JPH04114411A - Magnetic composition for microwave and millimeter wave - Google Patents

Abstract

PURPOSE:To simultaneously realize a very small half width of ferromagnetic resonance absorption, large residual flux density, and a small dielectric loss by a method wherein a part of the Fe site of a specific YIG ferrite is replaced with Mn, and at the same time, copper oxide and tin oxide are added. CONSTITUTION:In the composition indicated by (Y1-xGdx)w(Fe1-y-zAlyMnz)8-wO12, the composition wherein x, y and z and w are in the range of 0<=x<=0.35, 0<=y<=0.16, 0.01<=z<=0.04 and 3.02<=w<=3.06 is used as the main component, and copper oxide indicated by the form of CuO and the tin oxide indicated by the form of SnO2 of 0.5mol% or more and 2.0mol% or less are added and contained. As a result, a sufficiently small half width of paramagnetic resonance absorption, a sufficiently small dielectric loss and high residual magnetic flux density are given to the above-mentioned material, and as a result, the material which is very useful for the application of the material to the circuit element such as a latching type phase converter, a highly stable isolator and circulator and the like, can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a magnetic composition used in high frequency regions such as microwaves and millimeter waves.

<Conventional technology> Conventionally, as magnetic materials for high frequency, Mn-Mg ferrite, Ni-Zn ferrite, lithium ferrite, Y
IG ferrite etc. are used.

These have saturation magnetization (4πMs) values of 500 to 400.
It is an excellent material with 0 Gauss.

Among these, YIG ferrite is known as U.S. Patent No. 3,1
32,105, YsFesO+
Since the temperature coefficient (α) of 4πMs and 4πMs can be changed by substituting Gd and A1 in the composition consisting of When used in combination with a permanent magnet, it is an excellent material that can compensate for the temperature characteristics of the magnet, and is a material that can be applied to highly stable circuit elements such as isolators and circulators.

Furthermore, according to U.S. Pat. No. 3,419,496, this material has a low volume resistivity ρ of 7.0
It is said that it can be increased to 3Ω・Cl11. moreover,
According to Japanese Patent Publication No. 60-55970, the raw material Y2O
, and FeaOm at a mixing ratio of 38°63 to 39, respectively.
It is said that the ferromagnetic resonance absorption half width (ΔH) can be reduced to 16 oersteds when the content is 45 mol % and 61.37 to 60.55 mol %.

<Problem to be solved by the invention> However, YIG ferrite has problems such as ΔH and dielectric loss (
It has the disadvantage that loss values such as tan δ) become large enough to cause practical problems due to subtle compositional fluctuations. Further, when this material is used as a phase conversion element, a high residual magnetic flux density (Br) is required, but there is a problem in that Br is made thicker (then tan δ also becomes larger).

In view of the above problems, this invention was made to improve the drawbacks of conventional YIG ferrite, and YwFe
By replacing part of Y of YIG ferrite expressed by the general formula s-wo+x with Gd, α can be set to any value, and by replacing part of Fe with M, 4zMs can be set to any value. In addition, by replacing a part of Fe with Mn and simultaneously adding copper oxide and tin oxide, we achieved an extremely small value of ΔH.
The object of the present invention is to provide a magnetic material for microwaves and millimeter waves that simultaneously achieves a large r value and a small tan δ value by fixing the site ratio within a very limited narrow range.

Means for Solving the Problems> As a result of intensive research in order to solve these problems, the present inventors found that a part of the Fe site of YIG ferrite represented by the general formula YwFes -wO+a was replaced with Mn. At the same time, we found that an extremely small ΔH can be obtained by adding copper oxide and tin oxide, and we also found that a large ΔH can be obtained in a very narrow region where the ratio W of Y site to Fe site is between 3.02 and 3.06. They discovered that it is possible to simultaneously achieve a small tan δ.

That is, in order to solve the above-mentioned problems, the microwave/millimeter wave magnetic composition of the present invention (Y+-xGdjw
(In the composition represented by Fe+-y-zAjyMnjs-wo+*, x, y, z and W each satisfy 0≦x
≦0.35.0≦y≦0.16.0.01≦Z≦0.0
The main component is a composition in the range of 4.3.02≦w≦3.06, and copper oxide expressed in the form of CuO and SnO
0.5 mol% or more of tin oxide expressed in the form of □,
It is characterized in that it is added in an amount of 2.0 mol% or less.

Effect> According to the present invention, 4zMs can be arbitrarily set in the range of 350 to 1780 Gauss, and therefore a material having a value of 4zMs most suitable for the frequency used can be selected.

Further, since α can be arbitrarily set within the range of -910 to -2730 ppm/''C, the temperature characteristics of the magnet can be compensated when used in combination with a permanent magnet or the like.

Furthermore, since Br is high and loss values such as ΔH and janδ are extremely small, a magnetic material for microwaves and millimeter waves suitable for application to latching type phase converters, high-precision isolators, and circierators can be obtained. be able to.

The above-mentioned objects, features, and advantages of the present invention will be explained below by way of examples with reference to the drawings.

<Example> First, as raw materials, high purity YxOs, Fe*Os,
GdxOs, AI! *Os, MnOz, CuO and 5nOi were prepared. These raw materials are listed in Table 1 and Table 2.
The compositions were weighed so as to obtain the compositions shown in Table 3 and Table 3, and mixed in a ball mill for 16 hours. After drying this mixture, it was calcined at 1050° C. for 2 hours to obtain a calcined product. This calcined product was placed in a ball mill along with an organic binder, and
It was milled for 6 hours. After drying this pulverized material, it is granulated through a 50-mesh mesh, and the resulting powder is
g/am” pressure 311101X 3mm X 20
It was molded into a rectangular prism of mm and a ring with an outer diameter of 36 ma+, an inner diameter of 24 mm, and a thickness of 6 mm. These molded products are 1460
After firing at ~1490°C for 8 hours, the prismatic sintered body was machined to form spheres with a diameter of 1.3 mm and spheres with a diameter of 1.3 mm.
A cylindrical sample with a diameter of 3 mm and a length of 16 mm was obtained.

The temperature coefficient (α) and Curie temperature (Tc) of 4zMg and 4zMs were measured for the obtained spherical sample using a vibrating magnetometer, and
81 at GHz was measured.

Further, for the cylindrical sample, t and ariδ at 10 GHz were measured using an imaging method in a TMi01 cavity shaker.

Furthermore, for the Sunonobu sample, the conducting wire was wound with a pie filer to form a toroidal coil, and the frequency of 100Hz was
The residual magnetic flux density (Br) and coercive force (He) were measured.

Table 1 is (Yi-xGdx)w (Fei-y-zu
These are the measurement results when X and y of the composition represented by yMnz) a-wo+a were varied, and the amount of oxide expressed in the form of CuO and the amount of tin oxide expressed in the form of 51102 was varied. . Items marked with * in Table 1 are outside the scope of this invention, and all others are within the scope of this invention. Furthermore, the composition range of the experimental example shown in Table 1 is
It is shown in the composition diagram of FIG. The numbers in this drawing represent each sample number. Note that in FIG. 1, a region exhibiting a composition ratio within the range of the present invention is shown by a rectangle having vertices A, B, C, and D.

Here, (Yi-xGdjw (FeI-y-xAj
Let X and y of the composition represented by yMnja, 0° be (
The reason for limiting each to the range of 0≦x≦0.35.0≦y≦0.16 will be explained below.

y is 0.1 as in sample numbers 7.14.21 and 25
If it exceeds 6, Br becomes small and Te becomes low, which is not preferable.

Also, as in sample numbers 22, 23, 24 and 25,
If it exceeds 0.35, ΔH becomes large, which is not preferable.

Next, the reason why the amounts of Cu oxide expressed in the form of O and tin oxide expressed in the form of 5n02 were limited to 0.5 mol % or more and 2.0 mol % or less, respectively, will be explained.

First, sample numbers 2.9 and 16 are CuO and SnO
This is an example in which the addition amount of □ is t10% by mole, and is excluded from the scope of the present invention.

CuO and Sn as in sample number 3.10 and ]7
If the amount of ow added is 0.5 mol% or more,
If the improvement effect on ΔH is not significant (it is excluded from the scope of this invention).

CuO and 5n as in sample numbers 5.12 and 19
Those in which the amount of Oa added exceeds 2.0 mol%,
As ΔH increases, Br decreases, which is not preferable.

Here, the action of 5nOa is to compensate the valences of the divalent copper ion and the tetravalent tin ion, making the total trivalent (Yt-xGdx) w (FeI-y −
zAll yMnx)s-mol! The purpose is to incorporate each ion into the (Fen-y-iAl, MRI) site of the composition represented by the following without any difficulty in terms of charge. Therefore, instead of Snow, 5fOs, Ti1t, Genu
Similar effects can be obtained by using oxides of tetravalent ions such as sZr0a and Hf0i.

Next, Table 2 shows (Yt-xGdx)v (FeI-y
-zAj, Mn engineering), -,0□, Z
These are the measurement results when changing .

Sample numbers 26 to 30 in Table 2 are the compositions of sample number 4 in Table 1 with 2 changed, and sample numbers 31 to 35 in Table 2 are the samples in Table 1. Sample numbers 36 to 40 in Table 2 have the composition of sample number 18 in Table 1 with Z changed.

Items marked with * in Table 2 are outside the scope of this invention, and all others are within the scope of this invention.

The composition range of the experimental examples shown in Table 2 is shown in the composition diagram of FIG. 1, as in Table 1. The numbers in this drawing represent each sample number.

Here, (Yi-xGdlI)w (FeI-y-xA
The reason why Z in the composition represented by NyMnx)s-wo+a is limited to 0.01≦Z≦0.04 will be explained.

When 2 becomes 0.01 or less, as in sample numbers 26.31 and 36, ΔH becomes large, which is not preferable.

Also, as in sample numbers 30.35 and 40, 2 is 0.
If it exceeds 04, ΔH becomes large, which is not preferable.

Finally, Table 3 shows (Yi-xGax)w (FeI-y
-iU yMnz). -W of the composition represented by wO□
These are the measurement results when changing .

Sample numbers 41 to 45 in Table 3 are the compositions of sample number 4 in Table 1 with W changed, and sample numbers 46 to 50 in Table 3 are the samples in Table 1. Sample numbers 51 to 55 in Table 3 have the composition of sample No. 18 in Table 1 with W varied.

Items marked with * in Table 3 are outside the scope of this invention, and all others are within the scope of this invention.

The composition ranges of the experimental examples shown in Table 3 are shown in the composition diagram of FIG. 1, as in Tables 1 and 2. The numbers in this drawing represent each sample number.

Here, (Y+-xGdJw (Fe+-y-zAJy
Mnz)++-wO+z, W is 3.
The third reason for limiting the range to 02≦w≦3.06
When W is 3.02 or less, as in Sample Nos. 41.46 and 51, which will be explained with reference to the table and FIG. 2, tan δ increases, which is undesirable.

Also, as in sample numbers 45.50 and 55, W is 3.
06 or more, ΔH becomes large and Br becomes small (which is not preferable).

Figure 2 shows sample numbers 46 to 50 (Y, , Gdx
)=(Fe+-y-x uyMnz)a-wO+z W
and the common logarithm value of tanδ (log tanδ) and B
It is a diagram illustrating the relationship between r. As is clear from FIG. 2, a large r and a small tan δ can be achieved at the same time only when W is in the range of 3.02≦w≦3.06.

Note that the numbers in FIG. 2 represent each sample number.

<Effects of the Invention> As explained in detail below, the magnetic composition for microwaves and millimeter waves according to the invention has a tan δ of 8H, which is as small as 4 minutes, and a tan δ that is sufficiently small, T'i' L, . It also has a high 1°C and a large r, making it a very useful material for application to circuits such as radging type phase converters, highly stable isolators, and circulators. Furthermore, (Y+-xGdx)iu ()ei-yAIJn 8-WO12 by appropriately changing X and y within the scope of the present invention, 4πMs
can be set arbitrarily in the range of 350 to 1,780 Gauss, and a can be arbitrarily set in the range of -910 to -2,730 ppm/''C. Therefore, the value of 47LM s that is most suitable for the frequency to be used can be set. In addition, when used in combination with permanent magnets, it is possible to compensate for the mixed use characteristics of magnets.

[Brief explanation of drawings]

FIG. 1 shows (yi-xcdx), (Fei->, Al
yMnx) a-wo+a composition diagram showing the composition range of X and y, Figure 2 is number 4 in Table 3; 46-50
ni-・)tte (yi-xeax)w (Fei-y-z
It is a graph showing the relationship between W, the common logarithm value (log tan δ) of tan δ, and Br of uyMnz)a-wo+z. Figure 2 (X) (W)

Claims (1)

[Claims] (Y_1_-_xGd_x)_w(Fe_1_-_y_
-_zAl_yMn_z)_5_-_wO_1_2, x, y, z and w are respectively 0≦x≦0.35, 0≦y≦0.16, 0.01≦z≦
The main component is a composition in the range of 0.04, 3.02≦w≦3.06, and copper oxide expressed in the form of CuO and tin oxide expressed in the form of SnO_2 are each 0.5 mol% or more. A microwave/millimeter wave magnetic composition comprising 2.0 mol% or less of .