central Bureau of Standards of the Ministry of Economic Affairs and Consumer Cooperatives. V. Description of Invention (4) to 1150 ° C After annealing at a temperature below 8A / m These items of coercive magnetic field strength are achieved. Preferred examples of the application of the alloy according to the invention are relay parts such as yokes and armature. From a slab made with steelmaking technology to a thickness of 1.2nun, flat samples were cut, cleaned, and subjected to an annealing treatment under hydrogen and oxygen at 1.08 ° C / 4 hours, and thereafter Cooled in the furnace to 300 ° C. These samples were subjected to the environmental test described in DIN 50017 'The environmental test is 28 cycles, each cycle is at 551/90 to 96 humidity 8 hours and 16 hours at 25 and 95 to 99% humidity. Alloys with 36% to 81% by weight nickel content and some additives such as chromium, copper, and / or molybdenum have been studied (see Table 3) . Alloys with a nickel content of less than 55 weights! ¾ Ni alloys with a nickel content of more than 75% by weight clearly show a more corrosive appearance on the surface after the end of the climate change test (B. Gehrmann »H. Hattendorf > A. Kolb Telleps »W. Kramer j Materials and Corrosion, 48 535-541, 1997), and without the additional anti-corrosion control methods, it cannot meet the above-mentioned requirements for the corrosion resistance of a relay material 》 Coercive field strength as stated in Table 3 (known techniques) Shows that the magnetic properties required in accordance with DIN 17405 have been achieved in contrast-Table 3 Composition, He * A / m Max He * from DNI17405. Alloy iron nickel molybdenum chromium copper rhenium silicon Fe-36Ni 62.90 36,50 0, 01 0.03 0,03 0,27 0.18 12 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, Q) 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- BCr 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 (CMS) A4 specification (210X297mm) Please read the first. Note

I Page Order 5. Description of the Invention (5) A7 B7 Fe-50Ni 48t 85 50,70 0,01 M4 0,03 0,21 0,05 3,5 8 Fe-55Ni 43,70 55,45 0,0B 0 , 06 0,05 0.42 0,14 12,5 Fe-76Mi Cu (> 16,05 75,95 MO 2,00 4 96, 0,60 0,22 0,87 2,5 Fe-77Ni- TifNb 14 , 80 77,30 0 > 01 0,10 4,50 0,49 0,24 2,4 2,5 " Pe-77Ni- No ^ cu 13,85 77,15 3,45 α io 447 0 »53 0,33 0,85 2,5 »Ni-Mo 13,95 80,10 475 0,05 ot〇g 0,50 0,33 0,44 2,5 Fe-81Ni-lfo 12.45», 50 5, 27 0.03 0,05 0,43 0.13 1,23 2,5 After changing the climate test, the sulfur system was found in the corrosion of these samples by REM / energy dispersive X-ray analysis (REM / EDX) β (please first Read the notes on the back of the page and fill in this page again.) The improvement of the corrosion behavior of the present invention was accidentally caused by the easily corroded belt I. There is absolutely no nickel with a content of 35 to 65% by weight! Desulfurization is achieved. Preferably, this is done from a mixture of very similar chemical properties of rare earth metals and / or gangues and / or osmosis or convergence (Mischmetal). To ensure the stabilization of all sulfur, it is sufficient The rare earth metal atom must For example, if it is caused to form cesium sulfide with the largest planing amount CeS, the situation is when the planing atoms are present in the alloy more than the sulfur atoms. Accordingly, the content of cesium atoms (% by weight) ) Must be at least greater than the sulfur atom content (% by weight) of about 4.4 factors in order to achieve complete stabilization of sulfur via cyanide. The same conditions are valid for other rare earth metals lanthanum, scandium and / or titanium and the total amount of rare earth metals. Economy The Ministry of Central Standards Bureau ’s consumer goods cooperation printed as above, the addition of such strong deoxidizing and desulfurizing agents such as planing can reduce the magnetic properties through the residual reaction products in the material. Surprisingly, the addition of rare earths can be so The ground is proportional so that the permeability and coercive magnetic field strength fall within the general range of variation of fillers in accordance with conventional techniques. It is known that deoxygenation residues emerge from the contact surface of the relay, and Left between these surfaces and through them (oxidation residues) for higher hardness, and during the large switching process of the relay, this paper can be used in accordance with national standards CNS) A4 ^ # · (210X297 mm) A7 B7 1 8Λ 〇6 V. described invention (6) via the contact to damage to such a fine surface polishing. Therefore, in accordance with DIN 50602 (method M), the material of these relays should have a minimal amount of non-metals. Therefore, the maximum value of sulfide inclusions in linear SS should be less than 0.1 or less than 1.1, and the maximum value of oxide inclusions in cracked OA (alumina) should be less than 2.2, or Less than 3.2, or less than 4.2, the oxide content of the linear OS (Si 1 icate) should be less than 5.2, or less than 6.2, or less than 7.2, and spherical OG oxide inclusions should be »* · less than 8.2, or less than 9.2. For example, a nickel alloy with about 48% nickel and a small amount of manganese and silicon is melted in a 30 T electric arc furnace using steel mill technology (fillers E5407 and E0545), and is similar to a rare earth metal This corresponds to conventional fillers (fillers T4392, T5405 and T5406). Table 4 shows the correct composition. Table 4 Composition of fillers according to the conventional (T) and fillers according to the present invention CE) All data are% by weight (please read the note on the back «· Matters and then ^ ': write this page). Order _ rr : Printed Elements of Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs, Printed Elementary Knowledge Table, Inventive Limit Value Correction T2536 T5477 75488 T4392 T4505 T540G E540? E0545 Ν1 47,45 47,5 47,95 47.7 47,45 47,9 47,65 47.65 Ηα 0,45 0,40 0,36 0.38 0,40 0,38 0,39 0,41 0,5 Si 0,19 0.19 0,22 0,20 0,14 0,15 0,14 0,22 0,3 A1 0,005 0,005 0,007 0,009 0,007 0,008 0,005 0,005 0,010 Ms 0.001 OtOOQ3 0,0008 0,0001 0.0001 0,0002 0,0006 0,0008 0,002 C & 0,0004 0,0004 0,0003 0,0001 0,0002 0,0002 0,0003 Maximum M02 Cter------0,014 0,011 la------0/008 0,005 Rr-----0,001 0,001 Nd-----i 003 0,003 Metal Aggregate — _ 0,026 0,020 up to 0,050 S 0f 0020 0,0012 0,0007 0.0012 0. 0008 OJOIO 0,0010 0,0022 up to 0,0040 4,4 = * S 0,0044 0,0088 0 0,0020 0 , 0010 0,0015 0. oozo 0,0020 0,0020 0,0025 most 0,00 sister N 0,0010 0,0010 0,001 0,0010 oVooio C 0,011 o, o〇g 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 0,00 04 0,04 0,04 0,05 0,02 Uo 0.05 0,0,13 0,10 0,14 0,05 0,04 0t08 Cu 0t06 0,06 0,04 0,10 0,05 0, 05 0,05 U5 Co 0J2 0,01 (K04 0,02 0,02 0,02 0r03 B---0,001 a ooi 0,001 0,001 S- This paper size is applicable to the China National Standard (CNS) Α4 specification (210X297 mm) Printed by the Consumer Cooperatives of the China National Standards Bureau of the Ministry of Economic Affairs 418406 a7 _B7 V. Description of the invention (7) A small amount of boron can be added to improve the subsequent impact (such as in the fillers T4392, T5405, T5406, and E5407) According to the present invention, the cesium content (wt%) in the fillers E5407 and E0545 is greater than the sulfur content (wt%) by more than about 4.4 factors. After melting, the initial rolling and subsequent heat extraction consume The final thickness of the milk to about 4mm, and then a cold deformation to 1. Omm was connected. Thus, a circular sample having a diameter of 25.5 mm was punched out. This is valid for all fillers, up to E0545. Here, a section of about 1 SmniXl 5mmX5mm from a patterned sample is used, and its surface area is precisely ground. All samples were cleaned, and some samples were annealed at 970 ° C / 6 hours in an argon atmosphere, and then cooled in a furnace to below 300 ° C. All samples were subjected to a 2-day shortened climate test. The test was performed at a temperature / humidity change of 25 ° C and 55% humidity to 551 and 98% humidity regularly over a period of 3 hours. These samples were placed flat in a glass pan, so that the worsening of cracking at the bottom ' was dominant. Table 5 shows the results of the tests. Table 5 Environmental test results. Filler in a short environmental test: the total number of samples with corrosion / tested samples 970 ^ C / 6hrs 1030eC / 2hrs HyunT 5405 10/10 10/10 Each side has clearer spots Τ5406 10/10 10/10 There are clear spots on both sides of each sample Ε5407 0/10 0/10 Ε0545 ο / ι According to the present invention, no corrosion was found in the fillers E5407 and E0545, but in the two comparative fillers In T5405 and T5406, corrosion spots were found on both sides of each sample. _ -10, This paper is again applicable to China National Standard ^ (CNS) A4 (210 > < 297 public directors) — --------- install — (please read the note on the back *. Again 4; write this page) Order 4 η 418Α Π6 Α7 B7 V. Description of the invention (8) Such a strong deoxidizing and desulfurizing agent such as a planer, as mentioned above, can reduce the magnetic properties through the reaction products remaining on the material . Unexpectedly, the magnetic permeability and the coercive magnetic field strength ', as shown in the fillers E5407 and E0545 of the present invention, fall within the general variation range of the filler (which is melted according to the conventional knowledge), as shown in Table 6. . · Table 6: Magnetic value (τ) of the conventional filler and magnetic value (E) of the filler according to the present invention 'Tested on a sample of 1 mm thickness, which was subjected to 1080 ° C / 4 hours in a hydrogen environment Annealing and I—Cooling in the Market 'to 45Q ° C «Table 4 shows the composition of the filler material, the material number, the minimum coercive magnetic field, the minimum magnetic induction, τ intensity He, A / m in a field intensity of B, A / m 20 50 100 300 500 4000 Static value H4 max Rnil24 1-3911 u 0,20 0,45 0,70 0,90 1,00 1J8 Rnil2 L3Q26 12 0,50 〇, 〇uo 1,25 1.35 1,45 Rni8 L3927 8 0 , 50 0t90 1.10 1,25 1,35 1.45 mm -------- E5407 4,2 1,02 1,12 1J8 131 h 50 1,56 10200 97800 E0545 2.6 11690 133770 T2536 U 8000 179600 Τ43Θ2 3.8 1,07 U6 1,22 136 1,44 1,54 SOQO 154700 T5405 2,5 L06 1,14 L20 1,32 1,41 1,57 9200 142 100 T5477 2.76 1,08 1,17 1,21 1,34 1,42 lt53 8200 135100 T548S 5,21 1.P9 1,20 1,35 1.40 1,46 1,54 2600 99850---Note binding r Printed by the Consumer Cooperative of the Central Sample Bureau of the Ministry of Economic Affairs

The composition of the two fillers according to the present invention as shown in Table 2 is shown in Table 7 * The two compositions are considered in terms of the properties of Hatsune L and the hot drawing mill β. These two fillers are only substantially different through Content of rare earth metal varies

TtitrlNiMasiAlHeca T0626 T0624 36,2 36,45 0,25 0,2Θ max 0 * 5 0,20 0,19 max 0,3 0.009 0,009 max M10 0,0030 0 * 003 max 0,002 max 0,002--11- paper size Applicable to China National Standard (CNS) A4 specification (210X297 mm) 6 o 48 4H4

A B7 Ming i said cerLaRrNdM s ο N c pcrMOcuco Mingfa # Α 9 291702065402050025040204060505 ooooooggooooGO ο · ο * Team 0 'Team o' 0 * o 'ο, Team o' ο · 0,001 0,002 Max 0 · 〇Μ) 0,002 Max. , _ 0,0020 max. 0, 〇ΜΟ 0.0 coffee 0,009 max. M5 0 (002 0, Q1 0t 06 0f09 0,03 with the total rare earth metal 0. 054% spent filler T0626 formed cracks during the thermal deformation process and the initial rolling The obsolete / so high rare earth metal content results in poor thermal deformation properties. On the contrary, the filler T0624 is rolled to have a thickness of about 4 mm in the preliminary rolling and hot draw rolling. Because the chemical properties of the rare earth metals are similar, according to In the present invention, the sum of the contents of the rare earth metal planer, lanthanum, thorium, and “is limited to a maximum of 0.05% by weight to avoid a problem of thermal deformation. Table 8 shows the conventional (T) and the present invention (E) Based on the results of non-metallic inclusions of different fillers according to DIN 50602》 ::, Λ — —I — ---------- pack-(Please read the precautions on the back # · 土 写 本Page) Printed by the Central Bureau of Standards of the Ministry of Economy Cleanliness according to DIN50602: Maximum value (M method) Packing SS OA OS 桎 Limit value 0.1 or 1.1 2.2 or 3.2 or 4.2 5 · 2 or 8.2 or 7.2 E5407 Κ.Β. 2.1 KB E0545 LB, 2.2 LB. T4392 LK 2.2 LB. T5405 LB. 2.0 LB. T5406 Ka 2Λ LB. T5477 KB 2.1 Ka T5488 KR 2.0 Ί2536 ΚΛ 2.7 KB ^ OIOOOIODU «= & 8-00 * 8- & 8-8-8- £ · Filler T2536 has a maximum of _27 in a linear oxide inclusion. (Method M). This value is used as a wheel for the filler for relay article materials. -12 · Chinese paper standards (CNS) apply to each paper size A4 specification (210X297 mm) 4184 ^ 6 A7 B7 V. Description of the invention (10) The input system is too large. It causes wear and tear on the relay and further damages the ability of the relay. Therefore, according to the present invention, the non-metallic The content is limited by the following. According to DIN 50602, the maximum value of sulfide inclusions in linear SS is less than 0.1 or less than 1.1. According to DIN 50602, the oxidation of cracked OA (alumina) The maximum value of inclusions is less than 2.2 or less than 3.2 or less than 4 .. 2 according to DIN 5 0602, the maximum value of the linear oxide (Silicate) oxide inclusions is less than 5.2 or less than 6.2 or 7.2 'according to DIN 50602' the maximum value of the spherical oxide inclusions is less than 8.2 Or less than 9.2. All other fillers listed in Table 8 meet the conditions for non-metallic inclusion content. Please read the note ^ of ft- before binding the printing of the Consumers' Cooperative of the Central Economic and Technical Bureau of the Ministry of Economic Affairs of the People's Republic of China.

Claims (1)

418406 A8 B6 C8 D8 Employee Cooperative Cooperative of the Central Bureau of Samples of the Ministry of Economic Affairs System 6. Application for Patents 1. A soft magnetic iron-nickel-alloy with a nickel content of 35 to 65% by weight and one or more rare earths Metal, the rare earth metal is cesium, lanthanum, rubidium and thorium, and also has impurities generated due to the molten state, wherein the sum of the rare earth metals falls between 003 and 0.05% by weight. 2. The soft magnetic iron-nickel-alloy as described in the first item of the patent application scope, characterized in that the alloy contains a maximum content of 0.05 wt% absolute 4 f 3. The soft magnetic iron as the first item of the patent application scope -A nickel-alloy, characterized in that the alloy contains, as deoxidizing and / or desulfurizing additives, a maximum of 0.5% by weight manganese, a maximum of 0.5% by weight silicon, and a maximum of 0.00%. 2% by weight of magnesium, 0.002% by weight of calcium, o.oio% by weight of aluminum, 0.004% by weight of sulfur and 0.004% by weight of oxygen, and a small amount of other mixtures due to melting. 4. The soft magnetic iron-nickel-alloy according to item 1 of the patent application range is characterized in that the sum of the rare earth metal content (wt%) is at least 4.4 times higher than the sulfur content (wt%). 5. The soft magnetic iron-nickel-alloy according to item 1 of the application, characterized in that the alloy contains up to 0.002% by weight of boron. 6. —A method for melting soft magnetic iron as described in item 1 of the scope of patent application, characterized in that the melting of the alloy in the open-arc furnace occurs afterwards for deoxidation, desulfurization and Degassing in the package metallurgy. 7. The method of claim 6 in the scope of patent application, characterized in that the following parameters of the molten alloy are adjusted to: --- the maximum value of the linear sulfide inclusions is less than 0.1, or It is lower than 1.1, -14- The paper size is quickly used in China National Standard (CNS) A4 specification (210X297 mm) ------- II ---------- ΐτ ------ J ------ '* {Please read the precautions on the back before filling out this page) Age---I--f 418406 AS B8 C8 D8 VI. Application scope of patents----rupture OA (oxidation The maximum value of oxide content of aluminum) is less than 2.2 'or less than 3.2, or less than 4.2, and the maximum value of oxide content of linear OS (silicon oxide) is less than 5.2, or Below 6.2, or below 7.2, the maximum value of the spherical 0G oxide inclusion is below 8.2, or below 9.2. The method according to item 6 of the patent application, which is characterized by a coercive magnetic field strength of less than 8 A / m after the articles are manufactured from the alloy and the articles are annealed at a temperature between 800t and 1150 ° C. It has been achieved "/ 9.—A kind of soft magnetic iron · nickel · alloy application such as the scope of patent application No.1, which is used as a relay material" (Please read the precautions on the back before filling this page) Order η , Printed by the Bayer Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs-15 · This paper size applies to Chinese national standards (CNS > Α4 size (210X297 mm)