JP2004339047A - Ferrite ceramic composition for irreversible circuit device, irreversible circuit device and radio unit - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ferrite ceramic composition for an irreversible circuit device in which sufficient irreversibility is attained even in the use in ≤10 GHz or 30 to 60 GHz microwave band and magnetic loss is reduced. <P>SOLUTION: The ferrite ceramic composition for the irreversible circuit device contains a main component expressed by a general formula, (Sr<SB>1-x</SB>Ba<SB>x</SB>)O-n(Fe<SB>1-y-z</SB>Me<SB>y</SB>Sn<SB>z</SB>)<SB>2</SB>O<SB>3</SB>(0≤x≤1.0, 5.0<n≤6.5, y>0, z>0), wherein Me represents at least one kind of divalent metal elements. When Me is Zn, y and z are respectively 0<y≤0.29 and 0<z≤0.29. When Me is Cu, y and z are respectively 0<y≤0.33 and 0<z≤0.33. When Me is Co, y and z are respectively 0<y≤0.39 and 0<z≤0.39, and when Me is Ni, Mg or Mn, y and Z are respectively 0<y≤0.28 and 0<z≤0.28. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a ferrite porcelain composition for a non-reciprocal circuit device, a non-reciprocal circuit device, and a wireless device, and more particularly, to a microwave / millimeter wave band having a frequency of several GHz to several tens of GHz (hereinafter, simply referred to as “microwave band”). The present invention relates to a ferrite porcelain composition for a non-reciprocal circuit element suitable for use in the above), a non-reciprocal circuit element such as an isolator or a circulator formed using the ferrite porcelain composition, and a wireless device including the non-reciprocal circuit element. .

  As a non-reciprocal circuit device used in a microwave band such as a mobile phone and a millimeter-wave radar, a non-reciprocal circuit device that applies a DC magnetic field using a permanent magnet is conventionally known.

The irreversible circuit element uses a garnet-based ferrite represented by yttrium iron garnet Y ₃ Fe ₅ O ₁₂ (hereinafter referred to as “YIG”) or a spinel-based ferrite represented by Mg ferrite or NiCuZn ferrite. A direct current magnetic field is applied and driven by a permanent magnet such as a Sr ferrite magnet or the like.

  In the non-reciprocal circuit device, a garnet-based ferrite is generally used in a microwave band of several hundred MHz to several GHz, and a spinel-based ferrite is used in a microwave band of several tens GHz.

  That is, garnet-based ferrite has a large magnetic loss peak on the low magnetic field side in the ultra-high frequency range or microwave band of several hundred MHz to several GHz, so that a non-reciprocal circuit element with low magnetic loss cannot be obtained. Are driven on the higher magnetic field side than the ferromagnetic resonance peak.

  On the other hand, spinel-based ferrite is used in the microwave band of several tens of GHz, and is generally driven on the lower magnetic field side than the ferromagnetic resonance peak. That is, in the microwave band of several tens of GHz, since the ferromagnetic resonance peak and the low magnetic field loss peak are sufficiently separated, it is possible to obtain a nonreciprocal circuit device having sufficiently low magnetic loss even when driven at a low magnetic field. It is difficult to sufficiently saturate the spinel ferrite (saturation magnetization of about 0.4 T) with a permanent magnet, so that the magnet is driven at a lower magnetic field than the ferromagnetic resonance peak. Then, when a magnetic field is generated, the high-frequency magnetic field generates a right-handed circularly polarized wave and a left-handed negative circularly polarized wave in the direction of the DC magnetic field. A non-reciprocal circuit device is realized by utilizing such properties, which are different between circularly polarized waves and negative circularly polarized waves.

  That is, the complex magnetic permeability μ of the ferrite is represented by Expression (1), the real part μ ′ indicates the response of the magnetization, and the imaginary part μ ″ indicates the magnetic loss.

μ = μ′−jμ ″ (1)
'From that shows the response of the magnetization, the real part of the positive circularly polarized magnetic permeability mu ₊ mu _+' the real part of the complex permeability mu mu negative circularly polarized magnetic permeability mu _- real part of the mu _- 'and permeable The absolute value of the magnetic permeability difference Δμ (= μ ₊ ′ ₋ μ− ′) (hereinafter referred to as “absolute magnetic permeability difference | Δμ |”) indicates irreversibility, and therefore, the characteristics of ferrite are absolute magnetic permeability difference | Δμ | And the imaginary part μ ₊ ″ of the circularly polarized magnetic permeability μ ₊ .

  By the way, in a mobile phone used in a microwave band of several GHz, further reduction in the height, size, and cost of the device are required, and accordingly, the height and size of the irreversible circuit element are reduced. Therefore, cost reduction has been demanded.

  However, since a garnet-based ferrite requires a permanent magnet for applying a DC magnetic field, there is a limit to the reduction in height, size, and cost of a nonreciprocal circuit device.

  In the microwave band of several tens of GHz, a wireless device such as a small wireless LAN or a millimeter-wave radar equipped with a nonreciprocal circuit device is expected. As in the case of the system ferrite, since a permanent magnet is required, there is a limit in reducing the height, size, and cost of the nonreciprocal circuit device.

On the other hand, the self-bias operation type using Ba ferrite (BaO · _6Fe 2 _{O 3)} and Sr ferrite (SrO · _6Fe 2 _{O 3)} hexagonal magnetoplumbite ferrite of the like having a uniaxial magnetic anisotropy Has been conventionally known.

In the self-bias operation type non-reciprocal circuit device, for example, Ba ferrite has an anisotropic magnetic field Ha of 1.40 × 10 ³ kA / m, and Sr ferrite has 1.54 × 10 ³ kA. / M, the magnetic field is generated by driving the anisotropic magnetic field Ha without using a permanent magnet.

  As described above, the self-bias operation type nonreciprocal circuit element using the magnetoplumbite ferrite does not require a permanent magnet for applying a magnetic field such as garnet ferrite or spinel ferrite. Promising from the viewpoint of miniaturization, miniaturization, and cost reduction.

  As such a self-biasing operation type non-reciprocal circuit element which does not require such a permanent magnet, an isolator (non-reciprocal circuit element) is mounted together with a semiconductor chip in a microwave integrated circuit or a microwave circuit module in a surface mounting format. A technique has been proposed (Patent Document 1).

JP-A-11-17408

  However, conventional non-reciprocal circuit devices of the self-bias operation type cannot obtain sufficient irreversibility in a microwave band of 10 GHz or less, and have a large magnetic loss in a microwave band of 30 to 60 GHz. There is a problem that it is not suitable for use in the microwave band.

Figure 15 is a magneto each permeability components of the positive and negative circular polarization permeability mu _± of Sr ferrite as an example of a ferrite _{μ + ', μ + ",} μ -', μ -" shows the frequency characteristic of the . Horizontal axis represents the frequency (GHz), and the vertical axis permeability components of the positive and negative circular polarization permeability _{μ ± μ + ', μ +} ", μ -', μ -" is.

  FIG. 16 shows a magnetic permeability difference Δμ when Sr ferrite is used for a self-biased operation type non-reciprocal circuit device. The horizontal axis is frequency (GHz) and the vertical axis is magnetic permeability difference Δμ.

  As is clear from FIGS. 15 and 16, it is possible to drive at a higher magnetic field side than the ferromagnetic resonance peak in the microwave band of 10 to 30 GHz, and in the microwave band of 60 to 200 GHz, It can be driven on the low magnetic field side.

However, as shown in FIG. 15, in the microwave band of 30 to 60 GHz, the imaginary part μ ₊ ″ of the circularly polarized magnetic permeability greatly increases from the threshold value of 0.05, and the magnetic loss increases. As a result, a non-reciprocal circuit device with low loss cannot be obtained.

  On the other hand, as shown in FIG. 16, in the microwave band of 10 GHz or less, the magnetic permeability difference Δμ is less than 0.1, so that desired irreversibility cannot be obtained.

  That is, the conventional self-biased operation type non-reciprocal circuit device cannot obtain desired irreversibility in the microwave band of 10 GHz or less, while the magnetic loss increases in the microwave band of 30 to 60 GHz. was there.

  The present invention has been made in view of such problems, and it is possible to obtain sufficient irreversibility even when used in a microwave band of 10 GHz or less or 30 to 60 GHz, and to reduce magnetic loss. It is an object of the present invention to provide a ferrite porcelain composition for a non-reciprocal circuit device capable of performing the same, a self-bias type non-reciprocal circuit device manufactured using the ferrite porcelain composition, and a wireless device.

The present inventors have conducted intensive studies to achieve the above object, and found that a part of trivalent Fe ion (Fe ³⁺ ) contained in magnetoplumbite-type hexagonal ferrite was converted to tetravalent Sn ion (Sn ^4+). ) Can control the anisotropic magnetic field Ha, thereby improving the irreversibility of the ferrite porcelain composition and suppressing the magnetic loss.

In addition, when Fe ³⁺ is replaced with Sn ⁴⁺ , the charge balance is lost, but this can be corrected for charge with divalent metal ions.

The present invention has been made based on such knowledge, and the ferrite porcelain composition for a non-reciprocal circuit device according to the present invention (hereinafter, simply referred to as “ferrite porcelain composition”) has the general formula {(Sr ₁₋ Table with _{x Ba x) O · n (} Fe 1-yz Me y Sn z) 2 O 3} (0 ≦ x ≦ 1.0,5.0 <n ≦ 6.5, y> 0, z> 0) Is characterized in that Me is at least one divalent metal element.

  Further, as a result of earnest research by the present inventors, a ferrite porcelain composition using Zn, Cu, Co, Ni, Mn, and Mg as the divalent metal element and setting the content of the divalent metal element to a predetermined range. Is a ferrite porcelain composition for a nonreciprocal circuit device having a desired irreversibility and a small porcelain loss even when used in a microwave band of 10 GHz or less or 30 to 60 GHz without generation of a different phase. It was found that it is possible to obtain.

  That is, the ferrite porcelain composition of the present invention is characterized in that when the Me is Zn, the y and z are 0 <y ≦ 0.29 and 0 <z ≦ 0.29, respectively, and the Me is Cu. , The y and z are respectively 0 <y ≦ 0.33 and 0 <z ≦ 0.33. When the Me is Co, the y and z are each 0 <y ≦ 0. 39, 0 <z ≦ 0.39, and when Me is any of Ni, Mg or Mn, y and z are respectively 0 <y ≦ 0.28 and 0 <z ≦ 0. 28.

  By the way, in the non-reciprocal circuit device, as the distance between the permanent magnet and the ferrite porcelain composition is shorter, the transmission characteristics are deteriorated due to the influence of the eddy current loss generated in the permanent magnet. The eddy current is more likely to be generated as the specific resistivity ρ of the permanent magnet is smaller. Moreover, in the self-bias type non-reciprocal circuit device, since the ferrite porcelain composition itself generates a magnetic field, the influence of eddy current loss is very large. Therefore, it is necessary to reduce the eddy current loss in order to avoid the deterioration of the transmission characteristics in the self-bias type nonreciprocal circuit element, and it is necessary to increase the specific resistivity ρ of the ferrite porcelain composition.

  Then, as a result of intensive studies conducted by the present inventors, at least one of the Ca component and the Co component was added in a total amount of 0.001 to 0.8 mol based on 1 mol of the main component, and The finding that the specific resistance ρ can be increased by adding the total content of the Mn component and the Zr component in the ferrite porcelain composition in a range of 1.5% by weight or less in terms of oxide. Got.

  That is, the ferrite porcelain composition of the present invention contains at least one of a Ca component and a Co component as an auxiliary component, and the content of the Ca component and the Co component is 0.1 to 1 mol of the main component in total. 001 to 0.8 mol, and at least one of a Mn component and a Zr component as a subcomponent, and the content of the Mn and Zr is 1 in total in terms of oxide. 0.50% by weight or less (not including 0% by weight).

  Further, a nonreciprocal circuit device according to the present invention includes a ferrite member formed of the ferrite porcelain composition.

  Furthermore, a wireless device according to the present invention includes the non-reciprocal circuit device.

Ferrite ceramic composition according to the present invention as described in detail above, the general formula _{{(Sr 1-x Ba x} ) O · n (Fe 1-yz Me y Sn z) 2 O 3} (0 ≦ x ≦ 1 0.00, 5.0 <n ≦ 6.5, y> 0, z> 0), and Me is at least one divalent metal element. Desired irreversibility can be obtained even in the microwave band of 60 GHz, and a ferrite porcelain composition having small magnetic loss can be obtained.

  Further, the ferrite porcelain composition of the present invention contains 0.001 to 0.8 mol of at least one of a Ca component and a Co component as a subcomponent with respect to 1 mol of the main component. Since at least one of the Mn component and the Zr component is contained in a total of 1.50% by weight or less (not including 0% by weight) in terms of oxide, the specific resistivity ρ is large. A ferrite porcelain composition can be obtained, which makes it possible to reduce the effect of eddy current loss generated in the permanent magnet of the non-reciprocal circuit device, and to provide a self-bias type non-reciprocal circuit device having good transmission characteristics. Obtainable.

  Further, since the non-reciprocal circuit device according to the present invention includes a ferrite member formed using the ferrite porcelain composition, the non-reciprocal circuit device has a desired irreversibility even in a microwave band of several GHz to several tens of GHz. In addition, it is possible to obtain a non-reciprocal circuit device having small magnetic loss. In addition, since the ferrite porcelain composition can be driven by using the anisotropic magnetic field Ha, it does not require a permanent magnet, and can be reduced in size, height, and cost.

  Further, since the wireless device according to the present invention includes the above-mentioned non-reciprocal circuit device, even if it is used in a microwave band of 10 GHz or less or in a microwave band of 30 to 60 GHz, the magnetic loss is small. It is possible to obtain a miniaturized, low-profile, low-cost wireless device such as a mobile phone or a millimeter-wave radar equipped with a self-bias type non-reciprocal circuit element having a desired irreversibility.

  Next, embodiments of the present invention will be described in detail.

  The ferrite porcelain composition according to the present invention comprises a sintered body represented by the following general formula [A].

_{(Sr 1-x Ba x)} O · n (Fe 1-yz Me y Sn z) 2 O 3 ... [A]
Here, Me represents a divalent metal element, x is 0 ≦ x ≦ 1.0, and n is 5.0 <n ≦ 6.5. Moreover, y and z are y> 0 and z> 0, respectively, and the upper limit is determined according to the element used for Me.

Thus, the ferrite porcelain composition of the present invention is a magneto-pravant type ferrite represented by the general formula (Sr _1-x Ba _x ) OnFe ₂ O ₃ (where 0 ≦ x ≦ 1.0): A part of Fe ³⁺ is replaced with Sn ⁴⁺ and divalent metal ion Me ²⁺ .

Hereinafter, the reason why a part of Fe ³⁺ was replaced with Sn ⁴⁺ and Me ²⁺ will be described.

(1) Reason for Partially Replacing Fe ³⁺ with Sn ⁴⁺ Magnetoplumbite ferrite can generate a magnetic field by driving an anisotropic magnetic field Ha, but according to the experimental results of the present inventors, It has been found that by substituting a part of Fe ³⁺ with Sn ⁴⁺ , the anisotropic magnetic field Ha can be controlled in a decreasing direction.

  On the other hand, the internal magnetic field Hin is represented by Expression (2), and the frequency of the ferromagnetic resonance peak is represented by Expression (3).

Hin = Ha−N × Ms (2)
ω = γ × Hin (3)
Here, N is the demagnetizing field coefficient, Ms is the saturation magnetization (T), and γ is the gyro constant (= 3.51 × 10 ⁴ m / A · s).

That is, by substituting a part of Fe ³⁺ with Sn ⁴⁺ , the anisotropic magnetic field Ha changes in a decreasing direction. At this time, since the saturation magnetization Ms also fluctuates in the decreasing direction, the internal magnetic field Hin fluctuates as appropriate according to equation (2), and accordingly, the frequency of the ferromagnetic resonance peak also fluctuates according to equation (3).

  The decrease in the anisotropic magnetic field Ha causes the frequency of the ferromagnetic resonance peak to fluctuate. As a result, as shown in FIG. 1, the magnetic permeability difference between the real part of the circular polarization and the real part of the negative circular polarization. The frequency characteristic of Δμ can be changed from the characteristic indicated by the imaginary line to the characteristic indicated by the solid line as indicated by the arrow X, and has sufficient irreversibility even when used in a microwave band of 10 GHz or less. A ferrite porcelain composition can be obtained.

It is known that the imaginary part μ ₊ ″ indicating the magnetic loss becomes a Lorentz-shaped distribution curve with respect to the internal magnetic field Hin as shown in FIG. 2, and the magnetic resonance peak is obtained by changing the internal magnetic field Hin. At the same time, the frequency of the ferromagnetic resonance peak can be varied, and as a result, the imaginary part μ ₊ ″ can be reduced, and the magnetic loss at 30 to 60 GHz can be suppressed. It becomes possible.

(2) Reason for Partially Replacing Fe ³⁺ with Me ^{2+ The} charge balance is lost only by partially replacing Fe ³⁺ with Sn ⁴⁺ . Therefore, it is necessary to correct a charge by replacing a part of Fe ³⁺ with Me ²⁺ .

Here, the metal ion Me ²⁺ for correcting the electric charge is not particularly limited. However, when the electric charge is corrected using Zn, Cu, Co, Ni, Mn, or Mg, no foreign phase is generated. ,preferable. In particular, Co has a large magnetic anisotropy of the element itself, and can slow down the decrease in the anisotropic magnetic field Ha due to the substitution of Sn.

  However, when the metal element Me is Zn, y and z are respectively 0 <y ≦ 0.29 and 0 <z ≦ 0.29, and when the metal element Me is Cu, y and z are each 0 <y ≦ 0.33, 0 <z ≦ 0.33, and when the metal element Me is Co, y and z are respectively 0 <y ≦ 0.39, 0 <z ≦ 0.39, and the metal element Me is Ni, In the case of Mg or Mn, y and z are preferably 0 <y ≦ 0.28 and 0 <z ≦ 0.28, respectively.

  This is because if y and z exceed the upper limits, the contents of the metal elements Me and Sn become excessive, and the content of Fe becomes too small to have no magnetic anisotropy.

  In the general formula [A], n is set to 5.0 <n ≦ 6.5 because when n is out of this range, no magnetic anisotropy is exhibited, and a different phase is precipitated or sintered. This is because it is difficult to obtain a sufficient saturation magnetization.

In addition, y can have a charge balance in the stoichiometric composition in the same mole number as Sn ⁴⁺ , but has a high resistance in a composition in which y and z are not the same mole number due to element diffusion into the grain boundary or the like. Thus, a material having a low dielectric loss can be obtained, and this is true regardless of the x indicating the molar ratio between Sr and Ba.

  And the said ferrite porcelain composition is manufactured as follows.

  That is, a barium compound, a strontium compound, an iron compound, a tin compound, and a metal containing a divalent metal element as a ferrite raw material so that the composition components of the ferrite porcelain composition as a final product have a predetermined molar ratio. The compounds are appropriately weighed and mixed, wet-mixed by a ball mill, calcined in the air, and then wet-pulverized to prepare a calcined powder. Next, the calcined powder is kneaded with a binder resin to form a slurry, dehydrated and molded in a magnetic field, and then fired in the air, thereby producing a ferrite porcelain composition represented by the general formula [A]. You.

  In the above-described manufacturing process, impurities such as Mn, Cl, Ni, Zn, Mg, S, Ca, Cr, and Bi may be mixed at less than 0.4% by weight, and Zr or Si may be mixed during wet mixing. And the like may be mixed at less than 0.8% by weight, but this does not affect the characteristics of the present invention.

  Further, the ferrite porcelain composition of the present invention is not limited to the embodiment described above, and at least one of the Ca component and the Co component as a sub-component is mainly represented by the general formula [A]. It is also preferable that the total amount is 0.001 to 0.8 mol based on 1 mol of the component.

  That is, it is preferable that the ferrite porcelain composition is represented by the following general formula [B].

_{(Sr 1-x Ba x)} O · n (Fe 1-yz Me y Sn z) 2 O 3 + αCa + βCo ... [B]
Here, α and β are the content moles of the added Ca component and Co component with respect to 1 mole of the main component represented by the above-mentioned general formula [A], and satisfy the following formula [C].

0.001 ≦ α + β ≦ 0.8… [C]
In a non-reciprocal circuit device, as the distance between the permanent magnet and the ferrite porcelain composition is shorter, the transmission characteristics are deteriorated due to the influence of the eddy current loss generated in the permanent magnet. The eddy current is more likely to be generated as the specific resistivity ρ of the permanent magnet is smaller. Moreover, in the self-bias type non-reciprocal circuit device, since the ferrite porcelain composition itself generates a magnetic field, the influence of eddy current loss is very large.

  However, according to the research results of the present inventors, a ferrite porcelain composition having a large specific resistivity ρ is obtained by adding a predetermined amount of a Ca component and / or a Co component so as to satisfy the general formula [B]. As a result, it was found that the eddy current loss of the self-bias type non-reciprocal circuit device can be reduced, and the deterioration of the transmission characteristics can be avoided.

  Here, the reason why the molar amounts α and β of the Ca component and the Co component satisfy the above formula [C] is as follows.

  That is, when the total amount of the molar amounts α and β of the Ca component and the Co component is less than 0.001 mol per 1 mol of the main component, the effect of increasing the specific resistance ρ by the addition of the Ca component and / or the Co component Is not obtained, the signal transmission loss is large, and the transmission characteristics are deteriorated. Also, when the total molar amount α, β of the Ca component and the Co component exceeds 0.8 mol, the specific resistivity This is because ρ tends to decrease, signal transmission loss increases, and transmission characteristics may deteriorate.

  Further, in the ferrite porcelain composition of the general formula [A] or [B], the content of the Mn component and the Zr component as auxiliary components is 1.5% by weight or less (0% by weight) in terms of oxide. (Not included) can also increase the specific resistivity ρ. In particular, by adjusting the content of the Mn component and the Zr component in the general formula [B] to be 1.5% by weight or less (not including 0% by weight) in terms of oxide, the Ca component and the Co component are prepared. It is possible to obtain a larger specific resistivity ρ in combination with the effect of adding.

  In this case, the Mn component may be contained in the sintered body that is the main component, or the Mn compound may be added to the sintered body, and the Zr component may be added to the sintered body. In any case, the Mn component and the Zr component in the ferrite porcelain composition are adjusted so as to be 1.5% by weight or less (not including 0% by weight) in terms of oxide. A ferrite porcelain composition having a large specific resistivity ρ can be obtained, whereby further low eddy current loss can be achieved with a self-bias type nonreciprocal circuit device, and good transmission characteristics can be obtained.

  However, if the total content of the Mn component and the Zr component exceeds 1.5% by weight, the specific resistivity ρ may be rather lowered. Must be controlled so as to be 1.5% by weight or less in total.

  Next, a non-reciprocal circuit device using the ferrite porcelain composition will be described.

  FIG. 3 is a perspective view schematically showing a lumped constant circulator as one embodiment (first embodiment) of the nonreciprocal circuit device according to the present invention.

  The lumped-constant-type circulator is formed so that the microstrip lines 1a, 1b, and 1c cross each other at an interval of 120 ° C. The ferrite substrate 3 is in contact with the ferrite substrate 3 formed of the ferrite porcelain composition. A capacitor (not shown) is attached to the terminal portions 1a ', 1b', 1c 'of the microstrip lines 1a, 1b, 1c, and the resonance frequency is adjusted by the inductance of the ferrite substrate 3 and the capacitor.

  In the first embodiment, for example, when a current flows through the microstrip line 1a, a uniform rotating magnetic field is formed on the ferrite substrate 3 by a cross circuit formed by the microstrip lines 1a, 1b, and 1c. . Since the microwave ferrite is formed of the ferrite porcelain composition, it is possible to obtain a circulator having a small magnetic loss and sufficient irreversibility in a microwave band of 10 GHz or less or 30 to 60 GHz. In addition, since the ferrite porcelain composition is driven by the anisotropic magnetic field Ha, the circulator can be reduced in size, height and cost without requiring an external magnetic field such as a permanent magnet.

  FIG. 4A shows a strip line Y-junction type circulator as a second embodiment of the nonreciprocal circuit device, and FIG. 4B is a view taken along the line AA of FIG. 4A.

  In the second embodiment, the branch paths 4a, 4b, and 4c of the strip line 4 are joined in a Y-shape at a circular center 4d, and the branch paths 4a, 4b, and 4c are used for correction. Capacitor portions 5a, 5b and 5c are formed. Ferrite substrates 6 are provided on both upper and lower surfaces of the central portion 4d, and external conductors 7a and 7b are provided on upper and lower surfaces of the branch paths 4a, 4b and 4c so that the ferrite substrate 6 is sandwiched. ing.

Then, for example, when resonating in the TM ₁₁₀ mode, the high-frequency magnetic field input to the branch path 4a rotates its polarization plane as indicated by an arrow when passing through the ferrite substrate 6, and is output only to the branch path 4b. Form a circulator.

  Also in the second embodiment, since the ferrite substrate 6 is formed of the ferrite porcelain composition, the size and the size of the irreversibility are small and low enough in a microwave band of 10 GHz or less or 30 to 60 GHz. It is possible to obtain a circulator with a reduced height and reduced cost.

FIG. 5 shows a ferrite substrate circulator as a non-reciprocal circuit device according to a third embodiment, in which a Y-shaped strip line 10 is formed on the surface of a ferrite substrate 9. Even in this third embodiment, like the second embodiment, for example, if the resonating in TM ₁₁₀ mode, the high frequency magnetic field that is input to the branch passage 10a is polarization plane rotates on the ferrite substrate 9 Then, it is output only to the branch path 10b to form a circulator.

  Also in the third embodiment, since the ferrite substrate 9 is formed of the above-described ferrite porcelain composition, the magnetic loss is small in a microwave band of 10 GHz or less or 30 to 60 GHz, and the size and size of the irreversibility are small. It is possible to obtain a circulator with a reduced height and reduced cost.

  FIG. 6 is a perspective view schematically showing a waveguide type circulator as a fourth embodiment of the nonreciprocal circuit device. In the fourth embodiment, a Y-shaped waveguide 11 is used. A cylindrical ferrite column 12 is inserted into the center of the Y-branch, and operates in substantially the same manner as in the second and third embodiments to form a circulator. Since the ferrite column 12 is formed of the above ferrite porcelain composition, the magnetic loss is small in the microwave band of 10 GHz or less or 30 to 60 GHz, and the size, height, and cost of having sufficient irreversibility are reduced. It is possible to obtain a circulator that has been made.

  FIG. 7A is a perspective view schematically showing a non-radiative dielectric line Y-type circulator as a fifth embodiment of the non-reciprocal circuit device, and FIG. 7B is a perspective view of FIG. It is BB sectional drawing. In FIG. 7A, a pair of upper and lower metal plates is omitted.

In the fifth embodiment, the dielectric strips 13a, 13b, 13c are arranged at equal intervals to each other at 120 °, and a pair of disc-shaped ferrite substrates 14a, 14b are formed of the dielectric strips 13a, 13b, 13c. Plated metal plates 15a and 15b are provided on both upper and lower surfaces of the dielectric strips 13a, 13b and 13c and the ferrite substrates 14a and 14b. A resonator is constituted by the ferrite substrates 14a and 14b, and resonates in the _HE11δ mode.

  Also in the fifth embodiment, since the ferrite substrates 14a and 14b are formed of the above-described ferrite porcelain composition, the magnetic loss is small in a microwave band of 10 GHz or less or 30 to 60 GHz, and the irreversibility is small. -It is possible to obtain a circulator with a reduced height and reduced cost.

  FIG. 8 is a perspective view schematically showing a Faraday rotary isolator as a sixth embodiment of the non-reciprocal circuit device. The Faraday rotary isolator includes a ferrite rod 17 inserted through a supporting dielectric 16. And the resistance plates 18 a and 18 b are accommodated in the waveguide 19.

Then, for example, the input signal of the TE ₁₀ mode from the direction of the arrow C is converted to the TE ₁₁ mode by the square-circular converter 20a. Since the electric field of the input signal is perpendicular to the resistance plate 18a, it is not absorbed and reaches the ferrite rod 17, is decomposed into positive and negative circularly polarized waves, and the magnetic permeability difference Δμ between the positive and negative circularly polarized waves becomes a phase. As a result of the difference between the constants, the polarization plane rotates by the angle θ. As a result, the input signal passing through the ferrite rod 17 becomes parallel to the resistance plate 18b, and the input signal is absorbed.

On the other hand, the input signal in the TE ₁₀ mode from the direction of arrow D is converted to the TE ₁₁ mode by the square-circular converter 20b. Since the electric field of the input signal is perpendicular to the resistance plate 18b, the electric field reaches the ferrite rod 17 without being absorbed, is decomposed into positive and negative circularly polarized waves, and the plane of polarization rotates by the angle θ. The input signal passing through the ferrite rod 17 becomes perpendicular to the resistance plate 18a and is output from the waveguide 19, thereby forming an isolator in the direction of arrow D.

  Also in the sixth embodiment, since the ferrite rod 17 is formed of the ferrite porcelain composition, the magnetic loss is small in a microwave band of 10 GHz or less or 30 to 60 GHz, and a small irreversible small enough. -It is possible to obtain an isolator having a reduced height and reduced cost.

  FIG. 9 is a perspective view schematically showing a peripheral mode isolator as a seventh embodiment of the non-reciprocal circuit device. The seventh embodiment is formed of the above ferrite porcelain composition. A substantially trapezoidal strip line 22 is formed on the surface of the ferrite substrate 21, and a resistor 23 is formed on the surface of the ferrite substrate 21 so that a part of the strip line 22 overlaps the end of the strip line 22.

  When a high-frequency signal is input to the terminal 24a, the high-frequency magnetic field propagates through one end of the strip line 22 to the output side as shown by the arrow E due to the Faraday effect, and is output from the terminal 24b. On the other hand, when a high-frequency signal is input to the terminal 24b, the high-frequency signal is twisted in the direction of the resistor 23 and proceeds, and the high-frequency signal is absorbed by the resistor 23, thereby forming an isolator.

  Also in the seventh embodiment, since the ferrite substrate 21 is formed of the ferrite porcelain composition, the magnetic loss is small in a microwave band of 10 GHz or less or 30 to 60 GHz, and the irreversibility is small. -It is possible to obtain an isolator having a reduced height and reduced cost.

  FIGS. 10A and 10B are perspective views schematically showing a waveguide resonance type isolator as an eighth embodiment of the non-reciprocal circuit device, wherein the ferrite rods 26a to 26c are rectangular waveguides. It is inserted into a predetermined position of the tube 25.

This In the eighth embodiment, the fundamental mode waveguide 25, that is, when propagating in TE ₁₀ mode, the high frequency magnetic field rotating at a specific position, the circularly polarized wave. Circular polarization includes positive circular polarization and negative circular polarization. When one circular polarization, for example, positive circular polarization acts as a large magnetic loss, the other circular polarization, for example, negative circular polarization. Circularly polarized waves pass without being attenuated.

  Therefore, as shown in FIGS. 10A and 10B, an isolator can be formed by inserting ferrite rods 26a to 26c at specific positions where circular polarization occurs.

  Also in the eighth embodiment, since the ferrite rods 26a to 26c are formed of the above ferrite porcelain composition, the magnetic loss is small in a microwave band of 10 GHz or less or 30 to 60 GHz, and the irreversibility is small. -It is possible to obtain an isolator having a reduced height and reduced cost.

  FIG. 11 shows a cross strip line resonance type isolator as a ninth embodiment of the non-reciprocal circuit device.

  In the ninth embodiment, ground conductors 27a and 27b are formed on one surface of dielectrics 29a and 29b, and a cylindrical ferrite pillar 28 is buried in a substantially central portion of the dielectric 29, and a strip is formed. The line 30 is sandwiched between the dielectrics 29a and 29b. The strip line 30 has a matching capacitor portion 31 and a λ / 4 resonator 32 is formed on the strip line 30 so as to be able to contact the ferrite column 28. In the ninth embodiment, a circularly polarized wave is generated at the intersection between the strip line 30 and the λ / 4 resonator 32, so that an isolator is formed according to the same operation principle as that of FIG.

  Also in the ninth embodiment, since the ferrite column 28 is formed of the ferrite porcelain composition, the magnetic loss is small in a microwave band of 10 GHz or less or 30 to 60 GHz, and the size and size of the irreversibility are small. It is possible to obtain an isolator having a reduced height and reduced cost.

  FIG. 12 is a system configuration diagram showing one embodiment of the wireless device according to the present invention, in which 31 is the isolator shown in FIGS. 8 to 11, and 32 is the circulator shown in FIGS. It is.

  That is, when the modulation signal is input to a voltage controlled signal (Voltage Controlled Oscillator: VCO) 33, the wireless device is input to the coupler 34 via the isolator 31, and the modulation signal is transmitted to the circulator 32 and the mixer 36 by the coupler 34. The modulated signal input to the circulator 32 is transmitted from the antenna 35.

  On the other hand, the reception signal input to the antenna 35 is input to the mixer 36 via the circulator 32, and is mixed with the modulation signal from the coupler 34, and the reception frequency is reduced to obtain an IF signal (Intermediate Frequency). .

  In the present embodiment, since the above-described isolator and circulator are used, the magnetic loss is small enough for a mobile phone used in several GHz band, a wireless LAN used in several tens GHz band, and a millimeter wave radar. It is possible to obtain an irreversible wireless device that can be reduced in size, height, and cost.

  Next, examples of the present invention will be described specifically.

A ferrite porcelain composition having the composition shown in Table 1 and having the general formula {(Sr _1-x Ba _x ) _Onn (Fe _1-yz Zn _y Sn _z ) ₂ O ₃ } was prepared.

That is, BaCO ₃ (barium carbonate), Fe ₂ O ₃ (iron oxide), ZnO (zinc oxide), and tin oxide (SnO ₂ ) are prepared as ferrite raw materials, and these ferrite raw materials are defined as 0 ≦ x ≦ 1. 0, 5.0 ≤ n ≤ 6.6, 0 ≤ y ≤ 0.30, 0 ≤ z ≤ 0.30, weighed and blended, wet mixed with a ball mill, and calcined in air. Then, the powder was wet-pulverized to prepare a calcined powder having a specific surface area of about 5 m ² / g.

Next, the calcined powder is kneaded with a vinyl acetate-based binder to form a slurry. The slurry is subjected to dehydration molding in a magnetic field, and then fired in the air to produce a sintered body. The general formula {(Sr _1-x The ferrite porcelain compositions of Sample Nos. 1 to 23 represented by (Ba _x ) On · (Fe _{1 -yz} Zn _y Sn _z ) ₂ O ₃ } were obtained.

Next, the saturation magnetization Ms and the anisotropic magnetic field Ha of each of these samples were measured, and the relationship between frequency and complex magnetic permeability was simulated based on the measured saturation magnetization Ms and the anisotropic magnetic field Ha. And the permeability difference Δμ (irreversibility) at 40 GHz and the imaginary part μ ₊ ″ (magnetic loss) of the circularly polarized complex permeability.

  Here, the saturation magnetization Ms was measured by a VSM (sample vibration type magnetization measurement device).

  Further, the anisotropic magnetic field Ha was determined as follows. That is, first, using a network analyzer, the magnetic resonance frequency ω of a sample having a known demagnetizing factor N was measured without an external magnetic field, and the anisotropic magnetic field Ha was calculated based on Equation (4).

ω = γ · (Ha−N · Ms) (4)
Here, γ is a gyro constant (= 3.51 × 10 ⁴ m / A · s).

試料番号１は、従来から使用されているＳｒフェライト（異方性磁界Ｈａ：１５３６ｋＡ／ｍ）であり、１０ＧＨｚでは透磁率差Δμが０．０６（＜０．１）と小さく、所望の非可逆性を得ることができない。また、４０ＧＨｚでは虚数部μ_＋″が０．１０（≧０．０５）であり、磁気損失が大きい。 Table 1 shows the composition of each sample number, the saturation magnetization Ms, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ, and the imaginary part μ ₊ ″.

Sample No. 1 is a conventionally used Sr ferrite (anisotropic magnetic field Ha: 1536 kA / m). At 10 GHz, the magnetic permeability difference Δμ is as small as 0.06 (<0.1), and the desired irreversible. I can not get sex. At 40 GHz, the imaginary part μ ₊ ″ is 0.10 (≧ 0.05), and the magnetic loss is large.

  In Sample Nos. 11 and 17, since y and z were 0.30 and exceeded 0.29, the content of Fe was too low, and the anisotropic magnetic field was “0”, which was irreversible. Will not show.

  Also, in sample No. 23, since y exceeded 0.30 and 0.29, the anisotropic magnetic field became “0”, indicating no irreversibility, and n was 6.6 and 6.5. , The saturation magnetization Ms becomes as small as 0.004T, and a sufficient saturation magnetization cannot be obtained.

On the other hand, in sample numbers 2 to 10, 12 to 16, and 18 to 22, y and z are respectively 0 <y ≦ 0.29, 0 <z ≦ 0.29, and n is 5.0 <n ≦ 6. , 5, the anisotropic magnetic field Ha can be reduced as compared with the conventional Sr ferrite (Sample No. 1), whereby the absolute magnetic permeability difference | Δμ | is 0 at least in either 10 GHz or 40 GHz. , The desired irreversibility can be obtained, and the imaginary part μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced.

That is, the sample numbers 5 to 7, 12 to 16, and 18 to 22 can obtain the desired irreversibility because the absolute magnetic permeability difference | Δμ | is 0.1 or more at both 10 GHz and 40 GHz, and The portion μ ₊ ″ is also less than 0.05 and the magnetic loss is small, and it is possible to obtain a nonreciprocal circuit device that can be used in both of these microwave bands.

In sample numbers 2 to 4, the imaginary part μ ₊ ″ is 0.05 or more at 40 GHz and the magnetic loss is large, but the imaginary part μ ₊ ″ is 0 at 10 GHz and no magnetic loss occurs. , The absolute magnetic permeability difference | Δμ | is 0.1 or more, and desired irreversibility can be obtained.

In sample No. 8, the imaginary part μ ₊ ″ was 5.96 (≧ 0.05) at 10 GHz, and the magnetic loss was large. However, the imaginary part μ ₊ ″ was 0 at 40 GHz, and no magnetic loss occurred. In addition, the absolute magnetic permeability difference | Δμ | is 2.70, and sufficient irreversibility can be obtained.

In sample numbers 9 and 10, at 40 GHz, the absolute magnetic permeability difference | Δμ | was less than 0.1 and it was difficult to obtain the desired irreversibility, but at 10 GHz, the absolute magnetic permeability difference | Δμ | 0.1 or more, sufficient irreversibility can be obtained, and the imaginary part μ ₊ ″ is 0, so that no magnetic loss occurs.

As described above, the sample numbers 2 to 10, 12 to 16, and 18 to 22 obtain the desired irreversibility when the absolute magnetic permeability difference | Δμ | is 0.1 or more in at least one of 10 GHz and 40 GHz. It was also found that the imaginary part μ ₊ ″ was less than 0.05, so that the magnetic loss could be reduced.

FIG. 13 is a diagram showing the frequency characteristics of the magnetic permeability difference Δμ in sample No. 7 in comparison with a conventional Ba ferrite (BaO.6Fe ₂ O ₃ ), wherein a solid line indicates sample No. 7 and a broken line indicates Ba ferrite. Is shown. In the figure, the horizontal axis represents the frequency (GHz), and the vertical axis represents the magnetic permeability difference Δμ.

  As is apparent from FIG. 13, in the microwave band of several GHz, the permeability difference Δμ of Ba ferrite is less than 0.1 and it is difficult to obtain sufficient irreversibility. Was 0.1 or more, and it was found that sufficient irreversibility could be obtained.

FIG. 14 is a diagram showing the frequency characteristics of the imaginary part μ ₊ ″ in Sample No. 7 in comparison with a conventional Ba ferrite (BaO.6Fe ₂ O ₃ ), where the solid line indicates Sample No. 7 of the embodiment. The broken line indicates Ba ferrite, where the horizontal axis represents the frequency (GHz) and the vertical axis represents the imaginary part μ ₊ ″.

As is clear from FIG. 14, in the microwave band of 30 to 60 GHz, the imaginary part μ ₊ ″ of Ba ferrite greatly increases from 0.05, and the magnetic loss increases. The imaginary part μ ₊ ″ was almost 0, indicating that little magnetic loss occurred.

  As described above, the sample No. 7 has a desired irreversibility even when used in the microwave band of several GHz and 30 to 60 GHz, and a non-reciprocal circuit device with small magnetic loss can be obtained.

By the same method and procedure as in [Example 1], a ferrite porcelain of the general formula {(Sr _1-x Ba _x ) On · (Fe _1-yz Cu _y Sn _z ) ₂ O ₃ } having the composition shown in Table 2 A composition was made.

That is, BaCO ₃ (barium carbonate), Fe ₂ O ₃ (iron oxide), CuO (copper oxide), and tin oxide (SnO ₂ ) are used as ferrite raw materials, and 0 ≦ x ≦ 1.0, 5.0 ≦ n ≦ 6.6, 0 ≦ y ≦ 0.35, 0 ≦ z ≦ 0.35, and the general formula {(Sr _1-x Ba _x ) On · (Fe _1-yz Cu _y Sn to obtain a ferrite ceramic composition of the sample No. 31-56 represented by _{z) 2} O _3}.

Next, as in [Example 1], the saturation magnetization Ms of each sample, the anisotropy field Ha, the magnetic permeability difference Δμ (irreversibility) at 10 GHz and 40 GHz, and the imaginary part μ ₊ of the circularly polarized complex magnetic permeability ″ (Magnetic loss) was determined.

試料番号３１は、〔実施例１〕の試料番号１（表１）と同様、従来のＳｒフェライト（異方性磁界Ｈａ：１５３６ｋＡ／ｍ）であり、１０ＧＨｚでは絶対透磁率差｜Δμ｜が０．０６と小さく、所望の非可逆性を得ることができない。また４０ＧＨｚでは虚数部μ_＋″が０．１０（≧０．０５）であり、磁気損失が大きくなる。 Table 2 shows the composition of each sample number, the saturation magnetization Ms, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ, and the imaginary part μ ₊ ″.

Sample No. 31 is a conventional Sr ferrite (anisotropic magnetic field Ha: 1536 kA / m) similarly to Sample No. 1 (Table 1) of [Example 1], and the absolute magnetic permeability difference | Δμ | 0.06, and the desired irreversibility cannot be obtained. At 40 GHz, the imaginary part μ ₊ ″ is 0.10 (≧ 0.05), and the magnetic loss increases.

  In sample numbers 43 and 49, since y and z were 0.35 and exceeded 0.33, the content of Fe was too small, and the anisotropic magnetic field was also “0”, which was irreversible. Will not show.

  In sample numbers 50 and 56, n is 5.0 or 6.6, which is out of the range of 5.0 <n ≦ 6.5. It has been found that the saturation magnetization decreases and a sufficient saturation magnetization cannot be obtained.

On the other hand, in sample numbers 32 to 42, 44 to 48, and 51 to 55, y and z are respectively 0 <y ≦ 0.33, 0 <z ≦ 0.33, and n is 5.0 <n ≦ 6. , 5, the absolute magnetic permeability difference | Δμ | becomes 0.1 or more in at least one of 10 GHz and 40 GHz, so that desired irreversibility can be obtained, and the imaginary part μ ₊ ″ is also 0.05. And the magnetic loss can be reduced.

That is, in sample numbers 35 to 38, 44 to 48, and 51 to 55, the desired irreversibility can be obtained because the absolute magnetic permeability difference | Δμ | is 0.1 or more at both 10 GHz and 40 GHz, The imaginary part μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced, and a non-reciprocal circuit device usable in both microwave bands can be obtained.

In sample numbers 32 to 34, the imaginary part μ ₊ ″ becomes larger than 0.05 at 40 GHz and the magnetic loss increases, but the imaginary part μ ₊ ″ becomes 0 at 10 GHz and no magnetic loss occurs. When the absolute magnetic permeability difference | Δμ | is 0.1 or more, desired irreversibility can be obtained.

In sample No. 39, at 10 GHz, the imaginary part μ ₊ ″ was 1.66 (≧ 0.05) and the magnetic loss was large, but at 40 GHz, the imaginary part μ ₊ ″ was 0 and no magnetic loss occurred. And the absolute magnetic permeability difference | Δμ | is 0.13 (≧ 0.1), so that desired irreversibility can be obtained.

In sample numbers 40 to 42, the absolute magnetic permeability difference | Δμ | is less than 0.1 at 40 GHz, making it difficult to obtain the desired irreversibility. However, the absolute magnetic permeability difference | Δμ | 0.1 or more, the desired irreversibility can be obtained, and the imaginary part μ ₊ ″ is 0.01 or 0, and almost no magnetic loss occurs.

As described above, the sample numbers 32 to 42, 44 to 48, and 51 to 55 have a desired irreversibility because the absolute magnetic permeability difference | Δμ | is 0.1 or more in at least one of 10 GHz and 40 GHz. And the imaginary part μ ₊ ″ was also less than 0.05, confirming that the magnetic loss could be reduced.

By the same method and procedure as in [Example 1], a ferrite porcelain of the general formula {(Sr _1-x Ba _x ) On · (Fe _1-yz Co _y Sn _z ) ₂ O ₃ } having the composition shown in Table 3 A composition was made.

That is, BaCO ₃ (barium carbonate), Fe ₂ O ₃ (iron oxide), Co ₃ O ₄ (cobalt oxide), and tin oxide (SnO ₂ ) are used as ferrite raw materials, and 0 ≦ x ≦ 1.0, 0.0 ≦ n ≦ 6.6, 0 ≦ y ≦ 0.40, 0 ≦ z ≦ 0.40, and the general formula {(Sr _1-x Ba _x ) On · n (Fe _1-yz to obtain a Co _y Sn _{z) 2} O ₃ ferrite ceramic composition of the sample No. 61 to 75 represented by}.

Next, as in [Example 1], the saturation magnetization Ms of each sample, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ at 10 GHz and 40 GHz (irreversibility), and the imaginary part μ of the circularly polarized complex magnetic permeability ₊ ″ (Magnetic loss) was determined.

試料番号６１は、〔実施例１〕の試料番号１（表１）と同様、従来のＳｒフェライト（異方性磁界Ｈａ：１５３６ｋＡ／ｍ）であり、１０ＧＨｚでは絶対透磁率差｜Δμ｜が０．０６と小さく、所望の非可逆性を得ることができない。また４０ＧＨｚでは虚数部μ_＋″が０．１０（≧０．０５）であり、磁気損失が大きくなる。 Table 3 shows the composition of each sample number, the saturation magnetization Ms, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ, and the imaginary part μ ₊ ″.

Sample No. 61 is a conventional Sr ferrite (anisotropic magnetic field Ha: 1536 kA / m) similarly to Sample No. 1 (Table 1) of [Example 1], and the absolute magnetic permeability difference | Δμ | 0.06, and the desired irreversibility cannot be obtained. At 40 GHz, the imaginary part μ ₊ ″ is 0.10 (≧ 0.05), and the magnetic loss increases.

  In sample numbers 68 and 71, since y and z were 0.40 and exceeded 0.39, the content of Fe was too low, and the anisotropic magnetic field was also “0”, which was irreversible. Will not show.

  In sample numbers 72 and 75, n was 5.0 or 6.6, and the value of n was out of the range of 5.0 <n ≦ 6.5. It has been found that the saturation magnetization decreases and a sufficient saturation magnetization cannot be obtained.

On the other hand, in sample numbers 62 to 67, 69, 70, 73 and 74, y and z are respectively 0 <y ≦ 0.33, 0 <z ≦ 0.33, and n is 5.0 <n ≦ 6. 5, the anisotropic magnetic field Ha can be reduced, whereby the absolute magnetic permeability difference | Δμ | becomes 0.1 or more in at least one of 10 GHz and 40 GHz, and a desired irreversibility is obtained. The imaginary part μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced.

That is, in sample numbers 65 and 66, the absolute magnetic permeability difference | Δμ | was 0.1 or more at both 10 GHz and 40 GHz to obtain the desired irreversibility, and the imaginary part μ ₊ ″ was also 0.05. And the magnetic loss is reduced, and a non-reciprocal circuit device usable in both microwave bands can be obtained.

In sample No. 67, at 10 GHz, the imaginary part μ ₊ ″ becomes 0.09 (≧ 0.05) and the magnetic loss increases, but at 40 GHz, the imaginary part μ ₊ ″ becomes 0 and magnetic loss occurs. And the absolute magnetic permeability difference | Δμ | is also 0.16 (≧ 0.1), so that desired irreversibility can be obtained.

In sample numbers 69, 70, 73 and 74, the imaginary part μ ₊ ″ exceeds 0.05 at 40 GHz and the magnetic loss increases, but the imaginary part μ ₊ ″ is 0 at 10 GHz and the magnetic loss is 0. Does not occur, and the absolute magnetic permeability difference | Δμ | is 0.1 or more, so that sufficient irreversibility can be obtained.

As described above, in the sample numbers 62 to 67, 69, 70, 73, and 74, at least one of 10 GHz and 40 GHz, the absolute permeability difference | Δμ | As a result, the imaginary part μ ₊ ″ was also less than 0.05, and it was confirmed that the magnetic loss could be reduced.

By the same method and procedure as in [Example 1], a ferrite porcelain of the general formula {(Sr _1-x Ba _x ) On · (Fe _1-yz Ni _y Sn _z ) ₂ O ₃ } having the composition shown in Table 4 A composition was made.

That is, BaCO ₃ (barium carbonate), Fe ₂ O ₃ (iron oxide), NiO (nickel oxide), and tin oxide (SnO ₂ ) are used as ferrite raw materials, and 0 ≦ x ≦ 1.0, 5.0 ≦ n ≦ 6.6, 0 ≦ y ≦ 0.29, 0 ≦ z ≦ 0.29, and the general formula {(Sr _1-x Ba _x ) On · (Fe _1-yz Ni _y Sn to obtain a ferrite ceramic composition of the sample No. 81-93 represented by _{z) 2} O _3}.

Next, as in [Example 1], the saturation magnetization Ms of each sample, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ at 10 GHz and 40 GHz (irreversibility), and the imaginary part μ of the circularly polarized complex magnetic permeability ₊ ″ (Magnetic loss) was determined.

試料番号８１は、第１の実施例の試料番号１（表１）と同様、従来のＳｒフェライト（異方性磁界Ｈａ：１５３６ｋＡ／ｍ）であり、１０ＧＨｚでは絶対透磁率差｜Δμ｜が０．０６と小さく、所望の非可逆性を得ることができない。また４０ＧＨｚでは虚数部μ_＋″が０．１０（≧０．０５）であり、磁気損失が大きくなる。 Table 4 shows the composition of each sample number, the saturation magnetization Ms, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ, and the imaginary part μ ₊ ″.

Sample No. 81 is a conventional Sr ferrite (anisotropic magnetic field Ha: 1536 kA / m) similarly to Sample No. 1 (Table 1) of the first embodiment, and the absolute magnetic permeability difference | Δμ | 0.06, and the desired irreversibility cannot be obtained. At 40 GHz, the imaginary part μ ₊ ″ is 0.10 (≧ 0.05), and the magnetic loss increases.

  In Sample Nos. 86 and 89, both y and z were 0.29 and exceeded 0.28, so the Fe content was too low, and the anisotropic magnetic field was also “0”, which was irreversible. Will not show any sex.

  In Sample Nos. 90 and 93, n is 5.0 or 6.6, which is out of the range of 5.0 <n ≦ 6.5. It has been found that the saturation magnetization decreases and a sufficient saturation magnetization cannot be obtained.

On the other hand, in sample numbers 82 to 85, 87, 88, 91 and 92, y and z are respectively 0 <y ≦ 0.28, 0 <z ≦ 0.28, and n is 5.0 <n ≦ 6. 5, the anisotropic magnetic field Ha can be reduced, whereby the absolute magnetic permeability difference | Δμ | becomes 0.1 or more in at least one of 10 GHz and 40 GHz to obtain desired irreversibility. The imaginary part μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced.

That is, the sample numbers 82, 83, 87, 88, 91, and 92 can obtain a desired irreversibility because the absolute magnetic permeability difference | Δμ | is 0.1 or more at both 10 GHz and 40 GHz, The imaginary part μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced.

In sample numbers 84 and 85, the absolute magnetic permeability difference | Δμ | is less than 0.1 at 40 GHz and it is difficult to obtain the desired irreversibility, but at 10 GHz, the absolute magnetic permeability difference | Δμ | When it is 0.1 or more, sufficient irreversibility can be obtained, and when the imaginary part μ ₊ ″ becomes 0.01 or 0, magnetic loss can be suppressed.

As described above, in the sample numbers 82 to 85, 87, 88, 91, and 92, at least one of 10 GHz and 40 GHz, the absolute magnetic permeability difference | Δμ | As a result, the imaginary part μ ₊ ″ was also less than 0.05, and it was confirmed that the magnetic loss could be reduced.

In a similar manner and procedure as Example 1, a ferrite porcelain formula having the composition shown in Table _{5 {(Sr 1-X Ba} x) O · n (Fe 1-yz Mn y Sn z) 2 O 3} A composition was made.

That is, BaCO ₃ (barium carbonate), Fe ₂ O ₃ (iron oxide), MnO ₂ (manganese oxide), and tin oxide (SnO ₂ ) are used as ferrite raw materials, and 0 ≦ x ≦ 1.0, 5.0 ≦ n ≦ 6.6, 0 ≦ y ≦ 0.29, 0 ≦ z ≦ 0.29, and prepared by the general formula {(Sr _1-x Ba _x ) On · n (Fe _{1-yz M} n _y to obtain a sn _{z) 2} O ₃ ferrite ceramic composition of the sample No. 101 to 113 represented by}.

Next, as in [Example 1], the saturation magnetization Ms of each sample, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ at 10 GHz and 40 GHz (irreversibility), and the imaginary part μ of the circularly polarized complex magnetic permeability ₊ ″ (Magnetic loss) was determined.

試料番号１０１は、第１の実施例の試料番号１（表１）と同様、従来のＳｒフェライト（異方性磁界Ｈａ：１５３６ｋＡ／ｍ）であり、１０ＧＨｚでは絶対透磁率差｜Δμ｜が０．０６と小さく所望の非可逆性を得ることができない。また４０ＧＨｚでは虚数部μ_＋″が０．１０（≧０．０５）であり、磁気損失が大きくなる。 Table 5 shows the composition of each sample number, the saturation magnetization Ms, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ, and the imaginary part μ ₊ ″.

Sample No. 101 is a conventional Sr ferrite (anisotropic magnetic field Ha: 1536 kA / m) as in Sample No. 1 (Table 1) of the first embodiment. At 10 GHz, the absolute magnetic permeability difference | Δμ | 0.06 and the desired irreversibility cannot be obtained. At 40 GHz, the imaginary part μ ₊ ″ is 0.10 (≧ 0.05), and the magnetic loss increases.

  In Sample Nos. 106 and 109, both y and z were 0.29 and exceeded 0.28, so the Fe content was too low, and the anisotropic magnetic field was also “0”, which was irreversible. Will not show any sex.

  Further, in Sample Nos. 110 and 113, n is 5.0 or 6.6, which is out of the range of 5.0 <n ≦ 6.5, so that the sample no longer shows magnetic anisotropy and the saturation magnetization Ms is It has been found that the saturation magnetization decreases and a sufficient saturation magnetization cannot be obtained.

On the other hand, in sample numbers 102 to 105, 107, 108, 111 and 112, y and z are respectively 0 <y ≦ 0.29, 0 <z ≦ 0.29, and n is 5.0 <n ≦ 6. 5, the anisotropic magnetic field Ha can be reduced, whereby the absolute magnetic permeability difference | Δμ | becomes 0.1 or more in at least one of 10 GHz and 40 GHz, and a desired irreversibility is obtained. The imaginary part μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced.

That is, the sample numbers 102, 103, 107, 108, 111, and 112 can obtain the desired irreversibility because the absolute magnetic permeability difference | Δμ | is 0.1 or more at both 10 GHz and 40 GHz, The imaginary part μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced.

In sample numbers 104 and 105, the absolute magnetic permeability difference | Δμ | is less than 0.1 at 40 GHz and sufficient irreversibility cannot be obtained, but the absolute magnetic permeability difference | Δμ | When it is 1 or more, sufficient irreversibility can be obtained, and the imaginary part μ ₊ ″ is less than 0.05, so that magnetic loss can be suppressed.

As described above, in the sample numbers 102 to 105, 107, 108, 111, and 112, at least one of 10 GHz and 40 GHz, the absolute magnetic permeability difference | Δμ | As a result, the imaginary part μ ₊ ″ was also less than 0.05, and it was confirmed that the magnetic loss could be reduced.

In a similar manner and procedure as Example 1, a ferrite ceramic composition of the general formula _{{(Sr 1-X Bax)} O · n (Fe 1-yz Mg y Sn z) 2 O 3} having the composition shown in Table 6 Object was produced.

That is, BaCO ₃ (barium carbonate), Fe ₂ O ₃ (iron oxide), MgO (magnesium oxide), tin oxide (SnO ₂ ) are used as ferrite raw materials, and 0 ≦ x ≦ 1.0, 5.0 ≦ It is prepared so that n ≦ 6.6, 0 ≦ y ≦ 0.29, and 0 ≦ z ≦ 0.29, and has the general formula {(Sr _1-x Bax) On · n (Fe _1-yz Mg _y Sn _z ) was obtained ferrite ceramic composition of the sample No. 121 to 133 shown by ₂ O _3}.

Next, as in [Example 1], the saturation magnetization Ms of each sample, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ at 10 GHz and 40 GHz (irreversibility), and the imaginary part μ of the circularly polarized complex magnetic permeability ₊ ″ (Magnetic loss) was determined.

試料番号１２１は、〔実施例１〕の試料番号１（表１）と同様、従来のＳｒフェライト（異方性磁界Ｈａ：１５３６ｋＡ／ｍ）であり、１０ＧＨｚでは絶対透磁率差｜Δμ｜が０．０６と小さく、所望の非可逆性を得ることができない。また、４０ＧＨｚでは虚数部μ_＋″が０．１０（≧０．０５）であり、磁気損失が大きくなる。 Table 6 shows the composition of each sample number, the saturation magnetization Ms, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ, and the imaginary part μ ₊ ″.

Sample No. 121 is a conventional Sr ferrite (anisotropic magnetic field Ha: 1536 kA / m) similarly to Sample No. 1 (Table 1) of [Example 1], and the absolute magnetic permeability difference | Δμ | 0.06, and the desired irreversibility cannot be obtained. At 40 GHz, the imaginary part μ ₊ ″ is 0.10 (≧ 0.05), and the magnetic loss increases.

  In Sample Nos. 126 and 129, both y and z were 0.29 and exceeded 0.28, so that the Fe content was too low, and the anisotropic magnetic field was also “0”, which was irreversible. Will not show any sex.

  In sample numbers 130 and 133, n is 5.0 or 6.6, and the value of n is out of the range of 5.0 <n ≦ 6.5. It has been found that the saturation magnetization decreases and a sufficient saturation magnetization cannot be obtained.

On the other hand, in sample numbers 122 to 125, 127, 128, 131 and 132, y and z are respectively 0 <y ≦ 0.29, 0 <z ≦ 0.29, and n is 5.0 <n ≦ 6. 5, the anisotropic magnetic field Ha can be reduced, whereby the absolute magnetic permeability difference | Δμ | becomes 0.1 or more in at least one of 10 GHz and 40 GHz to obtain sufficient irreversibility. The imaginary part μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced.

That is, in sample numbers 122, 127, 128, 131, and 132, the absolute magnetic permeability difference | Δμ | was 0.1 or more at both 10 GHz and 40 GHz, and sufficient irreversibility could be obtained. μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced.

In sample No. 123, at 10 GHz, the imaginary part μ ₊ ″ becomes 0.05 and the magnetic loss increases, but at 40 GHz, the imaginary part μ ₊ ″ becomes 0 and no magnetic loss occurs, and the absolute magnetic permeability difference | Δμ Is also 0.24 (≧ 0.1), and sufficient irreversibility can be obtained.

In sample numbers 124 and 125, at 40 GHz, the absolute magnetic permeability difference | Δμ | was less than 0.1 and sufficient irreversibility could not be obtained, but at 10 GHz, the absolute magnetic permeability difference | Δμ | When it is 1 or more, sufficient irreversibility can be obtained, and the imaginary part μ ₊ ″ becomes 0, so that no magnetic loss occurs.

As described above, the sample numbers 122 to 125, 127, 128, 131, and 132 have a desired irreversibility because the absolute magnetic permeability difference | Δμ | is 0.1 or more in at least one of 10 GHz and 40 GHz. As a result, the imaginary part μ ₊ ″ was also less than 0.05, and it was confirmed that the magnetic loss could be reduced.

A ferrite porcelain composition of the general formula {(Sr _1-x Ba _x ) On · (Fe _1-yz Zn _y Sn _z ) ₂ O ₃ + αCa + βCo} having the composition shown in Table 7 was produced.

That is, SrCO ₃ (strontium carbonate), BaCO ₃ (barium carbonate), Fe ₂ O ₃ (iron oxide), ZnO (zinc oxide), and SnO _{3 were used} as ferrite raw materials by a method and procedure substantially similar to those of [Example 1]. ₂ (tin oxide) was weighed and mixed so that x = 0.2, n = 5.8, y = 0.12, and z = 0.13, and wet-mixed using a ball mill. Calcination was performed in this manner to prepare a calcined powder represented by the general formula {(Sr _1-x Ba _x ) On · n (Fe _1-yz Zn _y Sn _z ) ₂ O ₃ }.

Next, CaCO ₃ (calcium carbonate) and CoO (cobalt oxide) are added to 1 mol of the calcined powder (main component) so that the total content becomes 0 to 0.9000, and wet pulverization is performed. A calcined and pulverized product having a specific surface area of about 5 m ² / g was produced.

Next, the calcined and pulverized product is kneaded with a vinyl acetate-based binder resin to form a slurry, subjected to molding using a dehydration molding machine in a magnetic field, and then subjected to a calcination treatment in the atmosphere, and then performed by a general formula {(Sr _1-x Ba _x ) On · (Fe ₁ -yz Zn _y Sn _z ) ₂ O ₃ + αCa + βCo} to obtain ferrite porcelain compositions of sample numbers 141 to 169.

Next, as in [Example 1], the saturation magnetization Ms of each sample, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ at 10 GHz and 40 GHz (irreversibility), and the imaginary part μ of the circularly polarized complex magnetic permeability ₊ ″ (Magnetic loss) was determined.

  Further, the specific resistivity ρ of each sample was measured by a high resistance measuring machine using a four-terminal method.

  Furthermore, each sample was mounted on the non-radiative dielectric line Y-type circulator shown in the fifth embodiment (FIG. 7), and the signal transmission loss (insertion loss IL) was measured using a network analyzer. .

試料番号１４１〜１６９は、ｘ、ｙ、ｚ、及びｎが本発明範囲内であるので、絶対透磁率差｜Δμ｜が０．１以上となって所望の非可逆性を得ることができ、虚数部μ_＋″も０．０５未満となって磁気損失を低減することができる。 Table 7 shows the composition of each sample, the saturation magnetization Ms, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ, the imaginary part μ ₊ ″, the specific resistivity ρ, and the insertion loss IL.

In sample numbers 141 to 169, since x, y, z, and n are within the range of the present invention, the absolute magnetic permeability difference | Δμ | The imaginary part μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced.

Further, since the sample numbers 141, 142, 149, 156, and 165 have (α + β) values of less than 0.001, the resistivity ρ is as small as 1.2 to 1.4 × 10 ¹¹ Ω · cm and the insertion loss I is small. . L. Also increases to 1.01 to 1.03 dB.

Also. Since sample numbers 148, 155, 160, 164, and 169 have (α + β) values exceeding 0.8, the specific resistivity ρ is as small as 2.0 × 10 ^{9 to} 2.8 × 10 ¹⁰ Ω · cm. Loss I. L. It can also be seen that also increases from 1.26 to 1.54 dB.

On the other hand, the sample numbers 143 to 147, 150 to 154, 157 to 159, 161 to 163, and 166 to 168 have the (α + β) values in the range of 0.0010 to 0.800, and therefore have the specific resistivity ρ Is 1.6 × 10 ^{11 to} 1.8 × 10 ¹³ Ω · cm, and the insertion loss I.I. L. Is 0.55 to 0.99 dB, and the resistivity ρ is increased to increase the insertion loss I. L. Can be obtained.

By the same method and procedure as in [Example 7], the general formula {(Sr _1-x Ba _x ) On (Fe _1-yz Zn _y Sn _z ) ₂ O ₃ + αCa + βCo} (0 ≦ x ≦ 1.0 5.0 ≦ n ≦ 6.6, 0 ≦ y ≦ 0.30, 0 ≦ z ≦ 0.30, α = β = 0.25) The ferrite porcelain compositions of sample numbers 171 to 194 represented by Produced.

As a comparative example, a ferrite porcelain composition to which CaCO ₃ and CoO were not added was prepared.

Next, as in [Example 7], the saturation magnetization Ms of each sample, the anisotropy field Ha, the magnetic permeability difference Δμ (irreversibility) at 10 GHz and 40 GHz, and the imaginary part μ of the circularly polarized complex magnetic permeability ₊ ″ (Magnetic loss) and specific resistivity ρ were determined.

試料番号１７１は、従来のＳｒフェライトにＣａ成分及びＣｏ成分を添加したものであり、１０ＧＨｚでは絶対透磁率差｜Δμ｜が０．０５と小さく所望の非可逆性を得ることができない。また４０ＧＨｚでは虚数部μ_＋″が０．１１（≧０．０５）であり、磁気損失が大きくなる。 Table 8 shows the composition of each sample, the saturation magnetization Ms, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ, the imaginary part μ ₊ ″, and the specific resistivity ρ.

Sample No. 171 is obtained by adding a Ca component and a Co component to a conventional Sr ferrite. At 10 GHz, the absolute magnetic permeability difference | Δμ | is as small as 0.05, so that desired irreversibility cannot be obtained. At 40 GHz, the imaginary part μ ₊ ″ is 0.11 (≧ 0.05), and the magnetic loss increases.

  In sample numbers 181 and 187, since both y and z were 0.30 and exceeded 0.29, the Fe content was too low, and the anisotropic magnetic field was also “0”, which was irreversible. Will not show any sex.

  In sample numbers 188 and 194, n is 5.0 or 6.6, which is out of the range of 5.0 <n ≦ 6.5, so that the sample no longer shows magnetic anisotropy and the saturation magnetization Ms is It has been found that the saturation magnetization decreases and a sufficient saturation magnetization cannot be obtained.

On the other hand, in sample numbers 172 to 180, 182 to 186, and 189 to 193, since x, y, z, and n are within the range of the present invention, the absolute magnetic permeability difference | Δμ | As a result, the desired irreversibility can be obtained, and the imaginary part μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced.

  And, as is clear from Sample Nos. 171 to 194, it is found that the specific resistivity ρ is increased by adding 0.25 mol of each of the Ca component and the Co component as compared with the comparative example in which Ca component and Co component are not added.

By the same method and procedure as in [Embodiment 7], the general formula {(Sr _{1 -x} Ba _x ) On (Fe ₁ -yz Cu _y Sn _z ) ₂ O ₃ + αCa + βCo} (0 ≦ x ≦ 1. 0, 5.0 ≦ n ≦ 6.6, 0 ≦ y ≦ 0.35, 0 ≦ z ≦ 0.35, α = β = 0) to produce ferrite porcelain compositions of sample numbers 201 to 226. did.

As a comparative example, a ferrite porcelain composition to which CaCO ₃ and CoO were not added was prepared.

Next, as in [Example 7], the saturation magnetization Ms of each sample, the anisotropy field Ha, the magnetic permeability difference Δμ (irreversibility) at 10 GHz and 40 GHz, and the imaginary part μ of the circularly polarized complex magnetic permeability ₊ ″ (Magnetic loss) and specific resistivity ρ were determined.

試料番号２０１は、従来のＳｒフェライトにＣａ成分及びＣｏ成分を添加したものであり、１０ＧＨｚでは絶対透磁率差｜Δμ｜が０．０５と小さく所望の非可逆性を得ることができない。また４０ＧＨｚでは虚数部μ_＋″が０．１１（≧０．０５）であり、磁気損失が大きくなる。 Table 9 shows the composition of each sample, the saturation magnetization Ms, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ, the imaginary part μ ₊ ″, and the specific resistivity ρ.

Sample No. 201 is obtained by adding a Ca component and a Co component to a conventional Sr ferrite, and at 10 GHz, the absolute magnetic permeability difference | Δμ | is as small as 0.05, so that desired irreversibility cannot be obtained. At 40 GHz, the imaginary part μ ₊ ″ is 0.11 (≧ 0.05), and the magnetic loss increases.

  In Sample Nos. 213 and 219, both y and z were 0.35 and exceeded 0.33, so the Fe content was too low, and the anisotropic magnetic field was also “0”, which was irreversible. Will not show any sex.

  In sample numbers 220 and 226, n is 5.0 or 6.6, which is out of the range of 5.0 <n ≦ 6.5. It has been found that the saturation magnetization decreases and a sufficient saturation magnetization cannot be obtained.

On the other hand, in sample numbers 202 to 212, 214 to 218, and 221 to 225, since x, y, z, and n are within the range of the present invention, the absolute magnetic permeability difference | Δμ | As a result, the desired irreversibility can be obtained, and the imaginary part μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced.

  As is clear from Sample Nos. 201 to 226, it was found that the specific resistivity ρ was increased by adding 0.25 mol of each of the Ca component and the Co component, as compared with the comparative example in which no Ca component and Co component were added.

By the same method and procedure as in [Embodiment 7], the general formula {(Sr _{1 -x} Ba _x ) On (Fe ₁ -yz Co _y Sn _z ) ₂ O ₃ + αCa + βCo} (0 ≦ x ≦ 1. 0, 5.0 ≦ n ≦ 6.6, 0 ≦ y ≦ 0.40, 0 ≦ z ≦ 0.40, α = β = 0.25) Ferrite porcelain compositions of sample numbers 231 to 245 Was prepared.

As a comparative example, a ferrite porcelain composition to which CaCO ₃ and CoO were not added was prepared.

Next, as in [Example 7], the saturation magnetization Ms of each sample, the anisotropy field Ha, the magnetic permeability difference Δμ (irreversibility) at 10 GHz and 40 GHz, and the imaginary part μ of the circularly polarized complex magnetic permeability ₊ ″ (Magnetic loss) and specific resistivity ρ were determined.

試料番号２３１は、従来のＳｒフェライトにＣａ成分及びＣｏ成分を添加したものであり、１０ＧＨｚでは絶対透磁率差｜Δμ｜が０．０５と小さく所望の非可逆性を得ることができない。また４０ＧＨｚでは虚数部μ_＋″が０．１１（≧０．０５）であり、磁気損失が大きくなる。 Table 10 shows the composition of each sample, the saturation magnetization Ms, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ, the imaginary part μ ₊ ″, and the specific resistivity ρ.

Sample No. 231 is obtained by adding a Ca component and a Co component to a conventional Sr ferrite. At 10 GHz, the absolute magnetic permeability difference | Δμ | is as small as 0.05, so that desired irreversibility cannot be obtained. At 40 GHz, the imaginary part μ ₊ ″ is 0.11 (≧ 0.05), and the magnetic loss increases.

  In Sample Nos. 238 and 241, both y and z were 0.40 and exceeded 0.39, so the Fe content was too low, and the anisotropic magnetic field was also “0”, which was irreversible. Will not show any sex.

  In sample numbers 242 and 245, n is 5.0 or 6.6, and the value of n is out of the range of 5.0 <n ≦ 6.5. It has been found that the saturation magnetization decreases and a sufficient saturation magnetization cannot be obtained.

On the other hand, in sample numbers 232 to 237, 239, 240, 243, and 244, since x, y, z, and n are within the range of the present invention, the absolute magnetic permeability difference | Δμ | As a result, the desired irreversibility can be obtained, and the imaginary part μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced.

  Then, as is clear from each of the sample numbers 231 to 245, it was found that the specific resistance ρ was increased by adding 0.25 mol of each of the Ca component and the Co component as compared with the comparative example in which no Ca component and Co component were added. .

In substantially the same manner and procedure as in Example 7], the general formula _{{(Sr 1-x Ba x} ) O · n (Fe 1-yz Ni y Sn z) 2 O 3 + αCa + βCo} (0 ≦ x ≦ 1. 0, 5.0 ≦ n ≦ 6.6, 0 ≦ y ≦ 0.29, 0 ≦ z ≦ 0.29, α = β = 0.25) Ferrite porcelain compositions of sample numbers 251 to 263 Was prepared.

As a comparative example, a ferrite porcelain composition to which CaCO ₃ and CoO were not added was prepared.

Next, as in [Example 7], the saturation magnetization Ms of each sample, the anisotropy field Ha, the magnetic permeability difference Δμ (irreversibility) at 10 GHz and 40 GHz, and the imaginary part μ of the circularly polarized complex magnetic permeability ₊ ″ (Magnetic loss) and specific resistivity ρ were determined.

試料番号２５１は、従来のＳｒフェライトにＣａ成分及びＣｏ成分を添加したものであり、１０ＧＨｚでは絶対透磁率差｜Δμ｜が０．０５と小さく所望の非可逆性を得ることができない。また４０ＧＨｚでは虚数部μ_＋″が０．１１（≧０．０５）であり、磁気損失が大きくなる。 Table 11 shows the composition of each sample, the saturation magnetization Ms, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ, the imaginary part μ ₊ ″, and the specific resistivity ρ.

Sample No. 251 is obtained by adding a Ca component and a Co component to a conventional Sr ferrite, and at 10 GHz, the absolute magnetic permeability difference | Δμ | is as small as 0.05, so that desired irreversibility cannot be obtained. At 40 GHz, the imaginary part μ ₊ ″ is 0.11 (≧ 0.05), and the magnetic loss increases.

  In sample numbers 256 and 259, since both y and z were 0.29 and exceeded 0.28, the Fe content was too low, and the anisotropic magnetic field was also “0”, which was irreversible. Will not show any sex.

  In sample numbers 260 and 263, n is 5.0 or 6.6, and the value of n is out of the range of 5.0 <n ≦ 6.5. It has been found that the saturation magnetization decreases and a sufficient saturation magnetization cannot be obtained.

On the other hand, in sample numbers 252 to 255, 257, 258, 261 and 262, since x, y, z and n are within the range of the present invention, the absolute magnetic permeability difference | Δμ | As a result, the desired irreversibility can be obtained, and the imaginary part μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced.

  As is clear from the sample numbers 251 to 263, it was found that the specific resistivity ρ was increased by adding 0.25 mol of each of the Ca component and the Co component, as compared with the comparative example in which no Ca component and Co component were added.

In substantially the same manner and procedure as in Example 7], the general formula _{{(Sr 1-x Ba x} ) O · n (Fe 1-yz Mg y Sn z) 2 O 3 + αCa + βCo} (0 ≦ x ≦ 1. 0, 5.0 ≦ n ≦ 6.6, 0 ≦ y ≦ 0.29, 0 ≦ z ≦ 0.29, α = β = 0.25) The ferrite porcelain compositions of sample numbers 271 to 283 represented by: Was prepared.

As a comparative example, a ferrite porcelain composition to which CaCO ₃ and CoO were not added was prepared.

Next, as in [Example 7], the saturation magnetization Ms of each sample, the anisotropy field Ha, the magnetic permeability difference Δμ (irreversibility) at 10 GHz and 40 GHz, and the imaginary part μ of the circularly polarized complex magnetic permeability ₊ ″ (Magnetic loss) and specific resistivity ρ were determined.

試料番号２７１は、従来のＳｒフェライトにＣａ成分及びＣｏ成分を添加したものであり、１０ＧＨｚでは絶対透磁率差｜Δμ｜が０．０５と小さく所望の非可逆性を得ることができない。また４０ＧＨｚでは虚数部μ_＋″が０．１１（≧０．０５）であり、磁気損失が大きくなる。 Table 12 shows the composition of each sample, the saturation magnetization Ms, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ, the imaginary part μ ₊ ″, and the specific resistivity ρ.

Sample No. 271 is obtained by adding a Ca component and a Co component to a conventional Sr ferrite, and at 10 GHz, the absolute magnetic permeability difference | Δμ | is as small as 0.05, so that desired irreversibility cannot be obtained. At 40 GHz, the imaginary part μ ₊ ″ is 0.11 (≧ 0.05), and the magnetic loss increases.

  In Sample Nos. 276 and 279, both y and z were 0.29 and exceeded 0.28, so the Fe content was too low, and the anisotropic magnetic field was also “0”, which was irreversible. Will not show any sex.

  In sample numbers 280 and 283, n is 5.0 or 6.6, and the value of n is out of the range of 5.0 <n ≦ 6.5. It has been found that the saturation magnetization decreases and a sufficient saturation magnetization cannot be obtained.

On the other hand, in each of sample numbers 272 to 275, 277, 278, 281, and 282, since x, y, z, and n are within the range of the present invention, the absolute magnetic permeability difference | Δμ | As a result, desired irreversibility can be obtained, and the imaginary part μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced.

  And as is clear from each of the sample numbers 271 to 283, it was found that the specific resistance ρ was increased by adding 0.25 mol of each of the Ca component and the Co component as compared with the comparative example where no Ca component and Co component were added. .

In substantially the same manner and procedure as in Example 7], the general formula _{{(Sr 1-x Ba x} ) O · n (Fe 1-yz Mn y Sn z) 2 O 3 + αCa + βCo} (0 ≦ x ≦ 1. 0, 5.0 ≦ n ≦ 6.6, 0 ≦ y ≦ 0.29, 0 ≦ z ≦ 0.29, α = β = 0.25) Ferrite porcelain compositions of sample numbers 291 to 303 represented by Was prepared.

As a comparative example, a ferrite porcelain composition to which CaCO ₃ and CoO were not added was prepared.

Next, as in [Example 7], the saturation magnetization Ms of each sample, the anisotropy field Ha, the magnetic permeability difference Δμ (irreversibility) at 10 GHz and 40 GHz, and the imaginary part μ of the circularly polarized complex magnetic permeability ₊ ″ (Magnetic loss) and specific resistivity ρ were determined.

試料番号２９１は、従来のＳｒフェライトにＣａ成分及びＣｏ成分を添加したものであり、１０ＧＨｚでは絶対透磁率差｜Δμ｜が０．０５と小さく所望の非可逆性を得ることができない。また４０ＧＨｚでは虚数部μ_＋″が０．１１（≧０．０５）であり、磁気損失も大きくなる。 Table 13 shows the composition of each sample number, the saturation magnetization Ms, the anisotropic magnetic field Ha, the magnetic permeability difference Δμ, the imaginary part μ ₊ ″, and the specific resistivity ρ.

Sample No. 291 is obtained by adding a Ca component and a Co component to a conventional Sr ferrite. At 10 GHz, the absolute magnetic permeability difference | Δμ | is as small as 0.05, so that desired irreversibility cannot be obtained. At 40 GHz, the imaginary part μ ₊ ″ is 0.11 (≧ 0.05), and the magnetic loss increases.

  In Sample Nos. 296 and 299, both y and z were 0.29 and exceeded 0.28, so the Fe content was too low, and the anisotropic magnetic field was also “0”, which was irreversible. Will not show any sex.

  In Sample Nos. 300 and 303, n is 5.0 or 6.6, and the value of n is out of the range of 5.0 <n ≦ 6.5. It has been found that the saturation magnetization decreases and a sufficient saturation magnetization cannot be obtained.

On the other hand, in sample numbers 292 to 295, 297, 298, 301, and 302, since x, y, z, and n are within the range of the present invention, the absolute magnetic permeability difference | Δμ | As a result, the desired irreversibility can be obtained, and the imaginary part μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced.

  And, as is clear from each of the sample numbers 291 to 303, it was found that the specific resistivity ρ was increased by adding 0.25 mol of each of the Ca component and the Co component as compared with the comparative example in which no Ca component and Co component were added. .

In substantially the same manner and procedure as in Example 1], the general formula _{{(Sr 1-x Ba x} ) O · n (Fe 1-yz Zn y Sn z) 2 O 3} (x = 0.2, n = 5.8, y = 0.12, z = 0.13).

Next, with respect to 1 mol of this calcined powder (main component), 0.25 mol of CaCO ₃ (calcium carbonate) and 0.25 mol of CoO (cobalt oxide), MnO (manganese oxide) and ZrO ₂ (zirconium oxide) were added. These contents were added so that the total amount would be 0.05 to 1.60% by weight, and by the same method and procedure as in [Example 7], the general formula {(Sr _1-x Ba _x ) O · n Ferrite porcelain compositions of sample numbers 311 to 322 represented by (Fe _1-yz Zn _y Sn _z ) ₂ O ₃ + αCa + βCo} (α = β = 0.25) were produced.

Next, as in [Example 7], the magnetic permeability difference Δμ (irreversibility) of each sample at 10 GHz and 40 GHz, the imaginary part μ ₊ ″ (magnetic loss) of the circularly polarized complex permeability, and the specific resistivity ρ was determined.

各試料番号３１１〜３２２は、ｘ、ｙ、ｚ、ｎがいずれも本発明の範囲内にあるため、ｘ、ｙ、ｚ、及びｎが本発明範囲内であるので、絶対透磁率差｜Δμ｜が０．１以上となって所望の非可逆性を得ることができ、虚数部μ_＋″も０．０５未満となって磁気損失を低減することができる。 Table 14 shows the composition of each sample, the magnetic permeability difference Δμ, the imaginary part μ ₊ ″, and the specific resistivity ρ.

In each of sample numbers 311 to 322, since x, y, z, and n are all within the scope of the present invention, and x, y, z, and n are within the scope of the present invention, the absolute magnetic permeability difference | Δμ Is 0.1 or more, desired irreversibility can be obtained, and the imaginary part μ ₊ ″ is also less than 0.05, so that magnetic loss can be reduced.

However, in sample numbers 316 and 322, the total contents of the Mn component and the Zr component were 1.52% by weight and 1.68% by weight, respectively, and exceeded 1.50% by weight. Is as low as 1.4 to 1.7 × 10 ¹⁰ Ω · cm.

On the other hand, in sample numbers 311 to 315 and 317 to 321, the Mn component and / or the Zr component are added so that the total content is in the range of 1.50% by weight or less. It was found that ρ increased remarkably to 1.7 × 10 ¹³ Ω · cm or more.

By the same method and procedure as in [Example 1], the general formula {(Sr _1-x Ba _x ) On · (Fe _1-yz Zn _y Sn _z ) ₂ O ₃ (x = 0.2, n = 5 .8, y = 0.12, z = 0.13).

Then added to MnO the calcined powder to the (manganese oxide) and ZrO ₂ (zirconium oxide) total content thereof is 0.05 to 1.60 wt% (active ingredient), EXAMPLES The ferrite porcelain compositions of Sample Nos. 331 to 342 were produced by the same method and procedure as in Example 7].

Next, as in [Example 1], the magnetic permeability difference Δμ (irreversibility) at 10 GHz and 40 GHz of each sample and the imaginary part μ ₊ ″ (magnetic loss) of the circularly polarized complex magnetic permeability were determined. In the same manner as in [Example 7], the specific resistivity ρ of each sample was measured.

各試料番号３３１〜３４２は、ｘ、ｙ、ｚ、及びｎが本発明範囲内であるので、絶対透磁率差｜Δμ｜が０．１以上となって所望の非可逆性を得ることができ、虚数部μ_＋″も０．０５未満となって磁気損失を低減することができる。 Table 15 shows the composition of each sample number, the magnetic permeability difference Δμ, the imaginary part μ ₊ ″, and the specific resistivity ρ.

In each of Sample Nos. 331 to 342, since x, y, z, and n are within the range of the present invention, the absolute irreversibility can be obtained since the absolute magnetic permeability difference | Δμ | , The imaginary part μ ₊ ″ is also less than 0.05, so that the magnetic loss can be reduced.

However, in sample numbers 336 and 342, the total contents of the Mn component and the Zr component were 1.52% by weight and 1.68% by weight, respectively, and exceeded 1.50% by weight. Is extremely low at 8.1 to 9.7 × 10 ⁶ Ω · cm.

On the other hand, in sample numbers 331 to 335 and 337 to 341, since the Mn component and / or the Zr component are added so that the total content is in the range of 1.50% by weight or less, the specific resistivity is low. It was found that ρ was dramatically improved to 1.0 × 10 ¹⁰ Ω · cm or more.

In a similar manner and procedure as in Example 15], in the general formula of the composition shown in Table _{16 {(Sr 1-x Ba} x) O · n (Fe 1-yz Me y Sn z) 2 O 3} Ferrite porcelain compositions of sample numbers 351 to 356 represented were prepared.

  Next, the resistivity ρ of each sample was measured in the same manner as in [Example 7].

この表１６から明らかなように、Ｍｎ成分及びＺｒ成分の含有量の総計を０．９２重量％（Ｍｎ：０．９０重量％、Ｚｒ：０．０２重量％）とした試料番号３５１〜３５６は比較例に比べ、比抵抗率ρが約１０００倍であり飛躍的に増大することが分かった。 Table 16 shows the composition and specific resistivity ρ of each sample number. As Comparative Examples, the corresponding measurement results shown in Comparative Examples in Tables 8 to 13 are described.

As is clear from Table 16, the sample numbers 351 to 356 in which the total content of the Mn component and the Zr component was 0.92% by weight (Mn: 0.90% by weight, Zr: 0.02% by weight) It was found that the specific resistivity ρ was about 1000 times as much as that of the comparative example, and was dramatically increased.

In a similar manner and procedure as Example 14, the general formula of the composition shown in Table _{17 {(Sr 1-x Ba} x) O · n (Fe 1-yz Zn y Sn z) 2 O 3 + αCa + βCo} The ferrite porcelain compositions of sample numbers 361 to 366 represented by are prepared.

  Next, the resistivity ρ of each sample was measured in the same manner as in [Example 7].

この表１７から明らかなように、各試料には所定量のＣａ成分及びＣｏ成分が含有されているため、〔実施例１６〕に比べると増大量は小さいが、それでもＭｎ成分及びＺｒ成分の含有量の総計を０．９２重量％（Ｍｎ：０．９０重量％、Ｚｒ：０．０２重量％）とした試料番号３６１〜３６６は比較例に比べ、比抵抗率ρが約１００倍となり増大することが分かった。 Table 17 shows the composition and specific resistivity ρ of each sample number. Also, as comparative examples, the corresponding measurement results shown in Examples in Tables 8 to 13 are described.

As is clear from Table 17, since each sample contains a predetermined amount of Ca component and Co component, the amount of increase is smaller than that of [Example 16], but the content of Mn component and Zr component is still higher. Sample numbers 361 to 366 in which the total amount was 0.92% by weight (Mn: 0.90% by weight, Zr: 0.02% by weight) increased the specific resistivity ρ to about 100 times as compared with the comparative example. I understood that.

FIG. 3 is a diagram schematically showing a frequency characteristic of a magnetic permeability difference Δμ of the ferrite porcelain composition according to the present invention. It is a figure which shows the magnetic resonance half width of the ferrite porcelain composition which concerns on this invention. It is a perspective view showing a 1st embodiment of a nonreciprocal circuit device concerning the present invention. It is the front view (a) which shows 2nd Embodiment of the non-reciprocal circuit element which concerns on this invention, and the principal part top view (AA arrow view). It is a perspective view showing a 3rd embodiment of a nonreciprocal circuit device concerning the present invention. It is a perspective view showing a 4th embodiment of the non-reciprocal circuit device concerning the present invention. It is a perspective view showing a 5th embodiment of a nonreciprocal circuit device concerning the present invention. It is a perspective view showing a 6th embodiment of a nonreciprocal circuit device concerning the present invention. It is a top view showing a 7th embodiment of a nonreciprocal circuit device concerning the present invention. It is a perspective view showing an 8th embodiment of a nonreciprocal circuit device concerning the present invention. It is a perspective view showing a 9th embodiment of a non-reciprocal circuit device concerning the present invention. FIG. 1 is a system configuration diagram showing an embodiment of a wireless device according to the present invention. FIG. 3 is a diagram showing an example of frequency characteristics of a magnetic permeability difference Δμ of the ferrite porcelain composition of the present invention together with a comparative example (Ba ferrite). It is the figure which showed an example of the frequency characteristic of the imaginary part (micro | micron | mu) ₊ "of the ferrite porcelain composition of this invention with the comparative example (Ba ferrite). It is a figure which shows the frequency characteristic of each magnetic permeability component of the complex magnetic permeability of the conventional Sr ferrite. It is a figure which shows the frequency characteristic of the magnetic permeability difference (DELTA) micro of the conventional Sr ferrite.

Explanation of reference numerals

Reference Signs List 3 ferrite substrate 6 ferrite substrate 9 ferrite substrate 12 ferrite columns 14a, 14b ferrite substrate 17 ferrite rod 21 ferrite substrates 26a to 26c ferrite substrate 28 ferrite column 31 isolator 32 circulator

Claims (9)

Formula _{{(Sr 1-x Ba x} ) O · n (Fe 1-yz Me y Sn z) 2 O 3} (0 ≦ x ≦ 1.0,5.0 <n ≦ 6.5, y> 0 , Z> 0), wherein Me is at least one divalent metal element.   2. The ferrite porcelain composition for a non-reciprocal circuit device according to claim 1, wherein said Me is made of Zn, and said y and z are respectively 0 <y ≦ 0.29 and 0 <z ≦ 0.29.   2. The ferrite porcelain composition for a non-reciprocal circuit device according to claim 1, wherein the Me is made of Cu, and y and z are respectively 0 <y ≦ 0.33 and 0 <z ≦ 0.33. 3.   The ferrite porcelain composition for a non-reciprocal circuit device according to claim 1, wherein the Me is made of Co, and the y and z are respectively 0 <y ≦ 0.39 and 0 <z ≦ 0.39.   2. The device according to claim 1, wherein the Me is made of any one of Ni, Mn, and Mg, and the y and z satisfy 0 <y ≦ 0.28 and 0 <z ≦ 0.28, respectively. 3. Ferrite porcelain composition for non-reciprocal circuit devices.   It contains at least one of a Ca component and a Co component as an auxiliary component, and the content of the Ca component and the Co component is 0.001 to 0.8 mol in total with respect to 1 mol of the main component. The ferrite porcelain composition for a non-reciprocal circuit device according to claim 1.   It contains at least one of a Mn component and a Zr component as an accessory component, and the total content of the Mn component and the Zr component is 1.50% by weight or less (not including 0% by weight) in terms of oxide. The ferrite porcelain composition for a non-reciprocal circuit device according to any one of claims 1 to 6, wherein:   A nonreciprocal circuit device comprising a ferrite member formed of the ferrite porcelain composition according to any one of claims 1 to 7.   A wireless device comprising the non-reciprocal circuit device according to claim 8.

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