The invention relates to a glass-ceramic which can be used as dielectric in the high-frequency range (frequency>200 MHz), in particular in the gigahertz range (frequency f>1 GHz).
Special materials which have a very high relative permittivity ∈ combined with a very low dielectric loss (tan δ) are required for a number of applications in the high-frequency range. To avoid close-range detuning due to the body of a user (referred to as “body loading”), dielectric charging of antennae, filters and other devices is of particular importance. This requires dielectrics which have a high relative permittivity, with ∈>15, and a low dielectric loss (tan δ) of not more than 10−2, preferably lower, in the high-frequency range. Furthermore, the temperature dependence of the resonance frequency τf should be very small. Finally, such a material should be able to be processed in a very simple and inexpensive way in order to make near net shapes possible at low cost.
A number of ceramic materials which are processed by sintering processes are known in the prior art. These include a BiNbO4 system which has been disclosed in Mirsaneh et al., “Circularly Loaded Dielectric-Loaded Antennas: Current Technology and Future Challenges”, Adv. Funct. Materials 18, (2008), pp. 1-8, for use in the case of dielectrically charged antennae for the gigahertz range. This material is used for producing the two most widely used forms of antennae, the circularly polarized DLA helix antenna (D-LQH antenna) and the square patch antenna. For this purpose, a glass having the composition 30 mol % of Bi2O3, 30 mol % of Nb2O5, 30 mol % of B2O3 and 10 mol % of SiO2 is melted in a conventional way at 1250° C. for two hours.
This glass was poured into cylindrical moulds, depressurized at from 500 to 520° C. and slowly cooled to room temperature. Crystallization was subsequently carried out at various temperatures in the range from 600° C. to 1000° C. The optimal value for antennae applications is said to be, for a heat treatment at 960° C., a relative permittivity ∈ of 15 with a quality factor Q·f0 of 15 000 GHz and a temperature coefficient of the resonance frequency τr of −80 MK−1. The crystalline phase determined here was essentially orthorhombic BiNbO4.
This system using bismuth and niobium is very expensive in terms of the raw materials.
In addition, there are a number of sintered ceramic materials (cf. U.S. Pat. No. 6,184,845 B1, US 2007/063902 A1). In these references, a sintered ceramic material based on zirconium titanate or based on zirconium-tin titanate having a relative permittivity of about 36 is disclosed as dielectric material for the ceramic core of a dielectrically charged D-LQH antenna. The material is said to be produced by extrusion or pressing and subsequent sintering.
Further sintered materials are indicated in the review by M. T. Sebastian et al., “Low loss dielectric materials for LTCC applications”, International Materials Reviews, Vol. 53, 2008, pp. 57-90. Even though some of these materials are referred to as “glass-ceramics”, they are sintered materials since they are produced by sintering a mixture of vitreous and crystalline powders.
Dielectrics produced by sintering have a number of disadvantages: every sintering process is always accompanied by a certain shrinkage, which leads to geometric inaccuracies and corresponding final machining. Furthermore, every sintering process results in a certain residual porosity which is a disadvantage when the surface is metalized. The metal penetrates into the pores and increases the dielectric loss of the dielectric.
In addition, the production of sintered materials is fundamentally relatively complicated and expensive.
A first object of the invention is to provide an improved material which can be used as dielectric for high-frequency applications.
A second object of the invention is to provide an improved material which has a high relative permittivity.
A third object of the invention is to provide an improved material which has a low dielectric loss.
A fourth object of the invention is to provide an improved material for a dielectric, which should be able to be produced and processed in a very simple and inexpensive way.
A fifth object of the invention is to provide an improved antenna element which can be used in particular in a dielectrically charged antenna which can be reduced using a body loading.
According to the invention, these and other objects are achieved by a glass-ceramic which has at least the following constituents (in mol % on an oxide basis):
where Ba can be partly, preferably to an extent of up to 10%, replaced by Sr, Ca, Mg, where RE is lanthanum, another lanthanide or yttrium, and Ti can be partly, preferably to an extent of up to 10%, replaced by Zr, Hf, Y, Nb, V, Ta.
The object of the invention is solved completely in this way.
It has been found that homogeneous glasses which can subsequently be converted by a ceramicizing treatment into a homogeneous glass-ceramic which has a high relative permittivity, a low dielectric loss and a low temperature dependence of the resonance frequency can be melted using such a glass composition. The material can be produced as glass ceramic in a simple and inexpensive way and allows near net shaping by melt-technological processes, in particular by casting or optionally by pressing.
For the purposes of the present patent application, the term “glass-ceramic” refers to a material which, starting from a homogeneous glass produced by melting, is converted by means of a specific heat treatment into a partially crystalline body in which a large number of crystallites are distributed essentially homogeneously in a vitreous residual phase.
In an advantageous embodiment of the invention, the glass-ceramic has the following constituents (in mol % on an oxide basis):
where Ba can be partly, preferably to an extent of up to 10%, replaced by Sr, Ca, Mg, where Re is a lanthanide or yttrium, and Ti can be partly, preferably to an extent of up to 10%, replaced by Zr, Hf, Y, Nb, V, Ta.
Furthermore, the glass-ceramic can contain refining agents in customary amounts, preferably from 0.01 to 3 mol % of a refining agent which is preferably selected from the group consisting of Sb2O3 and As2O3.
The glass-ceramic of the invention preferably has a dielectric loss (tan δ) of not more than 10−2, preferably not more than 10−3, in high-frequency applications (f>200 MHz).
Furthermore, the glass-ceramic preferably has a relative permittivity ∈ of at least 15, preferably >18, preferably in the range from 20 to 80.
The glass-ceramic of the invention also preferably has a temperature dependence of the resonance frequency τf of not more than 200 ppm/K, preferably not more than 50 ppm/K, particularly preferably not more than 10 ppm/K.
In a further advantageous embodiment of the invention, the glass-ceramic of the invention has at least one mixed crystal phase based on RE, Ti, Si, O and optionally Ba, where Ba can be at least partly, replaced by Sr, Ca, Mg, where RE is a lanthanide or yttrium, and Ti can be at least partly replaced by Zr, Hf, Y, Nb, V, Ta.
In particular, the glass-ceramic of the invention can contain at least one mixed crystal phase selected from the group consisting of Ba, RE, TiO, RE2Ti2O7, RE2Ti2SiO9 and RE4Ti9O24, where RE is lanthanum, another lanthanide or yttrium, up to 10% of Ba can be replaced by Sr, Ca, Mg, and up to 10% of Ti can be replaced by Zr, Hf, Y, Nb, V, Ta.
The glass-ceramic of the invention can preferably have a proportion of crystalline material of at least 30% by volume, preferably up to 95% by volume.
The average crystallite size is preferably from 10 nm to 50 μm and is preferably in the range from 100 nm to 1 μm.
The glass-ceramic of the invention is particularly suitable as dielectric for a dielectric resonator, an electronic frequency filter element or an antenna element in the high-frequency range (f>200 MHz).
Use as dielectric for a cylindrical antenna element or a patch antenna element is particularly useful.
A dielectric according to the invention having a dielectric loss of not more than 10−2 in the high-frequency range can be produced by means of the following steps:
melting and homogenization of a starting glass containing the constituents (in mol % on an oxide basis):
where Ba can be partly, preferably to an extent of up to 10%, replaced by Sr, Ca, Mg, where RE is a lanthanide or yttrium, and Ti can be partly, preferably to an extent of up to 10%, replaced by Zr, Hf, Y, Nb, V, Ta;
pouring of the starting glass into a desired mould;
cooling of the starting glass to room temperature;
ceramicization of the starting glass by means of a heat treatment.
In a preferred embodiment of the invention, the starting glass comprises at least the following constituents (in mol % on an oxide basis):
where Ba can be partly, preferably to an extent of up to 10%, replaced by Sr, Ca, Mg, where RE is a lanthanide or yttrium, and Ti can be partly, preferably to an extent of up to 10%, replaced by Zr, Hf, Y, Nb, V, Ta.
The starting glass is preferably brought to near net shape by means of a hot forming process, in particular by casting, tube drawing, rod drawing or extrusion.
Further features and advantages of the invention can be derived from the following description of preferred examples with reference to the drawing.
Table 1 shows various glass compositions for a starting glass in the system Ba—La—Ti—Si—O.
The various glass samples of Examples 1 to 9 are firstly melted and homogenized in the usual way using conventional starting materials, with platinum crucibles, PT/RI crucibles, PT/RH crucibles, fused silica crucibles or aluminium oxide crucibles being able to be used. The samples are firstly melted at 1350° C. for 2 hours, then refined at 1400° C. for 30 minutes, stirred and homogenized by means of a platinum stirrer for 20 minutes, allowed to stand for 10 minutes and then poured into suitable moulds made of, for instance, steel, graphite, aluminium oxide or fused silica and then brought to near net shape.
After cooling to room temperature, the glass is subjected to a ceramicization step, which can be carried out, for example, by means of an infrared heating process or by means of a conventional process.
A typical ceramicization cycle by means of an infrared furnace is as follows:
heating at 300° C./min to 1050° C.;
hold at 1050° C. for 7 seconds;
heating to 1200° C. at a heating rate of 50 K/min;
hold at 1200° C. for 15 minutes;
cooling to about 500° C. at a cooling rate of about 50 K/min by switching off the furnace;
removal of the specimen from the furnace when a temperature of about 500° C. has been reached.
A ceramicization cycle in a conventional furnace is carried out by heat treatment at 925° C. for 15 hours.
If necessary, the mouldings can, after casting, be subjected to a file grinding or polishing treatment or in the case of the production of cylindrical mouldings, can be machined by centreless grinding of the cylindrical surface.
The proportion by volume of the crystalline phase in this sample is in the order of from about 50 to 70% by volume.
Relative permittivities ∈ were measured on samples 1 to 9; these were all greater than 15 and in the range from 20 to 50,
The samples also display a low dielectric loss and a high quality.
The quality Q is the reciprocal of the dielectric loss (tan δ):
Q=1/tan(δ)
The quality is measured by the Hakki-Coleman resonance method. The quality factor is determined here as the product of quality Q and measurement frequency f0.
All samples 1 to 9 had a quality factor Q·f0 in the range from 2000 to 3000 GHz. In the case of sample 1, a relative permittivity ∈ of 22.4 and a quality Q of 205 were measured at 10.09 GHz, i.e. a quality factor of 2068 was measured.
The temperature coefficient Σf of the resonance frequency is very low for all measured samples and is in the range −40 ppm/K<τf<40 ppm/K.
In uses as dielectric for antennae which are suitable, in particular, for mobile GPS antennae for mobile phones, the frequency range is above 200 MHz, in particular in the range from about 800 MHz to 70 GHz. The dielectric charging of the antenna reduces the sensitivity of the antenna to detuning by the user.