Glass-ceramic as dielectric in the high-frequency range

Patent metadata

Field	Value
Publication number	US-9272944-B2
Application number	US-201414283707-A
Country	US
Kind code	B2
Filing date	May 21, 2014
Priority date	Nov 24, 2011
Publication date	Mar 1, 2016
Grant date	Mar 1, 2016

Abstract

A glass-ceramic is disclosed, this glass-ceramic includes at least the following constituents (in mol % on oxide basis): SiO 2 1-30, Al 2 O 3 0-20, B 2 O 3 0-25, TiO 2 10-70, RE 2 O 3 0-35, BaO 5-35, SiO 2 +Al 2 O 3 +B 2 O 3 <25, where RE is lanthanum, another lanthanoid, or yttrium, and where Ti may be replaced in part, preferably up to 10%, by Zr, Hf, Y, Nb, V, Ta. A principal phase in the glass-ceramic is BaTi 4 O.

First claim

The invention claimed is:

1. A glass-ceramic comprising at least the following constituents (in mol % on oxide basis):
SiO 2 1-<25
Al 2 O 3 0-20
B 2 O 3 0-<24
TiO 2 10-70
RE 2 O 3 0.1-<4.9
BaO 5-35
SiO 2 +Al 2 O 3 +B 2 O 3 <25
wherein RE is selected from the group consisting of a lanthanoid and yttrium, and wherein Ti may be replaced in part by at least one constituent selected from the group consisting of Zr, Hf, Nb, V, and Ta.

2. The glass-ceramic of claim 1 , comprising at least the following constituents (in mol % on oxide basis):
SiO 2 2-20
Al 2 O 3 0-15
B 2 O 3 0-18
TiO 2 25-65
ZrO 2 1-15
RE 2 O 3 0.1-<4.9
BaO 10-30
SiO 2 +Al 2 O 3 +B 2 O 3 ≦20,
wherein RE is selected from the group consisting of a lanthanoid and yttrium, and wherein Ti may be replaced in part by at least one constituent selected from the group consisting of Zr, Hf, Nb, V, and Ta.

3. The glass-ceramic of claim 2 , comprising at least the following constituents (in mol % on oxide basis):
SiO 2 2-20
Al 2 O 3 0-15
B 2 O 3 0-5
TiO 2 40-65
ZrO 2 5-12
RE 2 O 3 0.1-<4.9
BaO 10-30
10≦SiO 2 +Al 2 O 3 +B 2 O 3 ≦20,
wherein RE is selected from the group consisting of a lanthanoid and yttrium, and wherein Ti may be replaced in part by at least one constituent selected from the group consisting of Zr, Hf, Nb, V, and Ta.

4. The glass-ceramic of claim 1 , comprising at least the following constituents (in mol % on oxide basis):
SiO 2 4-8
Al 2 O 3 7-11
B 2 O 3 0-1
TiO 2 45-55
ZrO 2 5-10
RE 2 O 3 0.1-<4.9
BaO 15-30
10≦SiO 2 +Al 2 O 3 +B 2 O 3 ≦20,
wherein RE is selected from the group consisting of a lanthanoid and yttrium, and wherein Ti may be replaced in part by at least one constituent selected from the group consisting of Zr, Hf, Nb, V, and Ta.

5. The glass-ceramic of claim 1 , comprising at least the following constituents (in mol % on oxide basis):
SiO 2 4.5-7
Al 2 O 3 8-10
B 2 O 3 0-0.5
TiO 2 48-55
ZrO 2 6-9
RE 2 O 3 0.1-<4.9
BaO 20-26
wherein RE is selected from the group consisting of a lanthanoid and yttrium, and wherein Ti may be replaced in part by at least one constituent selected from the group consisting of Zr, Hf, Nb, V, and Ta.

6. The glass-ceramic of claim 1 , comprising at least 0.005 mol % of a melting additive.

7. The glass-ceramic of claim 6 , wherein the melting additive is a low-melting additive of a eutectic composed of glass-forming components.

8. The glass-ceramic of claim 1 , comprising 0.01 up to 3 mol % of at least one refining agent selected from the group consisting of As 2 O 3 and Sb 2 O 3 .

9. The glass-ceramic of claim 1 , comprising a dielectric loss (tan δ) of not more than 10 −2 in the high-frequency range at a frequency f>200 MHz.

10. The glass-ceramic of claim 1 , having a relative permittivity ∈ of at least 15.

11. The glass-ceramic of claim 1 , having a resonance frequency with a certain temperature dependence, wherein an absolute value of said temperature dependence of said resonance frequency |τ f | not more than 200 ppm/K.

12. The glass-ceramic of any of claim 1 , comprising at least one solid solution phase based on Ba, Ti, and O, wherein Ba may be replaced at least in part by at least one constituent selected from the group consisting of Sr, Ca, and Mg, and wherein Ti may be replaced at least in part by at least one constituent selected from the group consisting of Zr, Hf, Nb, V, and Ta.

13. The glass-ceramic of claim 12 , wherein said least one solid solution phase based on Ba, Ti, and O, further comprises at least one selected from the group consisting of Al, RE, and Si, wherein RE is selected from the group consisting of a lanthanoid and yttrium.

14. The glass-ceramic of claim 1 , comprising at least one solid solution phase of the formula (BaO) x (RE 2 O 3 ) y (SiO 2 ) z (TiO 2 ) u , wherein RE is selected from the group consisting of a lanthanoid, and yttrium, wherein x, y, and z are all positive integer numbers smaller than five, wherein up to 10% of Ba may be replaced by at least one constituent selected from the group consisting of Sr, Ca, and Mg, and wherein up to 10% of the obligatory fraction of Ti may be replaced by at least one constituent selected from the group consisting of Zr, Hf, Nb, V, and Ta.

15. The glass-ceramic of claim 1 , comprising as predominant solid solution phase BaTi 4 O 9 , wherein Ba may be replaced in part by at least one constituent selected from the group consisting of La, Ca, and Sr, and wherein Ti may be replaced in part by at least one constituent selected from the group consisting of Zr, Hf, Y, Nb, V, and Ta.

16. The glass-ceramic of claim 1 , comprising as predominant solid solution phase Ba 4 Al 2 Ti 10 O 27 , wherein Ba may be replaced in part by at least one constituent selected from the group consisting of La, Ca, and Sr, and wherein Ti may be replaced in part by at least one constituent selected from the group consisting of Zr, Hf, Y, Nb, V, and Ta.

17. The glass-ceramic of claim 1 , having an average crystallite size of 10 nanometers to 50 micrometers.

18. A dielectric resonator, electronic frequency filter element, or antenna element for the high-frequency range, having a dielectric comprising a glass-ceramic according to claim 1 .

19. A method of producing a dielectric having a dielectric loss of not more than 10-2 in the high-frequency range, comprising the following steps:
melting and homogenizing a starting glass which comprises the following constituents (in mol % on oxide basis):
SiO 2 1-<25
Al 2 O 3 0-20
B 2 O 3 0-25
TiO 2 10-70
RE 2 O 3 0.1-<4.9
BaO 5-35
SiO 2 +Al 2 O 3 +B 2 O 3 <25

wherein RE is selected from the group consisting of a lanthanoid and yttrium, and wherein Ti may be replaced in part by at least one constituent selected from the group consisting of Zr, Hf, Nb, V, and Ta;
pouring the starting glass into a desired shape;
cooling the starting glass to room temperature;
ceramizing the starting glass by a heat treatment.

20. The glass-ceramic of claim 1 , wherein the RE 2 O 3 is present (in mol % on oxide basis) in an amount of 1 to 3.5.

Assignees

• Schott Ag

Inventors

• Hovhannisyan Martun
• Letz Martin
• Kissl Gordon

Classifications

• C03C2204/00

  Glasses, glazes or enamels with special properties · CPC title

• C03C3/068

  containing rare earths · CPC title

• C03B32/02

  Thermal crystallisation, e.g. for crystallising glass bodies into glass-ceramic articles {(C03B27/012 takes precedence)} · CPC title

• H01P7/10

  Dielectric resonators · CPC title

• C03C4/16

  for dielectric glass · CPC title