Spinel-based oxides containing magnesium, aluminum and titanium and methods of forming articles having same
US-11891340-B2 · Feb 6, 2024 · US
US12234192B2 · US · B2
| Field | Value |
|---|---|
| Publication number | US-12234192-B2 |
| Application number | US-202318394922-A |
| Country | US |
| Kind code | B2 |
| Filing date | Dec 22, 2023 |
| Priority date | Jul 23, 2018 |
| Publication date | Feb 25, 2025 |
| Grant date | Feb 25, 2025 |
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The disclosed technology generally relates dielectric materials and methods of forming the same, and more particularly to a combination of co-fireable dielectric materials that can be attached to each other without the use of adhesives. In an aspect, a composite article comprises a magnetic portion comprising a nickel zinc ferrite. The composite article additionally comprises a non-magnetic portion contacting the magnetic portion, the non-magnetic portion comprising a spinel-structured oxide comprising Mg 2-x Al 2x Ti 1-x O 4 and having a dielectric constant between about 7 and 14, wherein 0<x≤1.
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The invention claimed is: 1. A method of forming a composite article, the method comprising: providing a pre-sintered magnetic article, the providing the pre-sintered magnetic article including pre-sintering, at a temperature higher than the co-firing temperature, a nickel zinc ferrite having a dielectric constant in a range between 5 and 10; providing a green article contacting the pre-sintered magnetic article, the green article including one or more precursor oxides having a ratio of magnesium (Mg):aluminum (Al):titanium (Ti) of (2−x):(2x):(1−x), wherein 0<x<1; and sintering the green article by co-firing the pre-sintered magnetic article and the green article at a co-firing temperature between 1300° C. and 1450° C., the compositions of the one or more precursor oxides being such that co-firing causes the one or more precursor oxides to form a non-magnetic spinel-structured oxide including Mg 2-x Al 2x Ti 1-x O 4 having a dielectric constant between about 7 and 14. 2. The method of claim 1 wherein the pre-sintered magnetic article is shaped to form an inner portion of the composite article and the green article is shaped to surround the pre-sintered magnetic article. 3. The method of claim 2 further comprising, prior to sintering, inserting the inner portion into an opening formed in the green article, and wherein sintering by co-firing causes the green article to shrink by a larger percentage compared to the inner portion, thereby causing an outer portion including the non-magnetic spinel-structured oxide to shrink-wrap around the inner portion, such that the inner and outer portions are attached to each other without use of an adhesive. 4. The method of claim 1 wherein the non-magnetic spinel-structured oxide includes a solid solution of MgAl 2 O 4 and Mg 2 TiO 4 . 5. The method of claim 1 wherein the one or more precursor oxides include: one or more Mg-containing oxides selected from the group consisting of MgO 2 , MgAl 2 O 4 , and Mg 2 TiO 2 ; one or more Al-containing oxides selected from the group consisting of Al 2 O 3 and MgAl 2 O 4 ; and one or more Ti-containing oxides selected from the group consisting of a titanium oxide and Mg 2 TiO 2 . 6. The method of claim 5 wherein the one or more precursor oxides further includes excess Al 2 O 3 in an amount greater than zero and less than or equal to about 10 percent on the basis of a total weight of the one or more precursor oxides. 7. The method of claim 5 wherein the one or more precursor oxides further includes excess ZnTiO 3 in an amount greater than zero and less than or equal to about 10 percent on the basis of a total weight of the one or more precursor oxides. 8. The method of claim 1 wherein the non-magnetic spinel-structured oxide has a density between 3.498 g/cc and 3.569 g/cc. 9. The method of claim 1 wherein the pre-sintered magnetic article and the green article are co-fired at a co-firing temperature between 1350° C. and 1400° C. 10. The method of claim 1 wherein the non-magnetic spinel-structured oxide has a density between 3.50 g/cc and 3.55 g/cc. 11. A method of manufacturing a radio frequency circulator, the method comprising: providing a disk-shaped magnetic portion, the providing the disk-shaped magnetic portion including pre-sintering, at a temperature higher than the co-firing temperature, a nickel zinc ferrite having a dielectric constant in a range between 5 and 10; providing a green article contacting the disk-shaped magnetic portion, the green article including one or more precursor oxides having a ratio of magnesium (Mg):aluminum (Al):titanium (Ti) of (2−x):(2x):(1−x), wherein 0<x<1; and sintering the green article by co-firing the disk-shaped magnetic portion and the green article at a co-firing temperature between 1300° C. and 1450° C., the compositions of the one or more precursor oxides are such that co-firing causes the one or more precursor oxides to form a non-magnetic spinel-structured oxide including Mg 2-x Al 2x Ti 1-x O 4 , which surrounds the disk-shaped magnetic portion and has a dielectric constant between about 7 and 14. 12. The method of claim 11 wherein the disk-shaped magnetic portion is shaped to form an inner portion of the radio frequency circulator and the green article is shaped to surround the disk-shaped magnetic portion. 13. The method of claim 12 further comprising, prior to sintering, inserting the inner portion into an opening formed in the green article, and wherein sintering by co-firing causes the green article to shrink by a larger percentage compared to the inner portion, thereby causing an outer portion including the non-magnetic spinel-structured oxide to shrink-wrap around the inner portion, such that the inner and outer portions are attached to each other without use of an adhesive. 14. The method of claim 11 wherein the non-magnetic spinel-structured oxide includes a solid solution of MgAl 2 O 4 and Mg 2 TiO 4 . 15. The method of claim 11 wherein the one or more precursor oxides include: one or more Mg-containing oxides selected from the group consisting of MgO 2 , MgAl 2 O 4 , and Mg 2 TiO 2 ; one or more Al-containing oxides selected from the group consisting of Al 2 O 3 and MgAl 2 O 4 ; and one or more Ti-containing oxides selected from the group consisting of a titanium oxide and Mg 2 TiO 2 . 16. The method of claim 15 wherein the one or more precursor oxides further includes excess Al 2 O 3 in an amount greater than zero and less than or equal to about 10 percent on the basis of a total weight of the one or more precursor oxides. 17. The method of claim 15 wherein the one or more precursor oxides further includes excess ZnTiO 3 in an amount greater than zero and less than or equal to about 10 percent on the basis of a total weight of the one or more precursor oxides. 18. The method of claim 11 wherein the non-magnetic spinel-structured oxide has a density between 3.498 g/cc and 3.569 g/cc. 19. The method of claim 11 wherein the disk-shaped magnetic portion and the green article are co-fired at a co-firing temperature between 1350° C. and 1400° C. 20. The method of claim 11 wherein the non-magnetic spinel-structured oxide has a density between 3.50 g/cc and 3.55 g/cc.
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