JPWO2004113250A1 - Ferrite porcelain composition for nonreciprocal circuit element, nonreciprocal circuit element, and wireless device - Google Patents

Abstract

In the present invention, the main component of the ferrite porcelain composition is the general formula (Sr1-xBax) O.n (Fe1-yIny) 2O3 (0 ≦ x ≦ 1.0, 5.00 <n ≦ 6.00, 0 < y ≦ 0.30), or the general formula (Sr1-xBax) O.n (Fe1-zAlz) 2O3 (0 ≦ x ≦ 1.0, 5.00 <n ≦ 6.00, 0 <z ≦ 0.30) ), Or general formula (Sr1-xBax) O.n (Fe1-y-zInyAlz) 2O3 (0 ≦ x ≦ 1.0, 5.00 <n ≦ 6.00, 0 <y ≦ 0.30, 0 < z ≦ 0.30). The nonreciprocal circuit device obtained by using this composition can obtain sufficient nonreciprocity even when used in a microwave / millimeter wave band of 10 GHz or less or 30 to 60 GHz, and the porcelain loss is reduced. It is suitable for wireless devices used in the microwave and millimeter wave bands.

Description

  The present invention relates to a ferrite porcelain composition for a nonreciprocal circuit element, a nonreciprocal circuit element, and a radio apparatus, and in particular, a microwave / millimeter wave band (hereinafter, simply referred to as “microwave band”) having a frequency of several GHz to several tens GHz. ) Suitable for use in a nonreciprocal circuit element, a nonreciprocal circuit element such as an isolator or a circulator formed using the ferrite porcelain composition, and a wireless device including the nonreciprocal circuit element .

As a nonreciprocal circuit element used in a microwave band such as a cellular phone or a millimeter wave radar, a nonreciprocal circuit element that applies a DC magnetic field with a permanent magnet is conventionally known.
The nonreciprocal circuit element uses a garnet ferrite typified by yttrium iron garnet Y ₃ Fe ₅ O ₁₂ (hereinafter referred to as “YIG”), a spinel ferrite typified by Mg ferrite or NiCuZn ferrite, and a rare earth magnet. A DC magnetic field is applied and driven by a permanent magnet such as an Sr ferrite magnet.
In the nonreciprocal circuit element, garnet ferrite is usually used in the ultrahigh frequency / microwave band of several hundreds of MHz to several GHz, and spinel ferrite is used in the microwave band of several tens of GHz.
In other words, garnet-based ferrite has a large magnetic loss peak on the low magnetic field side in the ultra-high frequency or microwave band of several hundreds of MHz to several GHz, so that a non-reciprocal circuit element with low magnetic loss cannot be obtained. The magnetic field is driven on the higher magnetic field side than the ferromagnetic resonance peak.
On the other hand, spinel 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, the ferromagnetic resonance peak and the low magnetic field loss peak are sufficiently separated from each other, so that a nonreciprocal circuit element having sufficiently low magnetic loss can be obtained even when driven with a low magnetic field. In addition, since it is difficult to sufficiently saturate the spinel ferrite (saturation magnetization of about 0.4 T) with a permanent magnet, the permanent magnet is driven on the lower magnetic field side than the ferromagnetic resonance peak. When a magnetic field is generated, a high-frequency magnetic field generates a circularly polarized wave that rotates clockwise in the direction of the DC magnetic field and a negatively circularly polarized wave that rotates counterclockwise, but the complex permeability μ of the ferrite is positive. Unlike circularly polarized waves and negatively circularly polarized waves, non-reciprocal circuit elements are realized by utilizing such properties.
That is, the complex magnetic permeability μ of the ferrite is expressed by Equation (1), where the real part μ ′ indicates the magnetization response 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 the absolute magnetic permeability difference | Δμ | And the imaginary part μ ₊ ″ of the circularly polarized magnetic permeability μ ₊ can be evaluated.
By the way, cellular phones used in the microwave band of several GHz are required to further reduce the height, size, and cost of devices, and accordingly, reduce the height and size of nonreciprocal circuit elements. Therefore, cost reduction has been demanded.
However, since garnet ferrite requires a permanent magnet for applying a DC magnetic field, there is a limit to reducing the height, size and cost of nonreciprocal circuit elements.
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 element is expected, but if spinel ferrite is used for the nonreciprocal circuit element, As in the case of ferrite, a permanent magnet is required, so there is a limit to reducing the height, size, and cost of nonreciprocal circuit elements.
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 Such non-reciprocal circuit devices have also been known.
In the self-biased nonreciprocal circuit device, for example, Ba ferrite has an anisotropic magnetic field Ha of 1.40 × 10 ⁶ A / m, and Sr ferrite has 1.54 × 10 ⁶ A. Since the magnetic field has an anisotropic magnetic field Ha of / m, the magnetic field is generated by driving the anisotropic magnetic field Ha without requiring a permanent magnet.
As described above, the self-biased nonreciprocal circuit element using the magnetoplumbite type ferrite does not require a permanent magnet for applying a magnetic field such as garnet ferrite or spinel ferrite, and thus has a low profile of the nonreciprocal circuit element. Promising from the viewpoint of downsizing, miniaturization and cost reduction.
Then, as such a self-biased nonreciprocal circuit element that does not require a permanent magnet, an isolator (nonreciprocal circuit element) is mounted together with a semiconductor chip in a microwave integrated circuit or a microwave circuit module in a surface mount form. A technique has been proposed (Japanese Patent Laid-Open No. 11-17408).
However, conventional non-reciprocal circuit elements of the self-bias operation type cannot obtain sufficient irreversibility in the microwave band of 10 GHz or less, and magnetic loss is large in the microwave band of 30 to 60 GHz. There is a problem that it is not suitable for use in the microwave band.
FIG. 1 shows frequency characteristics of magnetic permeability components μ ₊ ′, μ ₊ ″, μ ₋ ′, and μ ₋ ″ of positive and negative circularly polarized magnetic permeability μ _± of Sr ferrite as an example of a magnetoplumbite type ferrite. . The horizontal axis represents frequency (GHz), and the vertical axis represents permeability components μ ₊ ′, μ ₊ ″, μ ₋ ′, and μ ₋ ″ of positive and negative circularly polarized magnetic permeability μ _± .
FIG. 2 shows the permeability difference Δμ when Sr ferrite is used in a self-biased nonreciprocal circuit device. The horizontal axis is frequency (GHz), and the vertical axis is permeability difference Δμ.
As apparent from FIGS. 1 and 2, the microwave band of 10 to 30 GHz can be driven on the higher magnetic field side than the ferromagnetic resonance peak, and the microwave band of 60 to 200 GHz can be driven from the ferromagnetic resonance peak. It can be driven on the low magnetic field side.
However, as shown in FIG. 1, in the microwave band of 30-60 GHz, the imaginary part μ ₊ ″ of the circularly polarized magnetic permeability increases significantly from the threshold value of 0.05, resulting in a large magnetic loss. Thus, a low-loss nonreciprocal circuit device cannot be obtained.
On the other hand, as shown in FIG. 2, in the microwave band of 10 GHz or less, the permeability difference Δμ is as small as less than 0.1, and desired irreversibility cannot be obtained.
That is, the conventional self-biased irreversible circuit element cannot obtain a 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. Even when used in a microwave band of 10 GHz or less or 30 to 60 GHz, sufficient irreversibility can be obtained, and magnetic loss can be reduced. It is an object of the present invention to provide a ferrite porcelain composition for non-reciprocal circuit elements that can be performed, a self-biased non-reciprocal circuit element manufactured using the ferrite porcelain composition, and a wireless device.

The inventors of the present invention have made extensive studies in order to achieve the above object. As a result, a portion of Fe ³⁺ contained in the magnetoplumbite type hexagonal ferrite is replaced with In ³⁺ to reduce the anisotropic magnetic field Ha. Can be controlled in the direction, thereby improving the irreversibility of the ferrite porcelain composition in the microwave band of 10 GHz or less, and further shifting the frequency of the ferromagnetic resonance peak to the low frequency side. It was possible to obtain the knowledge that magnetic loss in the microwave band of 30 to 60 GHz can be suppressed.
That is, the ferrite porcelain composition for non-reciprocal circuit elements according to the present invention (hereinafter simply referred to as “ferrite porcelain composition”) has the general formula {(Sr _1-x Ba _x ) O · n (Fe _{1- yz).} In _y ) ₂ O ₃ } (0 ≦ x ≦ 1.00, 5.00 ≦ n <6.00, 0 <y ≦ 0.30). .
According to the ferrite porcelain composition, the general formula {(Sr _1−x Ba _x ) O · n (Fe _1−y In _y ) ₂ O ₃ } (0 ≦ x ≦ 1.00, 5.00 ≦ n < 6.00, 0 <y ≦ 0.30), the desired irreversibility can be obtained even in the microwave band of 10 GHz or less or 30 to 60 GHz, and the magnetic loss can be reduced. A small ferrite porcelain composition can be obtained.
Conventionally, in the microwave band of 30 to 60 GHz, the irreversibility is good (see FIGS. 1 and 2), but there is a disadvantage that the magnetic loss is large.
Therefore, the present inventors have conducted intensive research. As a result, the anisotropic magnetic field Ha can be controlled in the increasing direction by substituting a part of the above-described Fe ³⁺ with Al ^3+. It was found that the peak frequency can be shifted to the high frequency side, and as a result, magnetic loss can be suppressed without impairing irreversibility even in the microwave band of 30 to 60 GHz.
That is, the ferrite ceramic composition according to the present invention, the general formula _{{(Sr 1-x Ba x} ) O · n (Fe 1-z Al z) 2 O 3} (0 ≦ x ≦ 1.00,5.00 ≦ n <6.00, 0 <z ≦ 0.30).
According to the ferrite porcelain composition, the general formula {(Sr _1−x Ba _x ) O · n (Fe _1−z Al _z ) ₂ O ₃ } (0 ≦ x ≦ 1.00, 5.00 ≦ n < 6.00, 0 <z ≦ 0.30), the magnetic loss can be reduced even in the microwave band of 30 to 60 GHz, and irreversible even in such a frequency band. And a ferrite porcelain composition having a low magnetic loss can be obtained.
Further, as a result of further diligent research by the present inventors, by replacing a part of Fe ³⁺ with In ³⁺ and Al ^{3 +} , a desired irreversibility and low in a microwave band of 10 GHz or less and 30 to 60 GHz. It was found that a ferrite porcelain composition adjusted to have magnetic loss can be obtained.
That is, the ferrite ceramic composition according to the present invention, the general formula _{{(Sr 1-x Ba x} ) O · n (Fe 1-y-z In y Al z) 2 O 3} (0 ≦ x ≦ 1.00 , 5.00 ≦ n <6.00, 0 <y ≦ 0.30, 0 <z ≦ 0.30).
According to the ferrite porcelain composition, the general formula {(Sr _1−x Ba _x ) O · n (Fe _{1− yz} −In _y Al _z ) ₂ O ₃ } (0 ≦ x ≦ 1.00, 5. 00 ≦ n <6.00, 0 <y ≦ 0.30, 0 <z ≦ 0.30), in addition to the above effects, variation of the anisotropic magnetic field Ha The saturation magnetization Ms can be changed while suppressing the magnetic field, thereby controlling the ferromagnetic resonance peak and the permeability difference, and the desired irreversibility and low magnetism even in the microwave band of 10 GHz or less or 30 to 60 GHz. It becomes possible to easily obtain a ferrite porcelain composition having a loss.
By the way, in the nonreciprocal circuit element, the shorter the distance between the permanent magnet and the ferrite porcelain composition, the more the transmission characteristics deteriorate due to the influence of eddy current loss generated in the permanent magnet. And this eddy current is easy to generate | occur | produce, so that the specific resistivity (rho) of a permanent magnet is small. In addition, in the self-biased nonreciprocal circuit element, the ferrite porcelain composition itself generates a magnetic field, and thus the influence of eddy current loss is very large. Therefore, in order to avoid deterioration of transmission characteristics in a self-biased non-reciprocal circuit element, it is necessary to reduce eddy current loss, and to that end, it is necessary to increase the specific resistivity ρ of the ferrite porcelain composition.
And as a result of the present inventors' extensive research, at least one of the Ca component and the Co component is added in a total amount of 0.001 to 0.8 mol with respect to 1 mol of the main component, The specific content ρ can be increased by adding the total content of the Mn component and the Zr component in the ferrite porcelain composition in the range of 1.5% by weight or less in terms of oxide. Obtained knowledge.
That is, the ferrite porcelain composition of the present invention includes at least one of a Ca component and a Co component as a subcomponent, and the content of the Ca component and the Co component is 0. 0 in total with respect to 1 mole of the main component. 001-0.8 mol is contained, and at least one of the Mn component and the Zr component is contained as a subcomponent, and the content of the Mn component and the Zr component is the total in terms of oxides. 1.50% by weight or less (excluding 0% by weight).
According to the above ferrite porcelain composition, 0.001 to 0.8 mol of at least one of Ca component and Co component as subcomponents is contained with respect to 1 mol of the main component, and the Mn component and Zr. Since at least one of the components is contained in the range of 1.50% by weight or less (not including 0% by weight) in terms of oxide, a ferrite porcelain composition having a large specific resistivity ρ Thus, the influence of eddy current loss generated in the permanent magnet of the nonreciprocal circuit element can be reduced, and a self-biased nonreciprocal circuit element having good transmission characteristics can be obtained.
The nonreciprocal circuit device according to the present invention includes a ferrite member formed of the ferrite porcelain composition.
According to the nonreciprocal circuit element, the nonreciprocal circuit element has desired nonreciprocity even in a microwave band of several GHz to several tens GHz, low magnetic loss, low dielectric loss tan δ, and high specific resistance ρ. Can be obtained. In addition, since the ferrite porcelain composition can be driven using the anisotropic magnetic field Ha, a permanent magnet is not required, and it is possible to reduce the size, height, and cost.
A wireless device according to the present invention includes the nonreciprocal circuit element.
According to the wireless device, since the non-reciprocal circuit element described above is provided, the magnetic loss is small in the microwave band of several GHz to several tens GHz, the desired non-reciprocity is provided, and the dielectric loss tan δ is low. It is possible to obtain a wireless device such as a mobile phone, a millimeter wave radar, and the like that is provided with a self-biased nonreciprocal circuit element having a large specific resistivity ρ and is reduced in size, height, and cost.

  FIG. 1 is a diagram showing frequency characteristics of each permeability component of the complex permeability of a conventional Sr ferrite. FIG. 2 is a diagram showing the frequency characteristics of the permeability difference Δμ of the conventional Sr ferrite. FIG. 3 is a diagram schematically showing frequency characteristics of the permeability difference Δμ of the ferrite porcelain composition according to the present invention. FIG. 4 is a diagram showing the magnetic resonance half width of the ferrite porcelain composition according to the present invention. FIG. 5 is a perspective view showing a first embodiment of a non-reciprocal circuit device according to the present invention. FIG. 6: is the front view (a) which shows 2nd Embodiment of the nonreciprocal circuit device based on this invention, and a principal part top view (AA arrow directional view). FIG. 7 is a perspective view showing a third embodiment of a non-reciprocal circuit device according to the present invention. FIG. 8 is a perspective view showing a fourth embodiment of a non-reciprocal circuit device according to the present invention. FIG. 9 is a perspective view showing a fifth embodiment of a non-reciprocal circuit device according to the present invention. FIG. 10 is a perspective view showing a sixth embodiment of a non-reciprocal circuit device according to the present invention. FIG. 11 is a plan view showing a seventh embodiment of a non-reciprocal circuit device according to the present invention. FIG. 12 is a perspective view showing an eighth embodiment of a non-reciprocal circuit device according to the present invention. FIG. 13 is a perspective view showing a ninth embodiment of a non-reciprocal circuit device according to the present invention. FIG. 14 is a system configuration diagram showing an embodiment of a radio apparatus according to the present invention.

Next, an embodiment of the present invention will be described in detail.
The ferrite porcelain composition according to the first embodiment of the present invention is represented by the following general formula [A].
_{(Sr 1-x Ba x)} O · n (Fe 1-y In y) 2 O 3 ... [A]
However, x is 0 ≦ x ≦ 1.0, n is 5.00 ≦ n <6.00, and y is 0 <y ≦ 0.30.
That is, the ferrite porcelain composition of the first embodiment is a magneto-plavant type represented by the general formula (Sr _1-x Ba _x ) O · nFe ₂ O ₃ (where 0 ≦ x ≦ 1.0). In ferrite, a part of Fe ³⁺ is substituted with In ³⁺ .
The reason why a part of Fe ³⁺ is substituted with In ³⁺ is as follows.
In the magnetoplumbite type ferrite, a magnetic field is generated by driving an anisotropic magnetic field Ha. However, according to the results of experiments by the present inventors, anisotropy is obtained by substituting a part of Fe ³⁺ with In ^3+. It has been found that the magnetic field Ha can be controlled in the decreasing direction. For example, when the Fe component of the Ba ferrite of the magnetoplumbite type is replaced with the In component, the anisotropic magnetic field Ha is higher than the anisotropic magnetic field of the Ba ferrite itself (1.40 × 10 ⁶ (A / m)). Decrease. At this time, the saturation magnetization Ms also changes in the decreasing direction.
On the other hand, the internal magnetic field Hin is expressed by Equation (2), and the frequency ω (= 2πfr) of the ferromagnetic resonance peak is expressed by Equation (3).
Hin = Ha−N × Ms (2)
ω = γ × Hin (3)
Here, N is a demagnetizing factor, Ms is a saturation magnetization (T), and γ is a gyro constant (= 2.21 × 10 ⁵ m / A · s).
Therefore, since the internal magnetic field Hin also varies as appropriate according to the variation of the anisotropic magnetic field Ha and the saturation magnetization Ms according to Equation (2), the frequency ω of the ferromagnetic resonance peak also varies according to Equation (3).
As the anisotropic magnetic field Ha decreases in this way, the frequency ω of the ferromagnetic resonance peak fluctuates. As a result, as shown in FIG. 3, the magnetic permeability of the real part of the positive and negative circular polarizations is obtained. The frequency characteristic of the difference Δμ can be changed from the characteristic indicated by the phantom line to the characteristic indicated by the solid line as indicated by the arrow X, and sufficient irreversibility can be obtained even when used in a microwave band of 10 GHz or less. It becomes possible to obtain a ferrite porcelain composition.
The imaginary part μ ₊ ″ indicating magnetic loss is known to be a Lorentzian distribution curve with respect to the internal magnetic field Hin (= ω / γ) as shown in FIG. As a result, the half width ΔH of the magnetic resonance peak can be reduced, and at the same time, the frequency ω of the ferromagnetic resonance peak can be shifted to the low frequency side. As a result, the imaginary part μ ₊ ″ can be reduced, It is possible to suppress magnetic loss at 30 to 60 GHz.
The present inventors have confirmed that a similar effect can be obtained by substituting a part of Fe ³⁺ with Sn ⁴⁺ . However, a part of Fe ³⁺ is replaced with Sn ⁴⁺ . When substituted, the charge balance is lost, so it is necessary to correct the charge with a divalent metal element such as Zn ²⁺ or Cu ²⁺ , while the In ion is trivalent, so Fe ³⁺ is replaced with In ^3+. However, the charge balance is not lost, and it is not necessary to correct the charge with a divalent metal element.
In the above general formula [A], y is set to 0 <y ≦ 0.30. When y exceeds 0.30, the In content becomes excessive, while the Fe content is excessively low. This is because the magnetic anisotropy is not exhibited, and the material cannot be used as a non-magnetic material.
In the above general formula [A], n is set to 5.00 ≦ n <6.00 because when n is outside this range, no magnetic anisotropy is exhibited, and a heterogeneous phase is precipitated or sintered. This is because a sufficient saturation magnetization Ms is not obtained, and the specific resistivity ρ is also reduced.
And the said ferrite porcelain composition is manufactured as follows.
That is, the barium compound, strontium compound, iron compound, and indium compound as ferrite raw materials are appropriately weighed and prepared so that the component composition of the ferrite ceramic composition as a final product has a predetermined molar ratio, After wet mixing, the mixture is calcined in the air and then wet pulverized to produce 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 above general formula [A]. The
Thus, in the ferrite porcelain composition of the first embodiment, a portion of Fe ³⁺ of the magnetoplumbite-type ferrite is replaced with In ³⁺ , so that a desired frequency band in the microwave band of 10 GHz or 30 to 60 GHz is obtained. A ferrite porcelain composition having irreversibility and low magnetic loss and suitable for non-reciprocal circuit elements can be obtained.
Next, the ferrite porcelain composition according to the second embodiment of the present invention will be described in detail.
The ferrite porcelain composition according to the second embodiment is represented by the following general formula [B].
_{(Sr 1-x Ba x)} O · n (Fe 1-z Al z) 2 O 3 ... [B]
However, x is 0 ≦ x ≦ 1.0, n is 5.00 ≦ n <6.00, and z is 0 <z ≦ 0.30.
That is, the ferrite porcelain composition of the second embodiment is a magneto-plavant type represented by the general formula (Sr _1-x Ba _x ) O · nFe ₂ O ₃ (where 0 ≦ x ≦ 1.0). In ferrite, a part of Fe ³⁺ is replaced with Al ³⁺ .
The reason why a part of Fe ³⁺ is substituted with Al ³⁺ is as follows.
The magnetoplumbite-type ferrite as described above, but by generating a magnetic field by driving the anisotropic magnetic field Ha, the experimental result of the present inventors, by substituting a part of Fe ³⁺ in the Al ³⁺ by Thus, it was found that the frequency ω of the ferromagnetic resonance peak can be shifted to the high frequency side. That is, also in the second embodiment, by replacing a part of Fe ³⁺ with Al ³⁺ , the half width ΔH of the magnetic resonance peak can be reduced as in the first embodiment. The frequency ω of the ferromagnetic resonance peak can be shifted to the high frequency side. As a result, the imaginary part μ ₊ ″ in the microwave band of 30 to 60 GHz can be reduced, and magnetic loss can be suppressed.
In other words, conventional magnetoplumbite type ferrites such as Br ferrite and Sr ferrite have the disadvantage of large magnetic loss, although they can satisfy irreversibility in the microwave band of 30-60 GHz. In this embodiment, by replacing part of Fe ³⁺ with Al ³⁺ , magnetic loss can be suppressed even in the microwave band of 30 to 60 GHz, and both irreversibility and low magnetic loss can be achieved. It is possible to obtain a ferrite porcelain composition that can be used.
In the above general formula [B], z is set to 0 <z ≦ 0.30. If Z exceeds 0.30, the Al content becomes excessive, while the Fe content is too low. This is because the magnetic anisotropy is not exhibited, and the material cannot be used as a non-magnetic material.
The ferrite porcelain composition of the second embodiment also uses the aluminum compound instead of the indium compound for the ferrite raw material, and the above general formula [B] by the method and procedure substantially the same as those of the first embodiment. It is possible to easily produce a ferrite porcelain composition represented by:
Next, the ferrite porcelain composition according to the third embodiment of the present invention will be described in detail.
The ferrite porcelain composition according to the third embodiment is represented by the following general formula [C].
_{(Sr 1-x Ba x)} O · n (Fe 1-y-z In y Al z) 2 O 3 ... [C]
However, x is 0 ≦ x ≦ 1.0, and n is 5.00 ≦ n <6.00. Further, y and z are 0 <y ≦ 0.30 and 0 <z ≦ 0.30, respectively.
That is, in the third embodiment, a part of Fe ³⁺ is substituted with both In ³⁺ and Al ³⁺ .
The reason for substituting a part of Fe ³⁺ with both In ³⁺ and Al ³⁺ is as follows.
By replacing a part of Fe ³⁺ with In ³⁺ , the anisotropic magnetic field Ha can be controlled as described above. In addition, by controlling a part of Fe ³⁺ with Al ³⁺ , the control can be performed. It is possible to change the saturation magnetization Ms while suppressing the fluctuation of the generated anisotropic magnetic field Ha, whereby the frequency ω of the ferromagnetic resonance peak depending on the saturation magnetization Ms (the above formulas (2) and (3)). And a magnetic permeability difference Δμ can be finely adjusted, and it becomes easy to obtain a desired irreversible and low magnetic loss ferrite porcelain composition in a microwave band of 10 GHz or less or 30 to 60 GHz.
In the general formula [C], y and z are set to 0 <y ≦ 0.30 and 0 <z ≦ 0.30, respectively. When y and z both exceed 0.30, In and Al This is because the Fe content becomes excessive, while the Fe content becomes too low to exhibit magnetic anisotropy and cannot be used as a non-magnetic material.
The ferrite porcelain composition of the third embodiment also uses a barium compound, a strontium compound, an iron compound, an indium compound, and an aluminum compound as a ferrite raw material, and is substantially the same method as in the first embodiment. The ferrite porcelain composition represented by the general formula [C] can be easily produced by the procedure.
As described above, in the third embodiment, a part of Fe ³⁺ of the magnetoplumbite type ferrite is replaced with In ³⁺ and Al ³⁺ , and therefore, in the microwave band of 10 GHz or 30 to 60 GHz, a desired non- A ferrite porcelain composition having reversibility, low magnetic loss, and suitable for non-reciprocal circuit elements can be obtained.
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 and Si may be mixed during wet mixing. Such impurities may be mixed at less than 0.8% by weight, but this does not affect the characteristics of the present invention.
The ferrite porcelain composition of the present invention is not limited to the above embodiment, and at least one of the Ca component and the Co component is represented by the general formulas [A] to [C]. It is also preferable to contain 0.001 to 0.8 mol in total with respect to 1 mol of the main component.
In this case, the ferrite porcelain composition is represented by the following general formulas [D] to [F].
_{(Sr 1-x Ba x)} O · n (Fe 1-y In y) 2 O 3 + αCa + βCo ... [D]
_{(Sr 1-x Ba x)} O · n (Fe 1-z Al z) 2 O 3 + αCa + βCo ... [E]
_{(Sr 1-x Ba x)} O · n (Fe 1-y-z In y Al z) 2 O 3 + αCa + βCo ... [F]
Here, α and β are the number of moles of added Ca component and Co component with respect to 1 mole of the main component represented by the general formulas [D] to [F], and satisfy the following formula [G]. ing.
0.001 ≦ α + β ≦ 0.8 [G]
In the nonreciprocal circuit element, the shorter the distance between the permanent magnet and the ferrite porcelain composition, the more the transmission characteristics deteriorate due to the influence of eddy current loss generated in the permanent magnet. And this eddy current is easy to generate | occur | produce, so that the specific resistivity (rho) of a permanent magnet is small. In addition, in the self-biased nonreciprocal circuit element, the ferrite porcelain composition itself generates a magnetic field, and thus 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 Ca component and / or Co component so as to satisfy the general formula [G]. As a result, it has been found that the eddy current loss of the self-biased nonreciprocal circuit element can be reduced, and deterioration of 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 [G] is as follows.
That is, when the total amount of moles α and β of the Ca component and the Co component is less than 0.001 mole with respect to 1 mole of the main component, the effect of increasing the specific resistivity ρ by the addition of the Ca component and / or the Co component. This is because the signal transmission loss is large and the transmission characteristics are deteriorated, and when the total amount of moles α and β of the Ca component and the Co component exceeds 0.8 mol, the specific resistivity is obtained. This is because ρ tends to decrease, and the signal transmission loss may increase, leading to deterioration in transmission characteristics.
Moreover, in the ferrite ceramic composition of the general formulas [A] to [F] described above, the contents of the Mn component and the Zr component are 1.5% by weight or less (not including 0% by weight) in terms of oxides. The specific resistivity ρ can be increased and the dielectric loss tan δ can be reduced by adding the Mn component and the Zr component so that In particular, in the general formulas [D] to [F], the Ca component and the Co component are prepared by adjusting the contents of the Mn component and the Zr component to 1.5% by weight or less (not including 0% by weight). It becomes possible to obtain a larger specific resistivity ρ in combination with the addition effect of.
In this case, the Mn component may be contained in the sintered body, which is the main component, or a 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 should be prepared so as to be 1.5% by weight or less (not including 0% by weight) in terms of oxides. Accordingly, a ferrite porcelain composition having a low dielectric loss tan δ and a large specific resistivity ρ can be obtained, which can achieve further low eddy current loss in a self-biased non-reciprocal circuit device and good transmission. Characteristics can be obtained.
In particular, Mn is a single element and has a plurality of valences, so that the charge balance can be adjusted and is particularly preferable for obtaining a high resistance magnetoplumbite type ferrite.
If the total content of the Mn component and the Zr component exceeds 1.5% by weight in terms of oxides, the dielectric loss tan δ and the specific resistivity ρ may be decreased. Is added, it is necessary to control the total content to be 1.5% by weight or less.
Next, a non-reciprocal circuit device using the above ferrite porcelain composition will be described.
FIG. 5 is a perspective view schematically showing a lumped constant circulator as an embodiment (first embodiment) of a non-reciprocal circuit device according to the present invention.
The lumped constant circulator is formed in a cross shape so that the microstrip lines 1a, 1b, and 1c are spaced from each other at 120 ° C., and the upper and lower surfaces of the microstrip lines 1a, 1b, and 1c are provided with an insulator layer 2. And the ferrite substrate 3 formed of the ferrite porcelain composition. Capacitors (not shown) are 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 capacitors.
In the first embodiment, for example, when a current is passed through the microstrip line 1a, a uniform rotating magnetic field is formed on the ferrite substrate 3 by the cross circuit formed by the microstrip lines 1a, 1b, and 1c. . And since the microwave ferrite 3 is formed with the said ferrite porcelain composition, it becomes possible to obtain a circulator having a sufficient nonreciprocity with a small magnetic loss in a microwave band of 10 GHz or less or 30 to 60 GHz. Moreover, 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. 6A is a stripline Y-junction circulator as a second embodiment of the nonreciprocal circuit device, and FIG. 6B is a view taken along the line AA of FIG. 6A.
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 portion 4d, and the branch paths 4a, 4b, and 4c are for correction. Capacitor portions 5a, 5b, and 5c are formed. A ferrite substrate 6 is provided on both upper and lower surfaces of the central portion 4d, and external conductors 7a and 7b are provided on both upper and lower surfaces of the branch paths 4a, 4b, and 4c so that the ferrite substrate 6 is sandwiched. ing.
For example, when resonating in the TM ₁₁₀ mode, the high frequency magnetic field input to the branch path 4a has its polarization plane rotated 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 above-described ferrite porcelain composition, it is small and low in magnetic loss and sufficient irreversibility in a microwave band of 10 GHz or less or 30 to 60 GHz. It becomes possible to obtain a circulator with a reduced height and reduced cost.
FIG. 7 shows a ferrite substrate circulator as a third embodiment of the non-reciprocal circuit device, in which a Y-shaped strip line 10 is formed on the surface of the ferrite substrate 9. Also in the third embodiment, as in the second embodiment, for example, when resonating in the TM ₁₁₀ mode, the high frequency magnetic field input to the branch path 10a rotates on the ferrite substrate 9 in the plane of polarization. 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-mentioned ferrite porcelain composition, it is small and low in magnetic loss and sufficient irreversibility in a microwave band of 10 GHz or less or 30 to 60 GHz. It becomes possible to obtain a circulator with a reduced height and reduced cost.
FIG. 8 is a perspective view schematically showing a waveguide circulator as a fourth embodiment of the non-reciprocal circuit element. In the fourth embodiment, a Y-shaped waveguide 11 is shown. A columnar ferrite column 12 is inserted in the center of the Y branch of this, and operates in substantially the same manner as in the second and third embodiments to form a circulator. And since the ferrite pillar 12 is formed with the above-mentioned ferrite porcelain composition, the magnetic loss is small in the microwave band of 10 GHz or less or 30 to 60 GHz, and sufficient irreversibility is achieved. It is possible to obtain a circulator made.
FIG. 9A is a perspective view schematically showing a non-radiative dielectric line Y-type circulator as a fifth embodiment of the nonreciprocal circuit device, and FIG. 9B is a diagram of FIG. 9A. It is BB sectional drawing. In FIG. 9A, a pair of upper and lower metal plates is omitted.
In the fifth embodiment, the dielectric strips 13a, 13b, and 13c are arranged at equal intervals of 120 °, and the pair of disk-like ferrite substrates 14a and 14b are formed of the dielectric strips 13a, 13b, and 13c. Further, flat 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. The ferrite substrates 14a and 14b constitute a resonator and resonate in the HE _11δ mode.
Also in the fifth embodiment, since the ferrite substrates 14a and 14b are 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 irreversible size is small. -It is possible to obtain a circulator with a reduced profile and cost.
FIG. 10 is a perspective view schematically showing a Faraday rotation type isolator as a sixth embodiment of the nonreciprocal circuit device. The Faraday rotation type isolator is a ferrite rod 17 inserted through a support dielectric 16. And resistance plates 18a and 18b are accommodated in the waveguide 19.
Then, for example, an input signal in TE ₁₀ mode from the direction of arrow C is converted to TE ₁₁ mode by the square-circular converter 20a. Since the electric field of the input signal is perpendicular to the resistor plate 18a, it reaches the ferrite rod 17 without being absorbed and is decomposed into positive and negative circularly polarized waves, and the permeability difference Δμ between the positive and negative circularly polarized waves is the phase. The polarization plane rotates by an angle θ due to a constant difference. As a result, the input signal that has passed through the ferrite rod 17 becomes parallel to the resistor plate 18b, and the input signal is absorbed.
On the other hand, the TE ₁₀ mode input signal 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 resistor plate 18b, it reaches the ferrite rod 17 without being absorbed and is decomposed into positive and negative circularly polarized waves, and the plane of polarization rotates by an angle θ. The input signal that has passed through the ferrite rod 17 becomes perpendicular to the resistor 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 above ferrite porcelain composition, the magnetic loss is small in the microwave band of 10 GHz or less or 30 to 60 GHz, and sufficient irreversibility is achieved. -It is possible to obtain an isolator that is reduced in height and cost.
FIG. 11 is a perspective view schematically showing a peripheral mode isolator as a seventh embodiment of a non-reciprocal circuit device, and the seventh embodiment is formed of the 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 as to partially overlap 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 portion of the strip line 22 to the output side as shown by an 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 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 substrate has a small magnetic loss and a sufficient irreversibility in a microwave band of 10 GHz or less or 30 to 60 GHz. -It is possible to obtain an isolator that is reduced in height and cost.
FIGS. 12A and 12B are perspective views schematically showing a waveguide resonance isolator as an eighth embodiment of the nonreciprocal circuit device, in which the ferrite rods 26a to 26c are rectangular waveguides. The tube 25 is inserted into a predetermined position.
In the eighth embodiment, when propagating through the waveguide 25 in the fundamental mode, that is, the TE ₁₀ mode, the high frequency magnetic field rotates at a specific position and becomes circularly polarized. 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 The circularly polarized wave passes through without being attenuated.
Therefore, as shown in FIGS. 12A and 12B, an isolator can be formed by inserting ferrite rods 26a to 26c at specific positions where circularly polarized waves are generated.
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 the microwave band of 10 GHz or less or 30 to 60 GHz, and sufficient irreversibility is achieved. -It is possible to obtain an isolator that is reduced in height and cost.
FIG. 13 shows a cross strip line resonance isolator as a ninth embodiment of a non-reciprocal circuit device.
In the ninth embodiment, the ground conductors 27a and 27b are formed on one surface of the dielectrics 29a and 29b, and a cylindrical ferrite column 28 is embedded in the substantially central portion of the dielectric 29 so as to strip. 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 pillar 28. In the ninth embodiment, since circular polarization occurs at the intersection of the strip line 30 and the λ / 4 resonator 32, an isolator is formed based on the same operating principle as in FIG.
Also in the ninth embodiment, since the ferrite column 28 is formed of the above-described ferrite porcelain composition, it is small and low in magnetic loss and sufficient irreversibility in a microwave band of 10 GHz or less or 30 to 60 GHz. It is possible to obtain an isolator with a reduced height and reduced cost.
FIG. 14 is a system configuration diagram showing an embodiment of a radio apparatus according to the present invention, in which 31 is the isolator shown in FIGS. 10 to 13 and 32 is the circulator shown in FIGS. It is.
That is, in this radio apparatus, when a modulation signal is input to a voltage control signal (Voltage Controlled Oscillator: VCO) 33, the modulation signal is input to the coupler 34 via the isolator 31. The modulated signal that is divided into two and 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, mixed with the modulation signal from the coupler 34, and the reception frequency is lowered to obtain an IF signal (Intermediate Frequency: intermediate frequency). .
In this embodiment, since the above-described isolator and circulator are used, even in a cellular phone used in the several GHz band, a wireless LAN used in the several tens GHz band, and a millimeter wave radar, the magnetic loss is small and sufficient. It is possible to obtain a wireless device that is irreversible and can be reduced in size, height, and cost.
Next, examples of the present invention will be specifically described.

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０．０５（＜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０．９６（≧０．０５）であり、磁気損失が大きい。
試料番号６は、ｙが０．３１であり、０．３０を超えているため、Ｆｅの含有量が過少となり、このため異方性磁界が「０」となって非可逆性を示さなくなった。
これに対して試料番号２〜５は、ｙが０＜ｙ≦０．３０、ｎが５．５０であるので、従来のＳｒフェライト（試料番号１）に比べて異方性磁界Ｈａを低下させることができ、これにより１０ＧＨｚ及び４０ＧＨｚの少なくともいずれか一方で絶対透磁率差｜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。
すなわち、試料番号４、５は１０ＧＨｚ及び４０ＧＨｚの双方で絶対透磁率差｜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となって磁気損失も生じず、これら双方のマイクロ波帯で使用できる非可逆回路素子を得ることが可能となる。
また、試料番号２は、４０ＧＨｚでは虚数部μ_＋″が０．１９となって０．０５以上となり、磁気損失が大きくなるが、１０ＧＨｚでは虚数部μ_＋″が０となって磁気損失が生じず、また、この１０ＧＨｚでは絶対透磁率差｜Δμ｜も０．１４（＞０．１）であり、所望の非可逆性を得ることができる。
また、試料番号３は、１０ＧＨｚでは虚数部μ_＋″が０．４１となって０．０５以上であるため、磁気損失が大きくなるが、４０ＧＨｚでは虚数部μ_＋″が０となって磁気損失が生じず、また、この４０ＧＨｚでは絶対透磁率差｜Δμ｜も０．５５（＞０．１）であり、所望の非可逆性を得ることができる。A ferrite porcelain composition represented by the general formula {SrO · n (Fe _1-y In _y ) ₂ O ₃ } having the composition shown in Table 1 was prepared.
That is, SrCO ₃ (strontium carbonate), Fe ₂ O ₃ (iron oxide), In ₂ O ₃ (indium oxide) are prepared as ferrite raw materials, and 0.00 ≦ y ≦ 0.31, n = 5.50 was weighed and prepared, wet-mixed with a ball mill, calcined in the air, and then 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 binder to form a slurry, which is dehydrated and molded in a magnetic field, and then fired in the air to produce a sintered body. The general formula {SrO · n (Fe to obtain a _{1-y in y) 2 O} 3 ferrite ceramic composition of the sample No. 1-6 represented by}.
Next, the saturation magnetization Ms and the anisotropic magnetic field Ha of each sample are measured, and the relationship between the frequency and the complex permeability is simulated based on the measured saturation magnetization Ms and the anisotropic magnetic field Ha, and 10 GHz. And the permeability difference Δμ (irreversible) at 40 GHz and the imaginary part μ ₊ ″ (magnetic loss) of the circularly polarized complex permeability.
Here, the saturation magnetization Ms was measured by VSM (sample vibration type magnetization measuring device).
The anisotropic magnetic field Ha was determined as follows. That is, first, using a network analyzer, the magnetic resonance frequency fr 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).
2πfr = γ · (Ha−N · Ms) (4)
Here, γ is a gyro constant (= 2.21 × 10 ⁵ m / A · s).
Furthermore, the specific resistivity ρ was measured by a four probe method using a high resistance measuring instrument.
Table 1 shows the composition of each sample number, saturation magnetization Ms, anisotropic magnetic field Ha, specific resistivity ρ, permeability difference Δμ, and imaginary part μ ₊ ″.

Sample No. 1 is a conventionally used Sr ferrite (anisotropic magnetic field Ha: 1536 kA / m). At 10 GHz, the permeability difference Δμ is as small as 0.05 (<0.1), and the desired irreversible. I can't get sex. At 40 GHz, the imaginary part μ ₊ ″ is 0.96 (≧ 0.05), and the magnetic loss is large.
Sample No. 6 had y of 0.31 and exceeded 0.30, so the Fe content was too low, so the anisotropic magnetic field was “0” and no irreversibility was observed. .
On the other hand, in sample numbers 2 to 5, since y is 0 <y ≦ 0.30 and n is 5.50, the anisotropic magnetic field Ha is reduced as compared with the conventional Sr ferrite (sample number 1). Thus, at least one of 10 GHz and 40 GHz, the absolute permeability difference | Δμ | is 0.1 or more, and a desired irreversibility can be obtained, and the imaginary part μ ₊ ″ is also 0.05. Therefore, the magnetic loss can be reduced.
That is, in Sample Nos. 4 and 5, the absolute permeability difference | Δμ | is 0.1 or more at both 10 GHz and 40 GHz, and the desired irreversibility can be obtained, and the imaginary part μ ₊ ″ is also 0. Magnetic loss does not occur, and a nonreciprocal circuit device that can be used in both microwave bands can be obtained.
In Sample No. 2, the imaginary part μ ₊ ″ becomes 0.19 at 40 GHz and becomes 0.05 or more, and the magnetic loss increases. However, at 10 GHz, the imaginary part μ ₊ ″ becomes 0 and magnetic loss occurs. Moreover, at 10 GHz, the absolute permeability difference | Δμ | is also 0.14 (> 0.1), and a desired irreversibility can be obtained.
In Sample No. 3, the imaginary part μ ₊ ″ is 0.41 at 10 GHz and is 0.05 or more, so that the magnetic loss increases. However, at 40 GHz, the imaginary part μ ₊ ″ is 0 and the magnetic loss is increased. In addition, at 40 GHz, the absolute permeability difference | Δμ | is also 0.55 (> 0.1), and a desired irreversibility can be obtained.

試料番号１１は、試料番号１（実施例１、表１）と同様、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０．０５（＜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０．９６（≧０．０５）であり、磁気損失も大きい。
試料番号１５はｚが０．３１であり、０．３０を超えているため、Ｆｅの含有量が過少となり、このため異方性磁界が「０」となって非可逆性を示さなくなった。
これに対して試料番号１２〜１４は、ｚが０＜ｚ≦０．３０であるので、従来のＳｒフェライト（試料番号１１）に比べて異方性磁界Ｈａを増加させることができ、強磁性共鳴ピークの周波数が高周波側にシフトし、その結果、虚数部μ_＋″も０となる。そして、１０ＧＨｚでは絶対透磁率差｜Δμ｜が０．１未満であり非可逆性を得ることはできないが、４０ＧＨｚでは絶対透磁率差｜Δμ｜は０．１以上であり、十分な非可逆性を得ることができる。すなわち、４０ＧＨｚのマイクロ波帯では非可逆性が良好で磁気損失の生じないフェライト磁器組成物を得ることができた。A ferrite porcelain composition represented by the general formula {SrO.n (Fe _1-z Al _z ) ₂ O ₃ } having the composition shown in Table 2 is produced by the same method and procedure as in [Example 1]. did.
That is, SrCO ₃ (strontium carbonate), Fe ₂ O ₃ (iron oxide), Al ₂ O ₃ (aluminum oxide) are prepared as ferrite raw materials, and 0.00 ≦ z ≦ 0.31, n = 5.50 was weighed and prepared, wet-mixed with a ball mill, calcined in the air, and then 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 binder to form a slurry, which is dehydrated and molded in a magnetic field, and then fired in the air to produce a sintered body. The general formula {SrO · n (Fe Ferrite porcelain compositions of sample numbers 11 to 15 represented by _1-z Al _z ) ₂ O ₃ } were obtained.
Next, for each of these samples, as in [Example 1], the saturation magnetization Ms, the anisotropic magnetic field Ha, and the specific resistivity ρ are measured, and based on the measured saturation magnetization Ms and the anisotropic magnetic field Ha, each sample is measured. The permeability difference Δμ (irreversible) at 10 GHz and 40 GHz of the sample and the imaginary part μ ₊ ″ (magnetic loss) of the circularly polarized wave complex permeability were determined.
Table 2 shows the composition of each sample number, the saturation magnetization Ms, the anisotropic magnetic field Ha, the specific resistivity ρ, the permeability difference Δμ, and the imaginary part μ ₊ ″.

Sample No. 11 is Sr ferrite (anisotropic magnetic field Ha: 1536 kA / m) conventionally used, similar to Sample No. 1 (Example 1, Table 1), and the permeability difference Δμ is 0.1 at 10 GHz. As small as 05 (<0.1), the desired irreversibility cannot be obtained. Further, at 40 GHz, the imaginary part μ ₊ ″ is 0.96 (≧ 0.05), and the magnetic loss is large.
Sample No. 15 had z of 0.31 and exceeded 0.30. Therefore, the Fe content was too small, so that the anisotropic magnetic field was “0” and no irreversibility was observed.
On the other hand, sample numbers 12 to 14 can increase the anisotropy magnetic field Ha as compared with the conventional Sr ferrite (sample number 11) because z is 0 <z ≦ 0.30. The frequency of the resonance peak shifts to the high frequency side, and as a result, the imaginary part μ ₊ ″ also becomes 0. At 10 GHz, the absolute permeability difference | Δμ | is less than 0.1, and irreversibility cannot be obtained. However, at 40 GHz, the absolute permeability difference | Δμ | is 0.1 or more, so that sufficient irreversibility can be obtained, that is, ferrite with good irreversibility and no magnetic loss in the 40 GHz microwave band. A porcelain composition could be obtained.

試料番号２１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０．０５（＜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０．９６（≧０．０５）であり、磁気損失も大きい。
試料番号２５はｙが０．３１であり、試料番号２６は、ｙ及びｚが０．３１であり、０．３０を超えているため、Ｆｅの含有量が過少となり、このため異方性磁界が「０」となって非可逆性を示さなくなった。
また、試料番号３２は、ｎが４．９０であり、５．００未満であるため、異方性磁界Ｈａが「０」となって非可逆性を示さなくなり、また比抵抗率ρも８．５×１０^６Ω・ｃｍと小さくなった。
また、試料番号３８は、ｎが６．００であるため、異方性磁界Ｈａが「０」となって非可逆性を示さなくなり、また比抵抗率ρも５．４×１０^６Ω・ｃｍと小さくなった。
これに対して試料番号２２〜２４、２７〜３１、及び３３〜３７は、ｙ及びｚがそれぞれ０＜ｙ≦０．３０、０＜ｚ≦０．３０、ｎが５．００≦ｎ＜６．００であるので、１０ＧＨｚ及び４０ＧＨｚの少なくともいずれか一方で絶対透磁率差｜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。
すなわち、試料番号２２、２７〜３１、及び３３〜３７は、１０ＧＨｚ及び４０ＧＨｚの双方で絶対透磁率差｜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も小さく、これら双方のマイクロ波帯で使用できる非可逆回路素子を得ることが可能となる。
また、試料番号２３、２４は、１０ＧＨｚでは絶対透磁率差｜Δμ｜が０．１未満であり、所望の非可逆性を得ることができなくなるが、４０ＧＨｚでは絶対透磁率差｜Δμ｜も０．１以上であり、所望の非可逆性を得ることができ、虚数部μ_＋″も０となって磁気損失が生じないことが分かる。
そして、Ｉｎ^３＋及びＡｌ^３＋の含有モル量、すなわちｙ及びｚを適宜調整することにより、試料番号２２、２７〜３１、及び３３〜３７のように１０ＧＨｚ及び４０ＧＨｚの双方で非可逆性と低磁気損失を両立させることのできるフェライト磁器組成物を得ることができる。In a similar manner and procedure as Example 1, the general formula having the composition shown in Table _{3 {(Sr 1-x Ba} x) O · n (Fe 1-y-z In y Al z) 2 O ₃ } was produced.
That is, SrCO ₃ (strontium carbonate), BaCO ₃ (barium carbonate), Fe ₂ O ₃ (iron oxide), In ₂ O ₃ (indium oxide), Al ₂ O ₃ (aluminum oxide) are prepared as ferrite raw materials. These ferrite raw materials are weighed so that 0 ≦ x ≦ 1.00, 0.00 ≦ y ≦ 0.31, 0.00 ≦ z ≦ 0.31, 4.90 ≦ n ≦ 6.00. The mixture was wet mixed with a ball mill, calcined in the air, and then 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 binder to form a slurry, and this slurry is dehydrated and molded in a magnetic field, and then fired in the air to produce a sintered body. The general formula {(Sr _1-x to obtain a _{Ba x) O · n (Fe} 1-y-z in y Al z) 2 O 3 ferrite ceramic composition of the sample No. 21-38 represented by}.
Next, for each of these samples, as in [Example 1], the saturation magnetization Ms, the anisotropic magnetic field Ha, and the specific resistivity ρ are measured, and based on the measured saturation magnetization Ms and the anisotropic magnetic field Ha, each sample is measured. The permeability difference Δμ (irreversible) at 10 GHz and 40 GHz of the sample and the imaginary part μ ₊ ″ (magnetic loss) of the circularly polarized wave complex permeability were determined.
Table 3 shows the composition of each sample number, the saturation magnetization Ms, the anisotropic magnetic field Ha, the specific resistivity ρ, the permeability difference Δμ, and the imaginary part μ ₊ ″.

Sample No. 21 is a conventionally used Sr ferrite (anisotropic magnetic field Ha: 1536 kA / m). At 10 GHz, the permeability difference Δμ is as small as 0.05 (<0.1), and the desired irreversible. I can't get sex. Further, at 40 GHz, the imaginary part μ ₊ ″ is 0.96 (≧ 0.05), and the magnetic loss is large.
In Sample No. 25, y is 0.31, and in Sample No. 26, y and z are 0.31 and exceed 0.30, so the Fe content is too low. Became “0” and showed no irreversibility.
In Sample No. 32, since n is 4.90 and less than 5.00, the anisotropic magnetic field Ha becomes “0” and does not show irreversibility, and the specific resistivity ρ is also 8. It was as small as 5 × 10 ⁶ Ω · cm.
In Sample No. 38, since n is 6.00, the anisotropic magnetic field Ha becomes “0” and does not show irreversibility, and the specific resistivity ρ is also 5.4 × 10 ⁶ Ω · cm. It became small.
On the other hand, in sample numbers 22-24, 27-31, and 33-37, y and z are 0 <y ≦ 0.30, 0 <z ≦ 0.30, and n is 5.00 ≦ n <6, respectively. Since the absolute permeability difference | Δμ | is 0.1 or more in at least one of 10 GHz and 40 GHz, the desired irreversibility can be obtained, and the imaginary part μ ₊ ″ is also 0.05. Therefore, the magnetic loss can be reduced.
That is, Sample Nos. 22, 27 to 31, and 33 to 37 can obtain the desired irreversibility because the absolute permeability difference | Δμ | is 0.1 or more at both 10 GHz and 40 GHz, and the imaginary part Since μ ₊ ″ is less than 0.05 and magnetic loss is small, it is possible to obtain a nonreciprocal circuit device that can be used in both microwave bands.
In Sample Nos. 23 and 24, the absolute permeability difference | Δμ | is less than 0.1 at 10 GHz, and a desired irreversibility cannot be obtained. However, at 40 GHz, the absolute permeability difference | Δμ | It is found that the desired irreversibility can be obtained and the imaginary part μ ₊ ″ is also 0 and no magnetic loss occurs.
Then, by appropriately adjusting the molar amount of In ³⁺ and Al ³⁺ , that is, y and z, irreversible and low magnetic properties at both 10 GHz and 40 GHz as in sample numbers 22, 27 to 31, and 33 to 37 A ferrite porcelain composition capable of achieving both losses can be obtained.

各試料番号４１〜６９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。
しかしながら、試料番号４１、４２、４９、５６、６５は（α＋β）値が０．００１未満であるため、比抵抗率ρが１．９×１０^９〜２．８×１０^１０Ω・ｃｍと小さく、挿入損失Ｉ．Ｌ．も１．０６〜１．２４ｄＢと大きくなる。
また、試料番号４８、５５、６０、６４、６９は（α＋β）値が０．８を超えているため、比抵抗率ρが１．６×１０^９〜２．９×１０^１０Ω・ｃｍ以下と小さく、挿入損失Ｉ．Ｌ．も１．０６〜１．５９ｄＢと大きくなる。
これに対して試料番号４３〜４７、５０〜５５、５７〜５９、６１〜６３、６６〜６８は、（α＋β）値が０．００１０〜０．８００の範囲内にあるため、比抵抗率ρは４．５×１０^１０〜１．８×１０^１３Ω・ｃｍであり、また挿入損失Ｉ．Ｌ．が０．４６〜０．９９ｄＢであり、比抵抗率ρを増大させて挿入損失Ｉ．Ｌ．を低減することのできるフェライト磁器組成物を得ることができる。A ferrite porcelain composition of the general formula {(Sr _1−x Ba _x ) O · n (Fe _1−yz In _y Al _z ) ₂ O ₃ + αCa + βCo} having the composition of Table 4 was prepared.
That is, using substantially the same method and procedure as in [Example 1], SrCO ₃ (strontium carbonate), BaCO ₃ (barium carbonate), Fe ₂ O ₃ (iron oxide), In ₂ O ₃ as ferrite raw materials. (Indium oxide), Al ₂ O ₃ (Aluminum oxide) are weighed and prepared so that x = 0.2, n = 5.5, y = 0.13, z = 0.13, and a ball mill is used. to after wet mixing, and calcining in air, the general formula _{{(Sr 1-x Ba x} ) O · n (Fe 1-y-z in y Al z) 2 O 3} calcined represented by A powder was prepared.
Subsequently, with respect to 1 mol of this calcined powder (main component), CaCO ₃ (calcium carbonate) and CoO (cobalt oxide) are added so that the total content is 0 to 0.9000 mol, and wet pulverization is performed. Then, a calcined pulverized product having a specific surface area of about 5 m ² / g was produced.
Next, this calcined and pulverized product is kneaded with a vinyl acetate binder resin to form a slurry, and further subjected to a molding process using a dehydrating molding machine in a magnetic field, and then subjected to a firing treatment in the atmosphere to obtain a general formula {(Sr _1-x Ba _x) to give the _{O · n (Fe 1-y} -z in y Al z) 2 O 3 + αCa + βCo ferrite ceramic composition of the sample No. 41-69 represented by}.
Next, as in [Example 1], the saturation magnetization Ms of each sample, the magnetic permeability difference Δμ (irreversible) at the anisotropic magnetic field Ha, 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.
Further, each sample was mounted on a non-radiative dielectric line Y-type circulator shown in FIG. 7, and a signal transmission loss (insertion loss IL) was measured using a network analyzer.
Table 4 shows the composition of each sample, the saturation magnetization Ms, the anisotropic magnetic field Ha, the permeability difference Δμ, the imaginary part μ ₊ ″, the specific resistivity ρ, and the insertion loss IL.

In each of sample numbers 41 to 69, x, y, z, and n are within the scope of the present invention, so that the absolute permeability difference | Δμ | is 0.1 or more and desired irreversibility can be obtained. In addition, the imaginary part μ ₊ ″ is also less than 0.05, and the magnetic loss can be reduced.
However, since the sample numbers 41, 42, 49, 56, and 65 have an (α + β) value of less than 0.001, the specific resistivity ρ is as small as 1.9 × 10 ^{9 to} 2.8 × 10 ¹⁰ Ω · cm. Insertion loss L. Is also increased to 1.06 to 1.24 dB.
Moreover, since the sample numbers 48, 55, 60, 64, and 69 have an (α + β) value exceeding 0.8, the specific resistivity ρ is 1.6 × 10 ^{9 to} 2.9 × 10 ¹⁰ Ω · cm or less. And insertion loss I.V. L. Is also increased to 1.06 to 1.59 dB.
On the other hand, since the sample numbers 43 to 47, 50 to 55, 57 to 59, 61 to 63, and 66 to 68 have (α + β) values in the range of 0.0010 to 0.800, the specific resistivity ρ Is 4.5 × 10 ^{10 to} 1.8 × 10 ¹³ Ω · cm, and insertion loss I.V. L. Is 0.46 to 0.99 dB, and the insertion loss I.D. L. It is possible to obtain a ferrite porcelain composition capable of reducing the above.

試料番号７１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０．０４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０．９７（≧０．０５）であり、磁気損失が大きくなる。
試料番号７６は、ｙが０．３１であり、０．３０を超えているため、Ｆｅの含有量が過少となり、このため異方性磁界も「０」となって非可逆性を示さなくなる。
また、各試料番号７１〜７６から明らかなように、Ｃａ成分及びＣｏ成分を各０．２５モル添加することにより、添加しない場合に比べ、比抵抗率ρが飛躍的に増大することが分かる。In a similar manner and procedure as Example 4, the general formula having the composition shown in Table _{5 {(Sr 1-x Ba} x) O · n (Fe 1-y In y) 2 O 3 + αCa + βCo} (x = 0 , N = 5.5, 0 ≦ y ≦ 0.31, α = β = 0.25).
Moreover, the ferrite porcelain composition which did not add Ca and Co as a comparative example was produced.
Next, as in [Example 1], the saturation magnetization Ms of each sample, the magnetic permeability difference Δμ (irreversible) at the anisotropic magnetic field Ha, 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.
Table 5 shows the composition of each sample number, the saturation magnetization Ms, the anisotropic magnetic field Ha, the permeability difference Δμ, the imaginary part μ ₊ ″, and the specific resistivity ρ.

Sample No. 71 is obtained by adding a Ca component and a Co component to conventional Sr ferrite. At 10 GHz, the absolute magnetic permeability difference | Δμ | is as small as 0.04, and a desired irreversibility cannot be obtained. At 40 GHz, the imaginary part μ ₊ ″ is 0.97 (≧ 0.05), and the magnetic loss increases.
In Sample No. 76, y is 0.31 and exceeds 0.30. Therefore, the Fe content is too small, so that the anisotropic magnetic field is also “0” and does not exhibit irreversibility.
Further, as is clear from the respective sample numbers 71 to 76, it can be seen that the addition of 0.25 mol of each of the Ca component and the Co component dramatically increases the specific resistivity ρ as compared with the case where the Ca component and the Co component are not added.

試料番号８１は、従来のＳｒフェライトにＣａ成分とＣｏ成分を添加したものであり、１０ＧＨｚでは絶対透磁率差｜Δμ｜が０．０４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４．９７（≧０．０５）であり、磁気損失が大きくなる。
試料番号８５は、ｚが０．３１であり、０．３０を超えているため、Ｆｅの含有量が過少となり、このため異方性磁界も「０」となって非可逆性を示さなくなる。
また、試料番号８１〜８５から明らかなように、Ｃａ成分及びＣｏ成分を各０．２５モル添加することにより、添加していない比較例に比べ、比抵抗率ρが飛躍的に増大することが分かる。In Example 4 the same method and procedure, the general formula having the composition shown in Table _{6 {(Sr 1-x Ba} x) O · n (Fe 1-z Al z) 2 O 3 + αCa + βCo} (x = 0 , N = 5.5, 0 ≦ z ≦ 0.31, α = β = 0.25).
Moreover, the ferrite porcelain composition which did not add Ca and Co as a comparative example was produced.
Next, as in [Example 4], the saturation magnetization Ms of each sample, the magnetic permeability difference Δμ (irreversible) at the anisotropic magnetic field Ha, 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.
Table 6 shows the composition of each sample number, the saturation magnetization Ms, the anisotropic magnetic field Ha, the permeability difference Δμ, the imaginary part μ ₊ ″, and the specific resistivity ρ.

Sample No. 81 is obtained by adding a Ca component and a Co component to conventional Sr ferrite, and the absolute permeability difference | Δμ | is as small as 0.04 at 10 GHz, and the desired irreversibility cannot be obtained. At 40 GHz, the imaginary part μ ₊ ″ is 4.97 (≧ 0.05), and the magnetic loss increases.
In Sample No. 85, z is 0.31 and exceeds 0.30, so the Fe content is too small. Therefore, the anisotropic magnetic field is also “0” and does not exhibit irreversibility.
Further, as is clear from the sample numbers 81 to 85, the addition of 0.25 mol of each of the Ca component and the Co component can dramatically increase the specific resistivity ρ as compared with the comparative example not added. I understand.

試料番号９１は、従来のＳｒフェライトにＣａ成分とＣｏ成分を添加したものであり、１０ＧＨｚでは絶対透磁率差｜Δμ｜が０．０４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４．９８（≧０．０５）であり、磁気損失が大きくなる。
試料番号９５は、ｚが０．３１であり、０．３０を超えているため、Ｆｅの含有量が過少となり、このため異方性磁界も「０」となって非可逆性を示さなくなる。
試料番号９６は、ｙ及びｚが共に０．３１であり、０．３０を超えているため、Ｆｅの含有量が過少となり、このため異方性磁界も「０」となって非可逆性を示さなくなる。
また、試料番号１０２、１０８は、ｎが４．９又は６．０であり、５．０≦ｎ＜６．０の範囲外となるため、磁気異方性を示さなくなり、非可逆性を示さなくなる。
また、試料番号９１〜１０８から明らかなように、Ｃａ成分及びＣｏ成分を各０．２５モル添加することにより、添加していない比較例に比べ、比抵抗率ρが飛躍的に増大することが分かる。In a similar manner and procedure as Example 4, the general formula having the composition shown in Table _{6 {(Sr 1-x Ba} x) O · n (Fe 1-y-z In y Al z) 2 O 3 + αCa + βCo} (X = 0, 5.0 ≦ n ≦ 6.0, 0 ≦ z ≦ 0.31, 0 ≦ z ≦ 0.31, α = β = 0.25) Ferrite of sample numbers 91 to 108 A porcelain composition was prepared.
Moreover, the ferrite porcelain composition which did not add Ca and Co as a comparative example was produced.
Next, as in [Example 4], the saturation magnetization Ms of each sample, the magnetic permeability difference Δμ (irreversible) at the anisotropic magnetic field Ha, 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.
Table 7 shows the composition of each sample number, the saturation magnetization Ms, the anisotropic magnetic field Ha, the permeability difference Δμ, the imaginary part μ ₊ ″, and the specific resistivity ρ.

Sample No. 91 is obtained by adding a Ca component and a Co component to conventional Sr ferrite, and the absolute permeability difference | Δμ | is as small as 0.04 at 10 GHz, and a desired irreversibility cannot be obtained. At 40 GHz, the imaginary part μ ₊ ″ is 4.98 (≧ 0.05), and the magnetic loss increases.
In Sample No. 95, z is 0.31 and exceeds 0.30, so the Fe content is too small. Therefore, the anisotropic magnetic field is also “0” and does not exhibit irreversibility.
In sample number 96, both y and z are 0.31 and exceed 0.30, so the Fe content is too low, and therefore the anisotropic magnetic field is also “0”, making it irreversible. Not shown.
In Sample Nos. 102 and 108, n is 4.9 or 6.0 and is outside the range of 5.0 ≦ n <6.0. Therefore, magnetic anisotropy is not exhibited and irreversibility is exhibited. Disappear.
Further, as is clear from the sample numbers 91 to 108, the addition of 0.25 mol of each of the Ca component and the Co component can dramatically increase the specific resistivity ρ as compared with the comparative example not added. I understand.

試料番号１１６は、Ｍｎ成分とＺｒ成分の含有量の総計が１．５２重量％であり、１．５０重量％を超えているため、誘電損失ｔａｎδが２５×１０^−４と大きく、また、比抵抗率ρも６．５×１０^６Ω・ｃｍと小さくなっている。
また、試料番号１２２も、Ｍｎ成分とＺｒ成分の含有量の総計が１．６８重量％であり、１．５０重量％を超えているため、誘電損失ｔａｎδが３０×１０^−４と大きく、また、比抵抗率ρも５．５×１０^６Ω・ｃｍと小さくなっている。
これに対して試料番号１１１〜１１５、及び１１７〜１２１は、Ｍｎ成分とＺｒ成分の含有量の総計が１．５０重量％以下の範囲でＭｎ成分やＺｒ成分を添加しているので、誘電損失ｔａｎδが１．０×１０^−４以下と小さく、また、比抵抗率ρも８．１×１０^９〜６．８×１０^１１Ω・ｃｍと大きくなっている。しかも、１０ＧＨｚ及び４０ＧＨｚで、絶対透磁率差｜Δμ｜が０．１以上なって所望の非可逆性を得ることができ、また、虚数部μ_＋″が０．０５未満となって磁気損失を抑制できることが分った。Ferrite porcelain compositions having the compositions shown in Table 8 were prepared by the same method and procedure as in [Example 1].
That is, SrCO ₃ (strontium carbonate), BaCO ₃ (barium carbonate), Fe ₂ O ₃ (iron oxide), In ₂ O ₃ (indium oxide), Al ₂ O ₃ (aluminum oxide) is used as a ferrite raw material, x = 0.10, 0.11 ≦ y ≦ 0.13, 0.04 ≦ z ≦ 0.06, 5.50 ≦ n ≦ 5.60 were weighed and prepared, and wet-mixed with a ball mill. After that, it was calcined in the atmosphere. Next, predetermined amounts of MnO and ZrO ₂ were added to the calcined product and 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 binder to form a slurry, and this slurry is dehydrated and molded in a magnetic field, and then fired in the air to produce a sintered body, containing a Mn component and a Zr component. to give the general formula _{{(Sr 1-x Ba x} ) O · n (Fe 1-y-z in y Al z) 2 O 3} ferrite ceramic composition of the sample No. 111 to 122 represented by.
Next, as in [Example 1], the specific resistivity ρ, the permeability difference Δμ (irreversible) of each sample at 10 GHz and 40 GHz, the imaginary part μ ₊ ″ (magnetic loss) of the circularly polarized complex permeability. Further, the dielectric loss tan δ was measured by the perturbation method.
Table 8 shows the composition of each sample number, the permeability difference Δμ, the imaginary part μ ₊ ″, the dielectric loss tan δ, and the specific resistivity ρ.

In Sample No. 116, the total content of the Mn component and the Zr component is 1.52% by weight and exceeds 1.50% by weight, so that the dielectric loss tan δ is as large as 25 × 10 ^−4, and the ratio The resistivity ρ is also as small as 6.5 × 10 ⁶ Ω · cm.
Sample No. 122 also has a total Mn component and Zr component content of 1.68% by weight, which exceeds 1.50% by weight, so the dielectric loss tan δ is as large as 30 × 10 ⁻⁴ , The specific resistivity ρ is also as small as 5.5 × 10 ⁶ Ω · cm.
On the other hand, since the sample numbers 111 to 115 and 117 to 121 add the Mn component and the Zr component in the range where the total content of the Mn component and the Zr component is 1.50% by weight or less, the dielectric loss The tan δ is as small as 1.0 × 10 ⁻⁴ or less, and the specific resistivity ρ is as large as 8.1 × 10 ^{9 to} 6.8 × 10 ¹¹ Ω · cm. In addition, at 10 GHz and 40 GHz, the absolute permeability difference | Δμ | is 0.1 or more and a desired irreversibility can be obtained, and the imaginary part μ ₊ ″ is less than 0.05, resulting in a magnetic loss. It was found that it can be suppressed.

試料番号１３１〜１４２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。
しかしながら、試料番号１３６、１４２は、Ｍｎ成分及びＺｒ成分の含有量の総計がそれぞれ１．５２重量％、１．６８重量％であり、１．５０重量％を超えているので、比抵抗率ρがそれぞれ１．１×１０^１０Ω・ｃｍ、９．５×１０^９Ω・ｃｍと小さい。
これに対して試料番号１３１〜１３５、及び１３７〜１４１は、Ｃａ成分及びＣｏ成分に加え、Ｍｎ成分とＺｒ成分が、総計で１．５０重量％以下の範囲で添加されているので、比抵抗率ρが１．２×１０^１３〜１．１×１０^１５Ω・ｃｍと飛躍的に増大することが分かった。In a similar manner and procedure as Example 4, the general formula having the composition shown in Table _{9 {(Sr 1-x Ba} x) O · n (Fe 1-y-z In y Al z) 2 O 3 + αCa + βCo} (X = 0, 5.0 ≦ n ≦ 6.0, 0 ≦ z ≦ 0.31, 0 ≦ z ≦ 0.31, α = β = 0.25) and a predetermined amount of MnO (oxidation Ferrite porcelain compositions of sample numbers 132 to 142 to which manganese) and ZrO ₂ (zirconium oxide) were added were prepared.
Next, as in [Example 4], the permeability difference Δμ (irreversible) 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.
Table 9 shows the composition of each sample, the permeability difference Δμ, the imaginary part μ ₊ ″, and the specific resistivity ρ.

In Sample Nos. 131 to 142, x, y, z, and n are within the scope of the present invention. Therefore, the absolute permeability difference | Δμ | is 0.1 or more, and desired irreversibility can be obtained. The imaginary part μ ₊ ″ is also less than 0.05, and the magnetic loss can be reduced.
However, since sample numbers 136 and 142 have a total content of Mn component and Zr component of 1.52% by weight and 1.68% by weight, respectively, exceeding 1.50% by weight, the specific resistivity ρ Are as small as 1.1 × 10 ¹⁰ Ω · cm and 9.5 × 10 ⁹ Ω · cm, respectively.
On the other hand, since the sample numbers 131 to 135 and 137 to 141 include the Mn component and the Zr component in addition to the Ca component and the Co component in a total range of 1.50% by weight or less, the specific resistance It was found that the rate ρ increased dramatically from 1.2 × 10 ^{13 to} 1.1 × 10 ¹⁵ Ω · cm.

  As described above in detail, the ferrite porcelain composition of the present invention can obtain sufficient irreversibility even when used in a microwave band of 10 GHz or less or 30 to 60 GHz, and can reduce magnetic loss. It is useful for circulators and isolators used in these microwave bands, and for wireless devices equipped with these circulators and isolators.

Claims (7)

Formula _{{(Sr 1-x Ba x} ) O · n (Fe 1-y In y) 2 O 3} (0 ≦ x ≦ 1.00,5.00 ≦ n <6.00,0 <y ≦ 0 30) A ferrite porcelain composition for non-reciprocal circuit elements, comprising the main component represented by .30). Formula _{{(Sr 1-x Ba x} ) O · n (Fe 1-z Al z) 2 O 3} (0 ≦ x ≦ 1.00,5.00 ≦ n <6.00,0 <z ≦ 0 30) A ferrite porcelain composition for non-reciprocal circuit elements, comprising the main component represented by .30). Formula _{{(Sr 1-x Ba x} ) O · n (Fe 1-y-z In y Al z) 2 O 3} (0 ≦ x ≦ 1.00,5.00 ≦ n <6.00,0 A ferrite porcelain composition for non-reciprocal circuit elements, comprising a main component represented by <y ≦ 0.30, 0 <z ≦ 0.30). The ferrite porcelain composition for a non-reciprocal circuit device according to any one of claims 1 to 3, comprising at least one of a Ca component and a Co component as a subcomponent, wherein the Ca component and The ferrite porcelain composition for nonreciprocal circuit elements, wherein the content of 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 any one of claims 1 to 4, comprising at least one of a Mn component and a Zr component as a subcomponent, wherein the Mn component and A ferrite porcelain composition for nonreciprocal circuit elements, wherein the content of the Zr component is 1.50% by weight or less (not including 0% by weight) in terms of oxide. A nonreciprocal circuit element comprising a ferrite member formed of the ferrite porcelain composition for a nonreciprocal circuit element according to any one of claims 1 to 5. A wireless device comprising the nonreciprocal circuit device according to claim 6.

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