US3763045A - Calcium-vanadium ferrimagnetic garnets - Google Patents

Calcium-vanadium ferrimagnetic garnets Download PDF

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US3763045A
US3763045A US00130343A US3763045DA US3763045A US 3763045 A US3763045 A US 3763045A US 00130343 A US00130343 A US 00130343A US 3763045D A US3763045D A US 3763045DA US 3763045 A US3763045 A US 3763045A
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substitution
garnets
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H Takamizawa
K Yotsuyanagi
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NEC Corp
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Nippon Electric Co Ltd
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Priority claimed from JP45057966A external-priority patent/JPS4920155B1/ja
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/26—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on ferrites
    • C04B35/2641—Compositions containing one or more ferrites of the group comprising rare earth metals and one or more ferrites of the group comprising alkali metals, alkaline earth metals or lead

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  • ABSTRACT Provided are magnetic materials suitable for use in microwave circuit elements and having excellent properties such as a very low value of the ferromagnetic resonance linewidth, high curie temperature, a suitably controllable value of the saturation magnetization and improved temperature stability of the saturation magnetization.
  • Such materials are obtained by substituting Ca ions located on the 24c site and Fe ions on the 16a site in calcium-vanadium garnets with Y ions and Sn ions, respectively, or by further substituting the ions located on the 24d site in the calcium-vanadium garnets thus modified with Ge ions.
  • the present invention relates to calcium-vanadium (Ca-V) ferrimagnetic garnets for use in microwave circuit elements operating in the VHF, UHF or SHF band range.
  • Ca-V calcium-vanadium
  • the required characteristics of magnetic materials for use in such microwave circuit elements are low magnetic losses and small temperature variations of the saturation magnetization values (4 11' Ms). Desired values of 4 11- Ms will vary according to the application of the magnetic materials.
  • the essential condition for reducing the magnetic loss is that the ferromagnetic resonance linewidth (AI-I) be as low as possible.
  • yttrium-iron garnets that have been most commonly used as magnetic materials in microwave applications offer the advantages of lower 4 7r Ms values, higher Curie temperatures and lower magnetic losses than conventional spinel-type ferrites such as nickel series ferrites or magnesium-manganese series ferrites. These advantages of the yttrium-iron series garnets are considerably offset by detects such as the necessity for the use of yttrium oxide which is an expensive raw materials and the need for sintering at extremely high temperatures and for long time intervals which are not suited for large-scale industrial production.
  • the unmodified Ca-V garnet is known for featuring high Curie temperatures in spite of low 4 1r Ms, but its high A H rendered practical application extremely difficult.
  • the object of the invention to provide improved microwave circuit element materials for use in the VHF, UHF or SHF band range, having excellent characteristics such as low ferromagnetic. resonance linewidth values and high Curie temperatures.
  • the garnet compositions are generally expressed by a normal formula unit (A (B (C90 where the first, second and third parentheses represent respectively the 240, 16a and 24d sites and A, B and C denote atoms occupying the respective sites.
  • Fe has a preference for the two different sub-lattice sites (the 16a and the 24d sites) and the Fe-Fe super-exchangeinteractions in each of and between these sub-lattic sites cause the Fe magnetic moments at the 16a and 24d sites to be coupled anti-ferromagnetically.
  • the garnet compositions manifest ferrimagnetism. It has been generally considered that the compositions manifest anti-ferromagnetism in case of the site balance and at which an abnormal phenomenon of A H occurs.
  • the value of 4 7r Ms is determined by the relative site unbalance in the magnetic moment between the 16a and 24d sites for which Fe has a strong preference, while the temperature variation of4 11- Ms changes with the numbers of iron ions located on each sub-lattice site, kinds of non-magnetic ions replacing the iron ions, and kinds of ions located on the 24c site.
  • the unmodified calcium-vanadium garnet can be expressed by a normal formula unit (Ca (Fe (Fe 1.5 1.5) 12- SUMMARY OF THE INVENTION
  • Ca (Fe (Fe 1.5 1.5) 12- SUMMARY OF THE INVENTION calcium-vanadium garnets are improved by substituting Ca ions on the 240 site and Fe ions on the 16a site with Y ions and Sn ions, respectively, or by further substituting ions on the 24d site in the thus-modified garnets with Ge ions.
  • the improved calcium-vanadium garnets are featured by sufficiently low A H values, high Curie temperatures, 41rMs values within controllable suitable ranges, small temperature variations in the value of 4wMs and low manufacturing costs.
  • the values of x and y are within the ranges of 0.3 x 0.5 and 1.2 y g 2.0, respectively. With such compositions, the value of A H is less than 10 oersteds.
  • the Y-and Sn-substituted Ca-V garnets can be further substituted with Ge.
  • the garnet compositions thus obtained can be expressed as in which at, y and 2 should be within the ranges of 0 x E 0.5, 1.0 g y 2.4 andO z 0.5,respectively and they should satisfy the relation of 1.5 0.5x 0.5y 0.5z 0. Where the difference of the numbers of Fe ions between 16a and 24d sites I (2 x) (1.5 0.5x
  • compositions satisfying the relation of 0.8 I 3x y z 1.2 should be excluded. It is preferable that x, y and 2 lie within the ranges of 0.25 x 0.5, 1.2 y 2.4 and 0.2 1 0.4, respectively.
  • the Y-, Snand Gesubstituted Ca-V garnets within such ranges have low A H of less than 20 oersteds.
  • FIGS. 1, 2 and 3 show, respectively, ferromagnetic resonance linewidths (A H), Curie temperatures and 4 1rMs as a function of x for the Y- and Sn-Substituted Ca-V ferrimagnetic garnets of this invention with the compositions expressed by the formula mentioned above;
  • FIG. 4 is a diagram illustrating the effective range of the values of x and y in the Y- and Sn-substituted Ca-V garnet compositions expressed as above;
  • FIG. 5 shows the effect of x on 4 qrMS and A H for the Y-, Snand Ge-substituted Ca-V garnet composition expressed by the mentioned formula where y 1.4 and z 0.3;
  • FIGS. 6 and 7 show the effect of y on A H and Curie temperature, respectively for the Y- and Sn-substituted Ca-V garnets;
  • FIG. 8 shows influence of z(Ge) on A H and 41rMs for the Y-, Snand Ge-substituted Ca-V garnet compositions expressed by the formula mentioned above;
  • FIG. 9 is a graph of the 41rMs versus temperature characteristics of garnet compositions of the prior art and of this invention which illustrates the advantages of this invention.
  • Table 1 lists the results of measurements for the unsubstituted, Ge-substituted, Sn-substituted, Snand Gesubstituted, Y- and Snsubstituted and Y-, Snand Gesubstituted Ca-V garnet compositions to demonstrate the successively promoted substitution effects, as regards a decrease in the linewidth A H and an increase in the Curie temperature.
  • Sample No. l, or unmodified Ca-V garnet has low 4 rrMs and high Curie temperature, but A H is as high as 370 (i.e., large magnetic loss). Therefore, practical use of this garnet is substantially impossible. It will be noted with No.
  • a H exhibits an extraordinarily large value near x 0.167 for y 0.5 by the abnormal phenomenon mentioned previously. But, A H decreases with increasing x beyond this value to reach A H 63 at x 0.5. In other words, A H has been improved to a value less than we of that at x 0. In similar manner, it takes an extraordinarily large value in the vicinity of x 0.067 for y 0.8, but decreases with increasing 1: beyond this point to reach A H 60 at x 0.5. Thus A H has been improved to a value of the order of /4 of that at x 0.
  • the slopes of these curves become less steep with increasing y.
  • the Curie temperature decreases 125, 110, 97, and 87 degrees Centigrade respectively with an increase in x from 0 to 0.5 for y 0.5, 0.8, 1.2, and 1.5.
  • the Curie temperature rises with increasing y, but the results of extensive experimentation conducted by us has proven that the Ca-V garnet compositions, which exhibit Curie temperatures most suitable for practical application, must have x and y values meeting the relation of x 0.35y 0.3.
  • the compositions which do not meet this relationship have been found to be difficult for reduction to practice in having low Curie temperature and large variations of 41rMs with temperature.
  • the hatched area indicates the effective range of the values of x and y, where z 0, in the garnet compositions expressed by the formula mentioned above.
  • the area between the lines of 3x y 0.8 and 3x y 1.2 is excluded, because the abnormal phenomenon of A H occurs there.
  • a rapid increase in A H for y 2.4 is attributed to the insufficiency of the prescribed sintering temperature of 1300C for the maturity of sintering with increasing Y.
  • 1: and y values are defined as 0 y 2.5; 1.5 0.5x 0.5y 0 in order to lower A H.
  • FIG. 7 which shows the effect of Y- substitution on Curie temperature, there isa tendency toward a gradual increase in the Curie temperature with increasing Y, demonstrating the possibility of compensating for the lowering of Curie temperature with increasing Sn content by Y-substitution.
  • FIG. 7 also indicates a tendency toward the lowering of Curie temperature for 1.5 0.5x 0.5y 0 that is, when vanadium content is nil.
  • the Y-substitution is effective for lowering AH and at the same time, elevating the Curie temperature. But, with an increase in Y-concentration, there arises the need for elevating the sintering tmperature to bring sintering to maturity. For these reasons, the effective x and y ranges are defined as follows: 0 y 2.5 and 1.5 0.5x 0.5y 0 for z 0; or 1.0 y 2.4 and 1.5 0.5x 0.5y 0.52 0 for z 0.
  • FIG. 8 shows the results of measurement for these samples, indicating both 41rMs and A H as a function of z. Data on Curie temperatures for these samples are shown in Table 4.
  • tn-Ms decreases with increasing Ge substitution.
  • values of 4'rrMs are 880, 530, and 200 respectively at z 0, 0.3,
  • a H decreases from 50 Oe at z 'with increasing z to reach a minimum 24 at z 0.5. As this point is passed, A H gradually increases with increasing Ge-substitution.
  • an optimum 1 range for low A H and small temperature variation of 4'n'Ms can be defined as 0 2 0.5. Therefore, materials suitable for practical use with low A H, such as less than 50 within 0 z 2 0.5 for x 0.3 and y 1.4, and optimum 41rMs values ranging be- Al-substituted yttrium iron garnet Y Fe Al O (curve 0) were prepared. All of these samples had roomtemperature 411-Ms values of the order of 500 gauss. FIG. 9 shows variation of 41rMs with temperature for these three samples.
  • Table 1 To evaluate how the proposed Ca-V garnet composi- Sintertions contribute to the improvement in A H, several g g cmpsmon Te 2: samples with x 0.3 and 0.5, y from 1.2 to 1.8, and z (gauss) (0e) (C) 0 were prepared by sintering between 1300C and (Ca )(Fe )(Fe v 1350C for 10 hours. Table 5 lists values of 41rMs, A H, z 1210 520 370 210 and Curie temperature for these samples.
  • the known Y- and ln-substituted Ca-V garaX m mnets had A H of the order of 2.0 Oe, Curie temperatures (FeMGCMVLQOZ 390 120 as low as 140C, and high 41rMs in excess of 1400 35 Ega, ,g,
  • Sintcr- Table 6 indicates that the Ca-V garnets according to ig s: this invention maintain excellent theoretical densities c (Gauss) (0e) ((3) in excess of 97 percent, whereas the theoretical density (Ca )(Fe Sn of the yttrium iron garnet is only 91.4 percent.
  • c Gibbs
  • Ca calcium Y tering at higher temperatures, 1450C or higher for in- ,f: stance
  • Ferrimagnetic garnets having compositions expressed by the formula:

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3855691A (en) * 1972-03-07 1974-12-24 Lignes Telegraph Telephon Method of making a magnetic material part with spatial distribution of the permeability
US3947372A (en) * 1972-08-11 1976-03-30 Hitachi, Ltd. Ferrimagnetic material
JPS5234394A (en) * 1975-08-01 1977-03-16 Nec Corp Microwave ferrite
US4125473A (en) * 1976-10-26 1978-11-14 Thomson-Csf Polycrystalline ferrimagnetic garnet having a narrow gyromagnetic resonance line width and a low magnetic moment
EP0635855A1 (en) * 1993-07-20 1995-01-25 Murata Manufacturing Co., Ltd. Magnetic material for high frequencies
US5620543A (en) * 1992-11-25 1997-04-15 Murata Manufacturing Co., Ltd. Method of manufacturing microwave magnetic material body
US6596255B2 (en) * 2000-05-25 2003-07-22 National Institute Of Advanced Industrial Science And Technology Tin-containing granular magnetic oxide particles and process for producing the same
US20040099837A1 (en) * 2002-11-18 2004-05-27 Kim Dong-Young YIG magnetic ceramic composition for microwave application and preparation method thereof
US20080165072A1 (en) * 2007-01-09 2008-07-10 Schlager Kenneth J High gain antenna and magnetic preamplifier

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3006855A (en) * 1959-04-29 1961-10-31 Bell Telephone Labor Inc Ferrimagnetic garnets
US3156651A (en) * 1962-03-28 1964-11-10 Bell Telephone Labor Inc Light transparent ferrimagnetic garnets
US3268452A (en) * 1963-07-10 1966-08-23 Bell Telephone Labor Inc Vanadium-containing garnets
US3447851A (en) * 1965-11-08 1969-06-03 Bell Telephone Labor Inc Ferrimagnetic light transmission garnets
US3639247A (en) * 1969-02-07 1972-02-01 Nippon Electric Co Calcium-vanadium series ferrimagnetic garnets
US3654162A (en) * 1970-10-01 1972-04-04 Gte Laboratories Inc Ferrimagnetic iron garnet having large faraday effect

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3006855A (en) * 1959-04-29 1961-10-31 Bell Telephone Labor Inc Ferrimagnetic garnets
US3156651A (en) * 1962-03-28 1964-11-10 Bell Telephone Labor Inc Light transparent ferrimagnetic garnets
US3268452A (en) * 1963-07-10 1966-08-23 Bell Telephone Labor Inc Vanadium-containing garnets
US3447851A (en) * 1965-11-08 1969-06-03 Bell Telephone Labor Inc Ferrimagnetic light transmission garnets
US3639247A (en) * 1969-02-07 1972-02-01 Nippon Electric Co Calcium-vanadium series ferrimagnetic garnets
US3654162A (en) * 1970-10-01 1972-04-04 Gte Laboratories Inc Ferrimagnetic iron garnet having large faraday effect

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Geller et al., Journal of Applied Physics , Vol. 35, No. 3, pp. 570 572, March 1964. *
Yudin et al. Physics Letters , Vol. 28A, No. 7, PP. 483 484, January, 1969. *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3855691A (en) * 1972-03-07 1974-12-24 Lignes Telegraph Telephon Method of making a magnetic material part with spatial distribution of the permeability
US3947372A (en) * 1972-08-11 1976-03-30 Hitachi, Ltd. Ferrimagnetic material
JPS5234394A (en) * 1975-08-01 1977-03-16 Nec Corp Microwave ferrite
JPS6019126B2 (ja) * 1975-08-01 1985-05-14 日本電気株式会社 マイクロ波フエライト
US4125473A (en) * 1976-10-26 1978-11-14 Thomson-Csf Polycrystalline ferrimagnetic garnet having a narrow gyromagnetic resonance line width and a low magnetic moment
US5620543A (en) * 1992-11-25 1997-04-15 Murata Manufacturing Co., Ltd. Method of manufacturing microwave magnetic material body
US5589096A (en) * 1993-07-20 1996-12-31 Murata Manufacturing Co., Ltd. Magnetic material for high frequencies
EP0635855A1 (en) * 1993-07-20 1995-01-25 Murata Manufacturing Co., Ltd. Magnetic material for high frequencies
US6596255B2 (en) * 2000-05-25 2003-07-22 National Institute Of Advanced Industrial Science And Technology Tin-containing granular magnetic oxide particles and process for producing the same
US20040099837A1 (en) * 2002-11-18 2004-05-27 Kim Dong-Young YIG magnetic ceramic composition for microwave application and preparation method thereof
US6899819B2 (en) 2002-11-18 2005-05-31 Electronics And Telecommunications Research Institute YIG magnetic ceramic composition for microwave application and preparation method thereof
US20080165072A1 (en) * 2007-01-09 2008-07-10 Schlager Kenneth J High gain antenna and magnetic preamplifier
US7528795B2 (en) * 2007-01-09 2009-05-05 Hiercomm, Inc. High gain antenna and magnetic preamplifier
US20090284422A1 (en) * 2007-01-09 2009-11-19 Schlager Kenneth J High Gain antenna and magnetic preamplifier

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NL172143B (nl) 1983-02-16
NL7104493A (nl) 1971-10-05
GB1281498A (en) 1972-07-12
NL172143C (nl) 1983-07-18
DE2116351C3 (de) 1978-08-31
DE2116351B2 (de) 1977-12-22
DE2116351A1 (de) 1972-01-13

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