阅读说明：本技术 合金和用于制备磁芯的方法 (Alloy and method for producing a magnetic core ) 是由 吉塞赫尔·赫择 维多利亚·布丁斯克 克里斯缇安·波拉克 于 2020-03-02 设计创作，主要内容包括：提供合金,由式Fe<Sub>a</Sub>Co<Sub>b</Sub>Ni<Sub>c</Sub>Cu<Sub>d</Sub>M<Sub>e</Sub>Si<Sub>f</Sub>B<Sub>g</Sub>X<Sub>h</Sub>表示,M是元素V、Nb、Ta、Ti、Mo、W、Zr、Cr、Mn和Hf中的至少一种,X指杂质及可选的元素P、Ge和C,a、b、c、d、e、f、g、h按原子％计且满足条件：0≤b≤40≤c<40.5≤d≤22.5≤e≤3.514.5≤f≤166≤g≤7h<0.51≤(b+c)≤4.5a+b+c+d+e+f+g＝100。合金具有至少50体积％的晶粒的平均尺寸小于100nm的纳米晶组织,≤1ppm的饱和磁致伸缩|λ<Sub>s</Sub>|、优选|λ<Sub>s</Sub>|≤0.5ppm,拥有中央线性部分的滞后回线,10000至15000、优选10000至12000的磁导率μ。(Providing an alloy of formula Fe a Co b Ni c Cu d M e Si f B g X h In which M is at least one of the elements V, Nb, Ta, Ti, Mo, W, Zr, Cr, Mn and Hf, X denotes impurities and optionally P, Ge and C, a, b, C, d, e, f, g, h are in atomic% and satisfy the condition: b is more than or equal to 0 and less than or equal to 40 and c<40.5≤d≤22.5≤e≤3.514.5≤f≤166≤g≤7h<0.51 ≦ (b + c) ≦ 4.5a + b + c + d + e + f + g — 100. The alloy has a nanocrystalline structure with at least 50% by volume of grains having an average size of less than 100nm, a saturation magnetostriction lambda of less than or equal to 1ppm s I, preferably lambda s A hysteresis loop with a central linear part, | ≦ 0.5ppm, a permeability μ of 10000 to 15000, preferably 10000 to 12000.)

1. An alloy of the formula Fe_aCo_bNi_cCu_dM_eSi_fB_gX_hWherein M is at least one of the elements V, Nb, Ta, Ti, Mo, W, Zr, Cr, Mn and Hf, a, b, C, d, e, f, g are in atomic%, X indicates impurities and optionally elements P, Ge and C, and a, b, C, d, e, f, g, h satisfy the following condition:

0≤b≤4

0≤c<4

0.5≤d≤2

2.5≤e≤3.5

14.5≤f≤16

6≤g≤7

h<0.5

1≤(b+c)≤4.5

wherein a + b + c + d + e + f + g is 100, and said alloy

Having a nanocrystalline structure in which at least 50% by volume of the grains have an average size of less than 100nm,

has a saturated magnetostriction lambda of less than or equal to 1ppm_sI, preferably | λ_s|≤0.5ppm，

Having a hysteresis loop with a central linear portion,

has a magnetic permeability mu of 10000 to 15000, preferably 10000 to 12000, and

has the advantages of<Remanence ratio B of 1.5%_r/B_s。

2. The alloy of claim 1, wherein 0.2 ≦ c <4, preferably 0.5 ≦ c ≦ 4, preferably 0.2 ≦ c ≦ 3, preferably 0.5 ≦ c ≦ 3.

3. The alloy of claim 1 or claim 2, wherein 0.2 ≦ b <4, preferably 0.5 ≦ b ≦ 4, preferably 0.2 ≦ b ≦ 3, preferably 0.5 ≦ c ≦ 3.

4. The alloy of any one of the preceding claims, further having a saturation induction greater than 1.0T.

5. The alloy of any one of the preceding claims, further having<Coercive field strength H of 1A/m_c。

6. Alloy according to any one of the preceding claims, further having an anisotropy field H of ≥ 60A/m, preferably ≥ 70A/m_k。

7. The alloy according to any one of the preceding claims, wherein X is C and h < 0.5.

8. An alloy according to any one of the preceding claims, wherein at least one element of the group Nb, Ta and Mo is present as M, wherein 2.5< e < 3.5.

9. An alloy according to any one of the preceding claims wherein Nb may be replaced entirely by Ta and up to 0.06 at% may be replaced by Mo.

10. The alloy of any one of the preceding claims, wherein 0.5< b ≦ 3 and 0.5< c ≦ 3 and 1 ≦ (b + c) ≦ 4.5.

11. An alloy according to any one of the preceding claims having a permeability of 11000 to 14000.

12. Magnetic core having an alloy according to any of the preceding claims 1 to 11.

13. The magnetic core according to claim 12, in the form of an endless belt core wound from a tape having a thickness of less than 50 μ ι η, preferably less than 25 μ ι η.

14. A method for preparing the magnetic core of claim 12 or claim 13, the method comprising:

winding a ribbon made of an amorphous alloy into an endless ribbon core, said alloy being of the formula Fe_aCo_bNi_cCu_dM_eSi_fB_gX_hWherein M is at least one of the elements V, Nb, Ta, Ti, Mo, W, Zr, Cr, Mn and Hf, a, b, C, d, e, f, g are in atomic%, X indicates impurities and optionally elements P, Ge and C, and a, b, C, d, e, f, g, h satisfy the following condition:

0≤b≤4

0≤c<4

0.5≤d≤2

2.5≤e≤3.5

14.5≤f≤16

6≤g≤7

h<0.5

1≤(b+c)≤4.5

wherein a + b + c + d + e + f + g is 100,

heat treating the endless belt core under application of a magnetic field of from 80kA/m to 200kA/m across the belt length and in five stages, wherein

In phase 1 over a time point t₀Until a time t₁Is heated from room temperature to T₁Wherein T is more than or equal to 300 DEG C₁T is less than or equal to 500 DEG C₁-t₀Is 0.5h to 2h,

in phase 2 over a time point t₁Until a time t₂From T₁Heating to T₂Wherein T is more than or equal to 400 DEG C₂T is less than or equal to 600 DEG C₂-t₁Is 0.5h to 6h,

in phase 3 over a time point t₂Until a time t₃From T₂Heating to T₃Wherein T is more than or equal to 400 DEG C₃T is less than or equal to 650 DEG C₃-t₂Is in the range of 0h to 1h,

in phase 4 at the slave time t₃Until a time t_3-1For a duration of time to maintain the temperature T₃Wherein t is_3-1-t₃Is 0.25h to 3h,

in phase 5 over a time point t_3-1Until a time t₄From T₃Cooling to room temperature, where t₄-t_3-1Is 2h to 4 h.

15. The method of claim 14, wherein T₃Between 520 ℃ and 620 ℃, preferably between 560 ℃ and 620 ℃, to achieve a saturation magnetostriction | λ s | ≦ 1ppm, preferably | λ s ≦ 0.5 ppm.

16. The method according to claim 15, wherein the saturation magnetostriction λ s is adjusted between 0 and +1ppm, preferably between 0 and +0.5 ppm.

17. The method of any one of claims 14 to 16, wherein the field strength of the magnetic field is varied or kept constant during the heat treatment.

18. The method of any one of claims 14 to 16, wherein the magnetic field is switched on or off during the heat treatment.

19. The method according to any one of claims 14 to 18, wherein at least three cores, preferably at least 25 cores, are stacked on top of each other and heat treated.

20. A method according to any one of claims 14 to 16, in which an electrically insulating layer is provided on at least one of the two surfaces of the tape prior to winding.

Technical Field

The invention relates to an alloy, in particular an iron-based alloy, and to a method for producing a magnetic core, in particular an annular strip core.

Background

Among metallic soft magnetic materials, Fe-based nanocrystalline materials are particularly promising candidates for inductors. These materials have developed over the past few decades and find increasing use both in high quality magnetic cores and components, and in shields, antennas and various magnetic sensors. Compared to other soft magnetic metal tip materials, nanocrystalline metal foils have good high frequency performance and small losses due to their relatively high specific resistance (typically 100-150 μ Ω cm) and their small band thickness of about 20 μm associated with fabrication. Therefore, the toroidally shaped tape core made of these materials is both technically competitive with soft magnetic ferrites and, due to its significantly smaller design size, also in terms of cost/benefit. Meanwhile, among all soft magnetic tip materials, the nanocrystalline soft magnetic material has far superior optimal soft magnetic property aging stability. Optimization of soft magnetic properties via alloy composition and heat treatment of nanocrystalline metals has focused primarily on the torroidal strip core in the high permeability area, with application frequencies of 50Hz to about 100kHz constituting the focus.

One example of a nanocrystalline soft magnetic iron-based alloy is Fe_73.8Nb₃Cu₁Si_15.6B_6.6Which is available under the trade name 800 commercially available. Existing soft magnetic nanocrystalline materials for making various inductors such as, for example800 performance is currently limited to>A high magnetic permeability range of 25000 to 200000. But for many applications a permeability below 20000 to 10000 is necessary.

Disclosure of Invention

The object is to provide an alloy having a magnetic permeability of between 10000 and 15000.

This problem is solved by the subject matter of the independent claims. The subject matter of the dependent claims is to expand.

According to the present invention, there is provided an alloy of formula Fe_aCo_bNi_cCu_dM_eSi_fB_gX_hWherein M is at least one of the elements V, Nb, Ta, Ti, Mo, W, Zr, Cr, Mn and HfA, b, C, d, e, f, g are in atomic%, X indicates impurities and optionally elements P, Ge and C, and a, b, C, d, e, f, g, h satisfy the following condition:

0≤b≤4

0≤c<4

0.5≤d≤2

2.5≤e≤3.5

14.5≤f≤16

6≤g≤7

h<0.5

1≤(b+c)≤4.5

wherein a + b + c + d + e + f + g equals 100.

As impurities, up to 0.1 wt.% aluminum, up to 0.05 wt.% sulfur, up to 0.1 wt.% nitrogen and/or up to 0.1 wt.% oxygen may be present, and present in a sum of up to 0.5 wt.%, preferably up to 0.2 wt.%, preferably up to 0.1 wt.%.

The maximum content of impurities and the sum of elements P, Ge and C (when one or more of elements P, Ge and C are present) is less than 0.5 atomic%, since h < 0.5. In some embodiments, none of elements P, Ge and C are present such that the maximum content of impurities is less than 0.5 atomic%.

The alloy has a nanocrystalline structure in which at least 50% by volume of the grains have an average size of less than 100nm, has a saturated magnetostriction lambda of 1ppm or less_sL, has a hysteresis loop with a central linear portion, and has a magnetic permeability μ of 10000 to 15000, preferably 10000 to 12000.

However, in the case of the iron-based nanocrystalline alloy, the performance of magnetostriction and permeability is contradictory. EP 1609159B 1 discloses a nanocrystalline iron-based alloy with which a permeability of about 10000 can be achieved. It had a saturation magnetostriction of 4.4 ppm. US 6507262B 2 discloses a nanocrystalline iron-based alloy having a saturated magnetostriction of less than 1ppm, but having a permeability of 40000. These alloys are therefore unsuitable for the desired use, both with a permeability between 10000 and 15000 and with a small magnetostriction of at most ± 1 ppm.

It has been surprisingly found that the nanocrystalline iron-based alloy according to the invention has a permeability of 10000 to 15000 and a saturation magnetostriction lambda of ≦ 1ppm_sA combination of | s. Therefore, a new use can be achieved, for example, in various parts such as a magnetic core made of a soft ferromagnetic body, the magnetic core is manufactured with the alloy according to the present invention instead of the soft ferromagnetic body, and can have a smaller volume without deteriorating the performance.

The lower limit of the permeability makes possible a sufficient inductance of the core, while the upper limit of the permeability and the saturation induction ensure a high current preloading capacity of the core without magnetically saturating it. Small magnetostriction lambda of 1ppm or less, preferably 0.5ppm or less_sIt is prevented that the core may be mechanically deformed with a change in magnetic properties, in particular a change in permeability.

In principle, for alloys with a permeability of approximately 10000 to 12000 and almost vanishing magnetostriction, the field of application is the production of common-mode chokes for frequency converters, solar converters, for ship drives, for railway drives, or for welders, or for reducing shaft currents in motors and generators. In particular with respect to those common mode chokes in which high common mode currents flow or in which a high inductance L is required in connection with the circuit. The common-mode choke through which the very high currents flow can be realized only with very low-conductivity alloys, as can be obtained from the german germany german corpusch schmelze GmbH&Co KG commercially available VP270 (having nominal composition 5.8 wt.% Ni, 1.0 wt.% Cu, 5.4 wt.% Nb, 6.4 wt.% Si, 1.7 wt.% B, balance Fe), VP250 (having nominal composition 11.6 wt.% Ni, 1.0 wt.% Cu, 5.3 wt.% Nb, 6.2 wt.% Si, 1.7 wt.% B, balance Fe) and VP220 (having nominal composition 11.6 wt.% Ni, 8.1 wt.% Co, 1.0 wt.% Cu, 5.3 wt.% Nb, 5.9 wt.% Si, 1.7 wt.% B, balance Fe), or induced by tensile stress500 (having a nominal composition of 1.0 wt.% Cu, 5.6 wt.% Nb, 8.8 wt.% Si, 1.5 wt.% B, balance Fe), which may also be achieved by the German Vacuumschmelze Gm, KangabH&CoKG is commercially available.

The advantages of an alloy with almost vanishing magnetostriction will be of interest first in the case of a permeability from 10000, since in this case the induced anisotropy energy K_u(K_u＝1/2B_s ²/(μμ_o) Is a residual anisotropy from magnetoelasticity (magnetoelasticity)

)K_magel＝3/2λ_sσ is of comparable size (where λ_sIs magnetostrictive, σ is mechanical tension or pressure). Thus, external tension or pressure on the core can affect the magnet quality (hysteresis loop shape). If it will magnetostriction lambda_sDirected in the zero direction, this effect can be minimized, since the magnetoelastic residual anisotropy K is thereby_magelAnd (4) disappearing. If the magnetostriction is not close to zero in this case, any mechanical tension or pressure on the core must be prevented, which is achieved by winding the core with copper wire. This is not possible in most cases. In the case of low-conductivity alloys such as VP270, VP250 and VP220, which in part have a high positive magnetostriction, it is of course also possible to influence the magnet quality by external tension or pressure on the core. However, induced anisotropy energy K_u(K_u＝1/2B_s ²/(μμ_o) Is still significantly larger, so that residual effects are rarely maintained.

The central part of the hysteresis loop is defined here as the part of the hysteresis loop between the points of the anisotropic field strength which mark the transition to saturation. The linear portion of this central portion of the hysteresis loop is defined herein by a non-linearity parameter NL, which can be calculated and described by:

wherein B is_auf(B_{Lifting of wine}) Or B_ab(B_Descend) Indicating by saturation polarization B_sStandard deviation of the magnetic polarization of the rising or falling branch of the hysteresis loop (Ausgleichsgeraden) between polarization intensity values of ± 75%. The smaller NL, the more linear the loop is. The alloy according to the invention has a NL value of less than 0.8%.

This form of hysteresis loop can be achieved by heat treating the amorphous alloy in a magnetic field oriented transverse to the length of the ribbon.

Furthermore, the alloy may have a permeability of from 10000 to 15000, preferably from 11000 to 14000 or 10000 to 12000, and also a saturated magnetostriction | λ ≦ 0.5ppm, preferably ≦ 0.1ppm_sAnd has a saturation induction greater than 1.0T. A saturation induction greater than 1.0T may guarantee a high current preloading capability together with a permeability from 10000 to 15000. It may also have<Remanence ratio B of 1.5%_r/B_sAnd/or<Coercive field strength H of 1A/m_cAnd/or an anisotropy field H of > 60A/m, preferably > 70A/m_k。

In one embodiment, the alloy has nickel, where 0.2 ≦ c < 4.

In one embodiment, X indicates carbon (C), and the carbon content h of the alloy is < 0.5.

In one embodiment, at least one element of the group Nb, Ta and Mo is present as M, wherein 2.5< e < 3.5.

Niobium Nb is preferred and may also be replaced entirely by tantalum Ta and partly by up to 0.6 atomic% molybdenum Mo. In some embodiments, the sum of Nb, Ta, and Mo is 2.5 atomic% < (Nb + Ta + Mo) <3.5 atomic%.

In some embodiments, the alloy contains nickel, where 0.2 ≦ c <4, preferably 0.5 ≦ c ≦ 4, preferably 0.2 ≦ c ≦ 3, preferably 0.5 ≦ c ≦ 3.

In some embodiments, the alloy contains cobalt, where 0.2 ≦ b <4, preferably 0.5 ≦ b ≦ 4, preferably 0.2 ≦ b ≦ 3, preferably 0.5 ≦ c ≦ 3.

In some embodiments, the alloy contains both Co and Ni, each at a minimum concentration of 0.2 atomic percent and each at a maximum concentration of 3 atomic percent, wherein the total concentration of the two elements is no more than 4.5 atomic percent, such that 0.2< b <3 and 0.2< c <3 and 1 < b + c < 4.5.

In some embodiments, the alloy contains both Co and Ni, each at a minimum concentration of 0.5 atomic percent and each at a maximum concentration of 3 atomic percent, wherein the total concentration of the two elements is no more than 4.5 atomic percent, such that 0.5< b <3 and 0.5< c <3 and 1 < b + c < 4.5.

According to the present invention, there is also provided a magnetic core having an alloy according to any one of the preceding embodiments. In one embodiment, the magnetic core is in the form of an endless belt core wound from a belt having a thickness of less than 50 μm.

The winding locations of the annular tape cores may be electrically isolated from each other to reduce eddy current losses. The electrical insulation may be provided by an electrically insulating coating applied to one or both sides of the belt, or by embedding or impregnating the wound endless belt core in an electrically insulating glue or resin.

Magnetic cores, which may also be in the form of toroids, may be used in so-called CMCs (common mode Choke) for high power applications. This use is usually only fitted with an exciter coil (single Turn CMC) and is in the case of dc meters of up to about 20A. One example is a magnetic core having the following dimensions: the inner diameter di is 76mm, the outer diameter da is 110mm, and the core height is 25 mm. In the case of such cores prepared from nanocrystalline substances with a tape thickness of about 18+/-3 μm and a core fill factor of about 80%, 650 to 900 tape layers in the amorphous state (Bandlagen) are wound up as a ring-shaped wire core.

The magnetic core may be provided by the following method. Winding a ribbon made of an amorphous alloy into an endless ribbon core, said alloy being of the formula Fe_aCo_bNi_cCu_dM_eSi_fB_gX_hWherein M is at least one of the elements V, Nb, Ta, Ti, Mo, W, Zr, Cr, Mn and Hf, a, b, C, d, e, f, g are in atomic%, X indicates impurities and optionally elements P, Ge and C, and a, b, C, d, e, f, g, h satisfy the following condition:

0≤b≤4

0≤c<4

0.5≤d≤2

2.5≤e≤3.5

14.5≤f≤16

6≤g≤7

h<0.5

1 ≦ (b + c) ≦ 4.5 wherein a + b + c + d + e + f + g equals 100.

The endless belt core is heat treated under application of a directional magnetic field of from 80kA/m to 200kA/m across the length of the belt. In one embodiment, the endless belt core is heat treated at a temperature of from 400 ℃ to 650 ℃ for 0.25 hours to 3 hours under the magnetic field.

In one embodiment, the heat treatment has five stages, wherein

In phase 1 over a time point t₀Until a time t₁Is heated from room temperature to T₁Wherein T is more than or equal to 300 DEG C₁T is less than or equal to 500 DEG C₁-t₀Is 0.5h to 2h,

in phase 2 over a time point t₁Until a time t₂From T₁Heating to T₂Wherein T is more than or equal to 400 DEG C₂T is less than or equal to 600 DEG C₂-t₁Is 0.5h to 6h,

in phase 3 over a time point t₂Until a time t₃From T₂Heating to T₃Wherein T is more than or equal to 400 DEG C₃T is less than or equal to 650 DEG C₃-t₂Is in the range of 0h to 1h,

in phase 4 at the slave time t₃Until a time t_3-1For a duration of time to maintain the temperature T₃Wherein t is_3-1-t₃Is 0.25h to 3h,

in phase 5 over a time point t_3-1Until a time t₄From T₃Cooling to room temperature, where t₄-t_3-1Is 2h to 4 h.

By this heat treatment, the magnetostriction can be finely adjusted so that | λ is achieved_sLess than or equal to 0.5ppm or lambda_sThe | is less than or equal to 0.1 ppm. In one embodiment, T₃At 520 to 620 DEG CPreferably between 560 ℃ and 620 ℃ to achieve saturated magnetostriction lambda_s|≤0.5ppm。

In one embodiment, in phase 3 of the heat treatment, the duration t₃-t₂Greater than 0h, i.e. 0h<t₃-t₂≤1h。

As impurities, up to 0.1 wt.% aluminum, up to 0.05 wt.% sulfur, up to 0.1 wt.% nitrogen and/or up to 0.1 wt.% oxygen may be present, and present in a sum of up to 0.5 wt.%, preferably up to 0.2 wt.%, preferably up to 0.1 wt.%.

The maximum content of impurities and the sum of elements P, Ge and C (when one or more of elements P, Ge and C are present) is less than 0.5 atomic%, since h < 0.5. In some embodiments, none of elements P, Ge and C are present such that the maximum content of impurities is less than 0.5 atomic%.

The field strength of the magnetic field can be varied or kept constant during the heat treatment. The magnetic field may be switched on or off during the heat treatment.

In one embodiment, at least three cores, preferably at least 25 cores, are stacked on top of each other and heat treated in the stack. This stacked arrangement of the magnetic cores during the heat treatment results in a better linearity of the hysteresis loop, which can be described by a non-linearity parameter.

The amorphous ribbon can be prepared by a rapid solidification technique and has a thickness of at most 50 μm, preferably at most 25 μm.

In one embodiment, the tape is provided with an electrically insulating layer on at least one of its two surfaces prior to winding. An electrically insulating layer may be used to reduce eddy currents and hence eddy current losses.

In one embodiment, X indicates carbon (C), and h indicates the carbon content of the alloy, where h < 0.5.

In one embodiment, at least one element of the group Nb, Ta and Mo is present as M, wherein 2.5< e < 3.5. Niobium Nb is preferred and may also be replaced entirely by tantalum Ta and partly by up to 0.6 atomic% molybdenum Mo. In some embodiments, the sum of Nb, Ta, and Mo is 2.5 atomic% < (Nb + Ta + Mo) <3.5 atomic%.

In some embodiments, the alloy contains both Co and Ni, each at a minimum concentration of 0.5 atomic percent and each at a maximum concentration of 3 atomic percent, wherein the total concentration of the two elements is no more than 4.5 atomic percent, such that 0.5< b <3 and 0.5< c <3 and 1 < b + c < 4.5.

Embodiments and examples will now be further elucidated with the aid of the figures and tables.

Drawings

Fig. 1 shows a schematic view of stacked endless belt cores during heat treatment.

Fig. 2 shows an example of a flat hysteresis loop.

Fig. 3 shows a diagram of the trend of the temperature and the magnetic field as a function of time for the thermal treatment of an endless belt core in a magnetic field.

Fig. 4 shows a graph of the dependence of permeability on annealing temperature.

Fig. 5 shows a graph of the dependence of saturation magnetostriction on annealing temperature.

FIG. 6 shows Fe in the alloy system_{Balance of}Co_xNi_yCu₁Nb₃Si₁₂B₈In the anisotropic properties K as a function of the Co and Ni contents in atomic%_uCoercive field H_cAnd magnetostriction lambda_sThe figure (a).

FIG. 7 shows the Fe as a function of the Co content in atomic% achieved in the case of alloying with Co addition_{Balance of}Co_xCu₁Nb₃Si_15.3B_6.8The fractions of initial permeability of (a) each relate to an alloy without Co addition, i.e. x is 0, for 2 different heat treatments in a magnetic field. The magnetic permeability achieved for x ═ 0 in each case is also shown in the figure.

FIG. 8 shows different annealing temperatures T for between 540 ℃ and 600 ℃_aFe (b) of_{Balance of}Co_xCu₁Nb₃Si_15.3B_6.8In as a function of the Co content in atomic%_sThe figure (a).

FIG. 9 shows a diagram forDifferent annealing temperatures T between 540 ℃ and 600 ℃_aFe (b) of_{Balance of}Co_xCu₁Nb₃Si_15.3B_6.8In as a function of the Co content in atomic%_sThe figure (a).

Detailed Description

In table 1, the properties of the comparative alloys are summarized. Table 1 shows the compositions of commercially available nanocrystalline alloys VP220, VP250, VP270 and VP800, the density ρ in the nanocrystalline state, and the polarization J in the amorphous and nanocrystalline states_sMagnetostriction lambda in nanocrystalline state_sAnd permeability μ in the nanocrystalline state, these alloys have a flat hysteresis loop.

TABLE 1

This comparison demonstrates that these alloys either have low permeability (VP 220, VP250, VP 270) below about 5500 with high magnetostriction of more than 6ppm or low magnetostriction (VP 800) with high permeability of at least 20000. As permeability decreases, magnetostriction increases significantly over 1 ppm. The properties of magnetostriction and permeability are therefore contradictory.

However, in some applications, if such an alloy is present, it may be possible to achieve a constructive improvement: the alloy having a value of lambda_sA small magnetostriction of | ≦ 1ppm, preferably from 0 to +1ppm, particularly preferably from 0 to +0.5ppm, and at the same time a permeability of less than 200000, preferably between 10000 and 15000.

According to the invention, this combination of properties is provided by an alloy of the formula Fe_aCo_bNi_cCu_dM_eSi_fB_gX_hWherein M is at least one of the elements V, Nb, Ta, Ti, Mo, W, Zr, Cr, Mn and Hf, a, b, C, d, e, f, g are in atomic%, X indicates impurities and optionally elements P, Ge and C, and a, b, C, d, e, f, g, h satisfy the following condition:

0≤b≤4

0≤c<4

0.5≤d≤2

2.5≤e≤3.5

14.5≤f≤16

6≤g≤7

h<0.5

1≤(b+c)≤4.5

wherein a + b + c + d + e + f + g equals 100.

In an advantageous embodiment, the alloy has Co and Ni as M, where 1 ≦ (b + c). ltoreq.4.5, preferably 2 ≦ (b + c). ltoreq.4.2 and 1 ≦ b.ltoreq.3 and 1 ≦ c.ltoreq.2.

As impurities, up to 0.1 wt.% aluminum, up to 0.05 wt.% sulfur, up to 0.1 wt.% nitrogen and/or up to 0.1 wt.% oxygen may be present, and present in a sum of up to 0.5 wt.%, preferably up to 0.2 wt.%, preferably up to 0.1 wt.%.

The maximum content of impurities and the sum of elements P, Ge and C (when one or more of elements P, Ge and C are present) is less than 0.5 atomic%, since h < 0.5. In some embodiments, none of elements P, Ge and C are present such that the maximum content of impurities is less than 0.5 atomic%.

The magnetic core may be provided in the shape of an amorphous ribbon by a rapid solidification technique. To produce a magnetic core in the form of an endless belt core, an amorphous belt is wound into an endless belt core and heat-treated under application of a magnetic field oriented transversely to the belt length direction, wherein a nanocrystalline structure is produced in which at least 50% by volume of the grains have an average size of less than 100nm, and a desired combination of small magnetostriction and magnetic permeability in the desired range from 10000 to 15000.

Further features of embodiments according to the invention are a maximum induction of at least 1.2T at H200A/m, a non-linearity parameter NL of less than 1%, a remanence ratio B of less than 1.5%_r/B_sCoercive field strength H less than 1A/m_cAn anisotropy field H of at least 60A/m, preferably at least 70A/m_k(magnetic field from which magnetic saturation is reached).

Fig. 1 shows a schematic view of stacked endless belt cores 10 during heat treatment and shows the application of a magnetic field 11 transverse to the belt length direction, as indicated by arrow 12. The magnetic cores 10 are stacked on each other to improve the linearity of the hysteresis loop. Magnetic fields from 80kA/m to 200kA/m can be used. The field strength of the magnetic field may be varied during the heat treatment, for example by switching the magnetic field on or off, or by keeping it nearly constant.

In table 2, the composition and magnetic properties of the different alloys are summarized, with examples 1 to 5 not being part of the invention and examples 6 to 16 being part of the invention. Examples 11 to 16 show preferred examples. The sample had the form of an annular ribbon core wound from an amorphous alloy. The wound endless belt cores are stacked on each other (stacked on an annealing frame) and heat-treated in this stacked state. The samples were heat treated at 570 ℃ for 0.5h under a magnetic field of about 200kA/m oriented across the length of the tape. At least three and preferably more than 25 belt cores may be stacked on top of each other to improve the straightness of the hysteresis loop.

The alloy according to the invention has a linear or flat hysteresis loop (F-loop). Fig. 2 shows an example of a flat hysteresis loop with high linearity performance. One measure of the straightness of the hysteresis loop is given by the ratio of the non-straightness, described by the non-straightness parameter NL (in%), which is calculated by the following equation:

wherein B is_auf(B_{Lifting of wine}) Or B_ab(B_Descend) Indicating by saturation polarization B_sIs ± 75% of the standard deviation of the magnetic polarization of the fitted line of rising or falling legs of the hysteresis loop between polarization intensity values. The smaller NL, the more linear the loop is. This form of hysteresis loop can be achieved by heat treating the amorphous alloy in a magnetic field oriented transverse to the length of the ribbon, as shown in fig. 1.

The conceptual remanence ratio B is also illustrated in FIG. 2_r/B_mCoercive field strength H_cAnisotropy field H_kAnd a magnetic permeability μ.

TABLE 2

Examples 1-5 are not embodiments according to the invention

Examples 6-16 are according to embodiments of the invention

Examples 11 to 16 are preferred embodiments according to the invention

Examples 6 to 16 in table 2 illustrate example alloys according to the present invention, with examples 11 to 16 being preferred. Example 6 the desired properties were achieved by a slight decrease in Si and boron content. However, a small total metalloid content (Si + B) may require special measures to be taken in ribbon preparation to ensure clean glass formation. Example 7 only marginally reached the lower limit of the target permeability range μ 10000 to 15000 and example 9 only marginally reached the upper limit of this range. Example 8 has higher raw material cost due to higher Co-content, which is undesirable in certain embodiments. Example 10 has a magnetostriction of 0.7ppm which may be too high for some applications. In contrast, examples 11 to 16 all had a permeability in the target range of 10000 to 15000 and a magnetostriction λ of 0.5ppm or less_s. These properties of the alloy according to the invention can be adjusted by adjusting the heat treatment.

Fig. 3 shows a diagram of the trend of the temperature and of the magnetic field as a function of time for the thermal treatment in a magnetic field of an endless strip core wound from an alloy in the amorphous state according to the invention in order to produce a nanocrystalline structure and desired magnetic properties. In one embodiment, the heat treatment has five stages, which are illustrated in fig. 3.

In phase 1 over a time point t₀Until a time t₁Duration of time from room temperature T₀Heating to T₁Wherein T is more than or equal to 300 DEG C₁T is less than or equal to 500 DEG C₁-t₀Is 0.5h to 2 h. In phase 2 over a time point t₁Until a time t₂From T₁Heating to T₂Wherein T is more than or equal to 400 DEG C₂T is less than or equal to 600 DEG C₂-t₁Is 0.5h to 6 h. In phase 3 over a time point t₂Until a time t₃From T₂Heating to T₃Wherein T is more than or equal to 400 DEG C₃T is less than or equal to 650 DEG C₃-t₂Is 0h to 1 h. In phase 4 at the slave time t₃Until a time t_3-1Is maintained at the plateau temperature T₃Wherein t is_3-1-t₃Is 0.25h to 3 h. In phase 5 over a time point t_3-1Until a time t₄From T₃Cooling to room temperature T₄Wherein (t)₄-t_3-1) Is 2h to 4 h. By this heat treatment, the permeability, in particular the magnetostriction, can be adjusted to provide the desired permeability from 10000 to 15000, preferably from 10000 to 12000, with a lambda_sA combination of | ≦ 0.5ppm, wherein the belt core also has a saturation induction greater than 1.0T and a hysteresis loop with a central linear portion.

FIG. 4 shows the permeability versus annealing temperature (i.e. plateau temperature T in stage 4 of the heat treatment of FIG. 3) for two alloys according to the invention and a comparative example₃) A graph of the correlation of (a). FIG. 4 shows VP800 (Fe-Cu) for a comparative alloy that is not part of the present invention₁Nb₃Si_15.5B_6.5) And an alloy according to the invention Fe-Cu_0.8Co_1.5Ni_1.0Nb_2.8Si_15.5B_6.5And Fe-Cu_0.8Co_2.5Ni_1.6Nb_2.8Si_15.5B_6.5Permeability μ after crystallization in a transverse field at an annealing temperature of 530 ℃ to 620 ℃. These results show that with the composition according to the invention low permeability in the desired range from 10000 to 15000 can be achieved.

FIG. 5 shows the saturation magnetostriction λ for two alloys according to the invention and a comparative example_sAnd the annealing temperature (i.e., plateau temperature T in stage 4 of the heat treatment of FIG. 3)₃) A graph of the correlation of (a). These results show that for the alloys according to the invention, by adjusting the annealing temperature, a saturated magnetostriction can be achieved|λ_s|≤0.5ppm。

As illustrated in fig. 4 and 5, the magnetic parameters μ and λ can be aligned by the annealing temperature_sA finer adjustment is made. This is particularly feasible for magnetostriction, without the permeability changing substantially. As shown in fig. 5, the magnetostriction can be changed from a positive value to a negative value by appropriately selecting the annealing temperature in the range between 560 ℃ and 620 ℃. Therefore, there is the possibility of adjusting the magnetostriction to "zero" by adjusting the annealing temperature, in particular for the preferred embodiment (| λ |)_sLess than or equal to 0.5 ppm).

In Table 3, the results are summarized for two nanocrystalline alloys that have a maximum + -1 ppm magnetostriction λ, with a flat hysteresis loop achieved by heat treatment in a magnetic field oriented transverse to the ribbon length direction_sAnd a magnetic permeability μ from 10000 to 12000.

TABLE 3

The permeability μ and magnetostriction of these alloys can be adjusted by changing the annealing temperature with the heat treatment shown in fig. 3_sA finer adjustment is made. This is particularly feasible for magnetostriction, without the permeability changing substantially. The magnetostriction can be changed from a positive value to a negative value by appropriately selecting the annealing temperature in the range between 560 ℃ and 620 ℃. Therefore, there is the possibility of adjusting the magnetostriction to "zero" by adjusting the annealing temperature, in particular for the preferred embodiment (| λ |)_s|<0.5 ppm).

In order to maintain good soft magnetic properties as much as possible (in particular coercive field H as small as possible)_cMagnetostriction lambda of-0_s) In the case of (2) realizing induced anisotropy K_uOr a decrease in permeability, the following scheme may be used to select Fe for the alloy system_aCo_bNi_cCu_dM_eSi_fB_gX_hAnd a suitable composition. Three factors A), B) and C) are taken into account here.

By the use of a metal consisting of Fe_{Balance of}Cu₁Nb₃Si_15.5B_6.6(VP800) can induce anisotropy K by pure transverse field annealing of an endless belt core made of belt material_uThe maximum of the belt is increased by about 30J/m³. This corresponds to a permeability of about μ ═ 20000. The addition of the elements Co and/or Ni instead of Fe content in this alloy system increases the potential for uniaxial anisotropy formation. By means of a suitable heat treatment, in contrast to systems without Co and/or Ni, a drastic increase in the induced anisotropy or a strong reduction in the permeability can be achieved as a result.

At a given saturation magnetization B_sIn the case of (2), mu-1/K is present_uOr specifically:

factor a): increase K_u

FIG. 6 shows Fe in the alloy system_{Balance of}Co_xNi_yCu₁Nb₃Si₁₂B₈In the anisotropic properties K as a function of the Co and Ni contents in atomic%_uCoercive field H_cAnd magnetostriction lambda_sThe figure (a).

In FIG. 6, the alloy system Fe is shown_{Balance of}Co_xNi_yCu₁Nb₃Si₁₂B₈In which the anisotropy energy K can be achieved by adding Co and Ni_u. In this alloy system with an Si content of 12 at% and a B content of 8 at%, the effect of the Co and Ni components on the induced anisotropy or on the soft magnetic properties can be observed particularly well. With increasing Co-and/or Ni content, an increase in the anisotropy energy occurs. This can be understood in the following way: with the occurrence of Fe-Co and Fe-Ni atom pairs, a field induced anisotropy K is formed_uThe degree of freedom of (a) is increased.

FIG. 7 shows Fe as a function of Co content in atomic%_{Balance of}Co_xCu₁Nb₃Si_15.3B_6.8Graph of initial permeability of (a). The inset shows the well-established data with a small Co content. FIG. 7 shows that Fe is included in the alloy system_{Balance of}Co_xCu₁Nb₃Si_15.3B_6.8With Co addition (in the alloy system according to the invention), the initial permeability can be reduced with increasing Co content, more precisely the induced anisotropy K_uAnd (4) improving. In the range of Co content below 1 at%, the initial permeability decreases linearly with Co content, and at higher contents, the effect is strongly flattened.

Factor B): keeping magnetostriction close to zero "

In order to maintain the Fe alloy in the case of the target alloy having Co and Ni components_{Balance of}Cu₁Nb₃Si_15.5B_6.6(VP800) good soft magnetic properties and very good loss properties, residual magnetostriction λ remaining after the nanocrystallization process was observed_s. In FIG. 6, Fe is shown in the alloy system_{Balance of}Co_xNi_yCu₁Nb₃Si₁₂B₈In the residual magnetostriction lambda after the nano-crystallization process_sSuch as by the addition of Co and Ni. In this alloy system with an Si content of 12 at% and a B content of 8 at%, the effect of the Co and Ni components on the induced anisotropy or on the soft magnetic properties can be observed particularly well. Again, with increasing Co-and/or Ni content, an increase in residual magnetostriction occurs. This is shown in fig. 6 for a very wide range of Co and/or Ni compositions.

A more detailed relationship can be derived from FIG. 8, which shows the different annealing temperatures T for between 540 ℃ and 600 ℃_aIn terms of the content of Co in atomic% for Fe_{Balance of}Co_xCu₁Nb₃Si_15.3B_6.8(alloy system according to the invention) saturation magnetostriction lambda_sThe influence of (c).

FIG. 9 shows Fe in the Co content range from 0 to 10 atomic%_{Balance of}Co_xCu₁Nb₃Si_15.3B_6.8Saturated magnetostriction lambda of_sA change in (c). In the case of a small amount of Co component (less than 2 atomic%), saturation magnetostriction lambda_sOnly a slight increase, and at high contents the rate of change is strongly increased.

Factor C): coercive field kept as small as possible

In order to maintain the Fe alloy in the case of the target alloy having Co and Ni components_{Balance of}Cu₁Nb₃Si_15.5B_6.6(VP800) good soft magnetic properties and very good loss properties, the retained coercive field H being observed after the nanocrystallization process_c. In this regard, FIG. 6 shows Fe in the alloy system_{Balance of}Co_xNi_yCu₁Nb₃Si₁₂B₈After the nano-crystallization process, coercive field H_cA change in (c). Essentially, with increasing Co-and/or Ni content, the coercive field H_cThis is understood to be due to the fact that with the advent of Fe and Co/Ni it is no longer entirely possible to ascertain the local crystallographic anisotropy of (ausmitetln) α -FeSi nanocrystals.

Based on the knowledge of A), B) and C), Fe-based compositions have been proposed_{Balance of}Cu₁Nb₃Si_15.5B_6.6Is used in<A combination of Co and Ni in the range of 4.5 atomic% as an additional alloy constituent to improve induced anisotropy K_uOr to a desired reduced permeability range. Both with Co and with Ni and with their combinations lead to an increase in the induced anisotropy. It was confirmed that too high Co content causes saturation magnetostriction lambda_sThe increase is strong. Therefore, a combination of Co and Ni is advantageously used to adjust the Co content necessary for a given anisotropy by the Ni fraction. On the other hand, the Ni content is not selected too high, so that the coercive field H can be set to be high_cKept as low as possible.

Thus, in some embodiments, the lowest concentration and the highest concentration are adjusted for Co and Ni. In some embodiments, the minimum concentration of each of Co and Ni is 0.2 atomic%, preferably 0.5 atomic%, and the maximum concentration of each is 3 atomic%, with the total concentration of both elements not exceeding 4.5 atomic%.

The purpose of the first example with both Co and Ni is to provide a permeability of μ 10000 after lateral field heating. To achieve 60J/m₃Induced anisotropy K of_uIt is desirable to replace Fe with a composition of about 4 to 4.5 atomic% of a dissimilar element. If the whole amount (4-4.5 atomic%) is realized with the element Co, it is possible that although the target induced anisotropy is reached and thereby the magnetic permeability is also lowered to μ ═ 10000, the magnetostriction will increase strongly towards the positive sign and good soft magnetic properties will not be maintained. Therefore, the necessary amount must be distributed to Co and Ni.

Depending on factor B), saturation magnetostriction lambda at Co contents of up to 2 atomic%_sOnly a slight improvement. On the other hand, depending on the factor C), too high a Ni content should not be chosen in order to avoid the coercive field H_cIs dramatically improved. Thus, a Co content of 2.5 at% and a Ni content of 1.6 at% may be selected to achieve the desired combination of properties, see alloy A of Table 3.

The purpose of the second example with both Co and Ni is to achieve a permeability of 12000 after lateral field heating. To reach 50J/m₃Induced anisotropy K of_uIt is necessary to replace Fe with a composition of a dissimilar element of about 2.5 to 3 atomic%. If the entire amount (2.5-3 atomic%) is realized with the element Co, it is possible that although the target induced anisotropy is reached and thereby also the permeability is reduced to μ 12000, the magnetostriction will already increase towards positive sign after the above-described embodiment is performed and will therefore not be completely able to do soSoft magnetic properties remain to be obtained. Therefore, the necessary amount must be distributed to Co and Ni.

Depending on factor B), saturation magnetostriction lambda at Co contents of up to 2 atomic%_sOnly a slight improvement. On the other hand, depending on the factor C), too high a Ni content should not be chosen in order to avoid the coercive field H_cIs dramatically improved. Thus, a combination of a Co content of 1.5 at% and a Ni content of 1 at% can be selected, see alloy B of Table 3.