US20180131068A1
2018-05-10
15/695,342
2017-09-05
Ceramic materials, devices, and methods for microwave applications. In some embodiments, a composition can include a material with a formula Ba4+xSm(2/3)(14βx+0.5y)Ti18βyAlyO54, with the quantity y being in a range 0<y<2, and the quantity x being in a range 0<x<2βy. Such a material can have a dielectric constant value greater than 60 and a Qf value greater than 10,000 at a frequency (f) at or less than 1 GHz. In some embodiments, a material having such properties can be implemented as a ceramic device and be utilized as a dielectric microwave resonator. Such a microwave resonator can be utilized as, for example, a narrowband radio-frequency (RF) filter.
Get notified when new applications in this technology area are published.
C04B2235/77 » CPC further
Aspects relating to ceramic starting mixtures or sintered ceramic products; Aspects relating to sintered or melt-casted ceramic products; Physical characteristics Density
C04B2235/76 » CPC further
Aspects relating to ceramic starting mixtures or sintered ceramic products; Aspects relating to sintered or melt-casted ceramic products; Physical characteristics Crystal structural characteristics, e.g. symmetry
C04B2235/3418 » CPC further
Aspects relating to ceramic starting mixtures or sintered ceramic products; Composition of constituents of the starting material or of secondary phases of the final product; Constituents and secondary phases not being of a fibrous nature; Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
C04B2235/3287 » CPC further
Aspects relating to ceramic starting mixtures or sintered ceramic products; Composition of constituents of the starting material or of secondary phases of the final product; Constituents and secondary phases not being of a fibrous nature; Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides Germanium oxides, germanates or oxide forming salts thereof, e.g. copper germanate
C04B2235/3286 » CPC further
Aspects relating to ceramic starting mixtures or sintered ceramic products; Composition of constituents of the starting material or of secondary phases of the final product; Constituents and secondary phases not being of a fibrous nature; Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides Gallium oxides, gallates, indium oxides, indates, thallium oxides, thallates or oxide forming salts thereof, e.g. zinc gallate
C04B2235/3281 » CPC further
Aspects relating to ceramic starting mixtures or sintered ceramic products; Composition of constituents of the starting material or of secondary phases of the final product; Constituents and secondary phases not being of a fibrous nature; Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides Copper oxides, cuprates or oxide-forming salts thereof, e.g. CuO or CuO
C04B2235/3262 » CPC further
Aspects relating to ceramic starting mixtures or sintered ceramic products; Composition of constituents of the starting material or of secondary phases of the final product; Constituents and secondary phases not being of a fibrous nature; Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
C04B2235/3232 » CPC further
Aspects relating to ceramic starting mixtures or sintered ceramic products; Composition of constituents of the starting material or of secondary phases of the final product; Constituents and secondary phases not being of a fibrous nature; Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides; Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof Titanium oxides or titanates, e.g. rutile or anatase
C04B2235/3229 » CPC further
Aspects relating to ceramic starting mixtures or sintered ceramic products; Composition of constituents of the starting material or of secondary phases of the final product; Constituents and secondary phases not being of a fibrous nature; Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides; Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide Cerium oxides or oxide-forming salts thereof
C04B2235/3227 » CPC further
Aspects relating to ceramic starting mixtures or sintered ceramic products; Composition of constituents of the starting material or of secondary phases of the final product; Constituents and secondary phases not being of a fibrous nature; Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides; Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide Lanthanum oxide or oxide-forming salts thereof
C04B2235/3224 » CPC further
Aspects relating to ceramic starting mixtures or sintered ceramic products; Composition of constituents of the starting material or of secondary phases of the final product; Constituents and secondary phases not being of a fibrous nature; Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
C04B2235/3215 » CPC further
Aspects relating to ceramic starting mixtures or sintered ceramic products; Composition of constituents of the starting material or of secondary phases of the final product; Constituents and secondary phases not being of a fibrous nature; Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides; Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide Barium oxides or oxide-forming salts thereof
C04B2235/3213 » CPC further
Aspects relating to ceramic starting mixtures or sintered ceramic products; Composition of constituents of the starting material or of secondary phases of the final product; Constituents and secondary phases not being of a fibrous nature; Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides; Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide Strontium oxides or oxide-forming salts thereof
H01P7/10 » CPC main
Resonators of the waveguide type Dielectric resonators
C04B35/462 » CPC further
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 titanium oxides or titanates based on titanates
Any and all applications for which a foreign or domestic priority claim is identified in the Application Data Sheet as filed with the present application are hereby incorporated by reference under 37 CFR 1.57. This application is a continuation of U.S. application Ser. No. 14/561,182 filed Dec. 4, 2014, entitled ENHANCED Q HIGH DIELECTRIC CONSTANT MATERIAL FOR MICROWAVE APPLICATIONS, which claims priority to and the benefit of the filing date of U.S. Provisional Application No. 61/912,463 filed Dec. 5, 2013, entitled ENHANCED Q HIGH DIELECTRIC CONSTANT MATERIAL FOR MICROWAVE APPLICATIONS, the benefits of the filing dates of which are hereby claimed and the disclosures of which are hereby expressly incorporated by reference herein in their respective entirety.
The present disclosure generally relates to high dielectric constant materials for microwave applications.
In some radio-frequency (RF) applications such as microwave applications, ceramic materials are often utilized as, for example, dielectric resonators. Such dielectric resonators can be implemented in devices such as narrowband filters.
In some implementations, the present disclosure relates to a composition including a material with a formula Ba4+xSm(2/3)(14βx+0.5y)Ti18βyAlyO54, with the quantity y being in a range 0<y<2, and the quantity x being in a range 0<x<2βy.
In some embodiments, the quantity x can be in a range 0<x<1β0.5y corresponding to barium content being in a range of 0% to 50%. In some embodiments, the quantity y can be approximately 0.5 and the quantity x can be in a range from approximately 0.01 to approximately 1.0. In some embodiments, the quantity y can be approximately 1.0 and the quantity x can be in a range from approximately 0.01 to approximately 0.5. In some embodiments, the quantity y can be approximately 1.4 and the quantity x can be in a range from approximately 0.01 to approximately 0.3.
In some embodiments, at least some of Sm can be substituted by another lanthanide including La, Ce, Pr, Nd or Gd. In some embodiments, the other lanthanide such as La or Nd can substitute up to approximately 50 atomic percent of Sm.
In some embodiments, at least some of Ba can be substituted by Sr. Sr can substitute up to approximately 30 atomic percent of Ba.
In some embodiments, the composition can further include a minor additive including manganese oxide, manganese carbonate, cerium oxide, copper oxide, germanium oxide, silica or gallium oxide. The minor additive can constitute less than approximately 2 percent by weight. The minor additive can be cerium oxide or manganese oxide; and such a minor additive can constitutes less than 0.5 percent by weight.
In some embodiments, a composition having one or more of the foregoing features can further include a high Q second phase material. The high Q second phase material can include TiO2, BaTi4O9 or Ba2Ti9O20.
According to a number of implementations, the present disclosure relates to a dielectric resonator having a ceramic device configured as a microwave resonator. The ceramic device includes a material with a formula Ba4+xSm(2/3)(14βx+0.5y)Ti18βyAlyO54, with the quantity y being in a range 0<y<2, and the quantity x being in a range 0<x<2βy.
In some embodiments, the material can have a dielectric constant value that is greater than 60 for frequencies less than or equal to 1 GHz. Such a dielectric constant value can be in a frequency range that is greater than or equal to 700 MHz and less than or equal to 1 GHz. In some embodiments, the material can have a Qf value that is greater than 10,000, with the quantity Q being a quality factor, and the quantity f being a frequency expressed in GHz.
In accordance with some teachings, the present disclosure relates to a narrowband radio-frequency (RF) filter having an input port and an output port, and one or more dielectric resonators implemented between the input port and the output port. Each of the one or more dielectric resonators includes a ceramic device. The ceramic device includes a material with a formula Ba4+xSm(2/3)(14βx+0.5y)Ti18βyAlyO54, with the quantity y being in a range 0<y<2, and the quantity x being in a range 0<x<2βy.
In a number of implementations, the present disclosure relates to a method for fabricating a tungsten bronze material having titanium (Ti) in a plurality of octahedral sites. The method includes substituting aluminum (Al) for at least some of the titanium (Ti) in the octahedral sites to yield a dielectric constant value greater than 60 and a Qf value greater than 10,000 at a frequency (f) at or less than 1 GHz. The method further includes adjusting contents of A1 and A2 sites to compensate for charge imbalance resulting from the aluminum substitution of titanium.
In some embodiments, the tungsten bronze material can be represented by a formula [A2]4[A1]10Ti18βyAlyO54. In some embodiments, substantially all of the A2 sites can be occupied by barium (Ba) and at least some of the A1 sites can be occupied by samarium (Sm), such that the adjusting includes adding x formula unit of Ba and (2/3)x formula unit of Sm to the A1 sites. In some embodiments, the method can further include substituting at least some of the samarium with another lanthanide (Ln) to yield a temperature coefficient of resonant frequency (Οf) that is less negative.
For purposes of summarizing the disclosure, certain aspects, advantages and novel features of the inventions have been described herein. It is to be understood that not necessarily all such advantages may be achieved in accordance with any particular embodiment of the invention. Thus, the invention may be embodied or carried out in a manner that achieves or optimizes one advantage or group of advantages as taught herein without necessarily achieving other advantages as may be taught or suggested herein.
FIG. 1 shows that in some embodiments, a ceramic device such as a puck can include a material having one or more features as described herein.
FIG. 2 shows that in some embodiments, a ceramic puck having one or more features as described herein can include a center aperture dimensioned to allow, for example, tuning of the ceramic puck when utilized as a microwave resonator.
FIG. 3 shows an example of a tunable microwave resonator configuration.
FIG. 4 shows an example of a cavity filter having a plurality of cavities arranged between radio-frequency (RF) ports.
FIG. 5 shows an example of an RF system that can utilize one or more of the filter device of FIG. 4.
FIG. 6 shows a process that can be implemented to fabricate a ceramic material having one or more features as described herein.
FIG. 7 shows a process that can be implemented to press-form a shaped object from a powder material prepared as described herein.
FIG. 8 shows example stages associated with the process of FIG. 7.
FIG. 9 shows a process that can be implemented to sinter formed objects having one or more features as described herein.
FIG. 10 shows example stages associated with the process of FIG. 9.
The headings provided herein, if any, are for convenience only and do not necessarily affect the scope or meaning of the claimed invention.
Disclosed are compositions that can include materials having relatively high dielectric constant values and enhanced Q values. Examples of such materials are described herein in greater detail. Also described herein are examples of how such materials can be manufactured. Also described herein are examples of devices and applications in which such materials can be utilized.
In some radio-frequency (RF) applications such as microwave applications (e.g., low-frequency (700 MHz-1 GHz) applications), materials with a dielectric constant greater than 60 and having a desired or optimized quality factor Q can be desirable. For example, a Qf (product of Q and frequency f) value greater than 10,000 in the foregoing frequency range (700 MHz to 1 GHz range) can be desirable. Further, such a material preferably has a temperature coefficient of resonant frequency that is near zero. Conventional high-dielectric-constant materials typically do not have sufficient Q and/or require expensive raw materials such as Ga or Ge.
Disclosed are various examples of materials that can meet desired Q specifications or requirements without the expensive raw materials in their respective compositions. Also disclosed are examples of how such materials can be implemented in low-frequency microwave applications. Although described in such low-frequency context, it will be understood that one or more features of the present disclosure can also be implemented in other RF applications.
Various examples of dielectric materials and associated methods are described in U.S. Pat. No. 8,318,623 which is expressly incorporated by reference in its entirely and to be considered part of the specification of the present application.
Some compounds with an orthorhombic tungsten bronze structure can be represented by a general formula
Ba6β3xLn8+2xTi18O54,ββ(1)
where Ln can be a lanthanide such as lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm) or gadolinium (Gd). Such a structure can be implemented for microwave dielectric applications due to their high dielectric constants (e.g., 60-100) and their ability to be tuned to a near zero temperature coefficient of resonant frequency.
In some applications, it is additionally desirable to minimize or reduce the dielectric loss tangent (tan Ξ΄) or to maximize or increase the quality factor Q (an inverse of dielectric loss tangent, 1/tan Ξ΄) of a dielectric material used for microwave applications, since such a property typically yields sharper resonances and sharper transitions for filter applications.
From a crystallographic perspective, the foregoing materials can be represented as
[A2]4[A1]10Ti18O54.ββ(2)
Typically, the 10 available A1 sites are rhombic while the 4 available A2 sites are pentagonal. The Ti atoms typically occupy octahedral sites. The A1 sites may be occupied by Ba atoms, Ln atoms, or may be vacant. The A2 sites may be occupied by Ba or Ln atoms. Although described in the context of rhombic sites, it will be understood that one or more features of the present disclosure can also be implemented in other types of sites.
For the orthorhombic tungsten bronze structure represented by Formula 1, it is generally understood that the value of Q can be optimal when the quantity x has a value of 2/3 (0.667), where substantially all of the Ba atoms reside in the pentagonal A2 sites and substantially all of the lanthanide (Ln) atoms reside in the rhombic A1 sites. A number of studies have shown that the value of Q is typically maximum when the lanthanide (Ln) chosen is Sm, and decreases with increasing lanthanide size in the order of, for example, Nd, Pr, Ce and La. The Gd material shows a very limited solid solution range and typically yields a relatively low Q as well.
Among the foregoing lanthanide examples, Sm and Gd are lanthanides that yield negative temperature coefficient of resonant frequency (Οf) values. The other lanthanides Nd, Pr, Ce and La series all yield positive Οf values. In the context of dielectric resonators, temperature coefficient of resonant frequency (Οf) is typically a combination of temperature coefficient of dielectric constant of a resonator, temperature coefficient of the resonator cavity, and the coefficient of thermal expansion of the resonator.
Based on the foregoing properties of the example lanthanides, a typical design strategy can involve blends of two lanthanides such as Sm and Nd or Sm and La to achieve temperature compensated ceramic bodies. Aside from such design considerations based on physical properties, availability and/or cost of raw materials can also impact designs of ceramic devices. For example, there is a demand for ceramic solutions for microwave materials that do not contain scarce and/or costly elements such as neodymium (Nd), gallium (Ga) or germanium (Ge). Samarium (Sm) and lanthanum (La) are significantly less scarce for rare earth elements.
As described in U.S. Pat. No. 8,318,623, as well as in, for example, U.S. Pat. Nos. 5,182,240, 5,185,304 and 5,310,710, at least some of the titanium in tungsten bronze material can be substituted by, for example, aluminum. The resulting charge imbalance can be compensated by adding Ln material (e.g., Nd, a mixture of Nd and Sm, a mixture of Nd and Y, or a mixture of Sm and non-lanthanide Bi) into the vacant A1 lattice site(s) (e.g., in Formula 2). It is also noted that in the tungsten bronze material of Formula 1 (Ba6β3xLn8+2xTi18O54), for x values less than or equal to 2/3 where Ln=Nd (in the BaOβNd2O3βTiO2 ternary system), the resulting phase is chemically compatible with the high Q rutile form of TiO2 (with Οf being greater than approximately 500 ppm/Β° C.).
In some embodiments, aluminum (Al) can be substituted for titanium (Ti) in the octahedral site to yield, contrary to published findings, highest or enhanced Q material at approximately 1 GHz for x values less than or equal to 2/3. In the context of Formula 2, the foregoing substitution of Ti by Al can be represented as
[A2]4[A1]10Ti18βyAlyO54,ββ(3)
where y unit of Ti is substituted by y unit of Al.
As described herein, charge imbalance resulting from substitution of Ti+4 with Al+3 can be compensated by appropriate occupations of the A1 and/or A2 sites by, for example, Ln+3 and/or Ba+2, respectively. In the context of such Ln and Ba, Formula 3 can be expressed as a modified form of Formula 1, as one of the following example formulas
Ba6β3xLn8+2x+(y/3)Ti18βyAlyO54,ββ(4A)
Ba6β3x+(y/2)Ln8+2xTi18βyAlyO54, andββ(4B)
Ba6β3xβyLn8+2x+yTi18βyAlyO54,ββ(4C)
where the charge imbalance of y (+4 of Ti to +3 of Al) can be compensated by adding an appropriate amount of Ba (+2), Ln (+3), or a mixture of the two. For example, in Formula 4A, charge balancing can be achieved by adding Ln3+, with the formula unit of y/3 to account for the +3 charge. In Formula 4B, charge balancing can be achieved by adding Ba2+, with the formula unit of y/2 to account for the +2 charge. In Formula 4C, charge balancing can be achieved by subtracting y formula unit of Ba (+2) and adding y formula unit of Ln (+3). It is noted that Formulas 4A and 4B are extreme cases involving only one type of addition (of Ln or Ba), and that the charge imbalance may also be compensated with a mixture of Ln3+ and Ba2+ (such as the example of Formula 4C). Previous studies have taught that the Q is optimal only if all of the barium remains on the A2 site and the lanthanide remains on the A1 site. However, the present disclosure shows that such is not necessarily true.
It is noted that in Formula 4, there are 10 available rhombic A1 sites. Accordingly, and in the context of the example of Formula 4A, a limit can be imposed, where formula unit of 8+2x+(y/3) has a maximum value of 10. In such a configuration, the maximum value for y is 2 when x=2/3. In terms of Al substitution of Ti, the maximum amount of aluminum which may be substituted for titanium is 2 formula units (y=2).
Based on the foregoing limit of 2 formula units of aluminum substitution of titanium, aluminum content can be expressed as
aluminum percent=100(y/2),ββ(5)
where y represents the formula units of aluminum in the composition of Formula 4A. For example, when y=2 in which Formula 4A becomes Ba4Ln10Ti16Al2O54 (with x=2/3), aluminum percent is 100%. In another example, when y=1 and x has a value of 2/3 based on the formula units for barium (6β3x) being equal to 4, Formula 4A becomes Ba4Ln9.667Ti17AlO54, with aluminum percent being 50%. Note that in both cases (of aluminum percent of 100% and 50%), all of the charge compensation for the aluminum substitution comes from adding additional Ln3+ to the A1 site.
In some embodiments, where the compensation of the aluminum substitution at least partially occurs by adding Ba2+ to the A1 site, the maximum amount of barium which can fit into the A1 site can depend on the foregoing aluminum percent, due to charge balance considerations. The maximum amount of barium which can be placed in the A1 site (Bamax) is equal to 2β(aluminum percent)/50. The barium percent (in the A1 site) can then be expressed as (NBaβ4)/Bamax, where NBa is the total number of formula units of Ba. Equivalently, barium percent can be expressed as
barium percent=(NBaβ4)/(2β(aluminum percent)/50),ββ(6)
where NBa is the number of barium atoms in the formula (e.g., 6β3xβy in Formula 4). For example, in the case of aluminum percent being 100 (yielding a zero denominator), barium percent is zero, with no barium in the A1 sites and all of the Ba atoms occupying the A2 sites. In another example, the 50%-aluminum configuration that yields the example formula Ba4Ln9.667Ti17AlO54 also results in barium percent of zero, since all of the available aluminum is compensated by additional Ln3+ in the A1 site. Examples of non-zero barium percent configurations are described herein in greater detail.
As described herein in reference to the example of Formula 4C, an aluminum substitution of titanium by an amount of y formula units can be charge-compensated by an addition of lanthanide (by y formula units) and a subtraction of barium (by y formula units). In the context of zero barium percent configurations, a 100%-aluminum configuration can yield Ba4Ln10Ti16Al2O54, and a 50%-aluminum configuration can yield Ba4Ln9.667Ti17AlO54. In the context of non-zero barium percent configurations, at least some of the barium can occupy the A1 sites.
In configurations where more than four formula units of barium are present, Formula 4C can be expressed as
Ba4+xβ²Ln8+2x+yβ(2/3)xβ²Ti18βyAlyO54,ββ(7)
where xβ² represents the additional formula units of barium. Equivalently, xβ² can be expressed as xβ²=NBaβ4. Such an increase in Ba (+2) can be charge balanced by a decrease of (2/3)xβ² formula units of Ln(+3). In Formula 7, the aluminum substitution formula unit quantity y can be greater than zero and less than or equal to 2 as described herein, such that 0<yβ€2. The extra-barium formula unit xβ² can be greater than or equal to zero, and less than or equal to a maximum value of 2βy, such that 0β€xβ²β€2βy. Such a maximum value of 2βy can be calculated by, for example, assuming that the Ln formula unit of 8+2x+yβ(2/3)xβ² (of Formula 7) and the additional Ba formula unit of xβ² sum to the maximum A1 occupation number of 10 (e.g., 8+2x+yβ(2/3)xβ²+xβ²=10). The quantity xβ² can be solved to yield xβ²=2βy.
In some embodiments, all four A2 sites can be occupied by barium and the additional xβ² formula units of barium can occupy A1 sites. In such embodiments, since all four of the A2 sites are occupied by 6β3xβy formula units (barium number in Formula 4C), 6β3xβy can be set to equal 4, which yields an expression x=(2/3)β(1/3)y. Substituting such an expression of x into the subscript of Ln in Formula 7, the subscript becomes 8+2[(2/3)β(1/3)y]+yβ(2/3)xβ², which in turn can be expressed as (2/3)[14+(1/2)yβxβ²]. Accordingly, Formula 7 can be expressed as
Ba4+xβ²Ln(2/3)[14+0.5yβx]Ti18βyAlyO54,ββ(8)
where the aluminum substitution formula unit quantity y can be greater than zero and less than or equal to 2, such that 0<yβ€2. The extra-barium formula unit xβ² can be greater than or equal to zero, and less than or equal to a maximum value of 1β0.5x, such that 0β€xβ²β€1β0.5y. Such a maximum value of 1β0.5y can be calculated by, for example, assuming that the Ln formula unit of (2/3)[14+0.5yβxβ²] (of Formula 8) and the additional Ba formula unit of xβ² sum to the maximum A1 occupation number of 10 (e.g., (2/3)[14+0.5yβxβ²]+xβ²=10). The quantity xβ² can be solved to yield xβ²=1β0.5y. It is noted that in Formula 8, the four formula units of Ba occupy all of the four A2 sites; and such occupation is reflected in the Ln formula unit of (2/3)[14+0.5yβxβ²].
In embodiments where lanthanide is samarium (Ln=Sm), Formula 8 can be expressed as
Ba4+xβ²Sm(2/3)[14+0.5yβxβ²]Ti18βyAlyO54.ββ(9)
In such a system, the substitution of aluminum (Al) for titanium (Ti) as described herein can yield high Q rutile form of TiO2 being chemically compatible with Formula 1 (Ba6-3xLn8+3xTi18O54) when the value of x is less than or equal to 2/3, similar to the foregoing neodymium (Nd) system (Ln=Nd). In some embodiments of the Sm system, one or more lanthanides having positive Οf values can be introduced to compensate for the negative Οf value associated with Sm. For example, some of Sm can be substituted by another lanthanide such as La, Ce, Pr, Nd or Gd. In some embodiments, the other lanthanide can be La or Nd, and such lanthanide can substitute up to approximately 50 percent (e.g., mole %) of Sm.
Although various examples are described in the context of barium, it will be understood that one or more of other alkaline earth metals can replace at least some of the barium content. For example, strontium (Sr) can be included, and its content percent can be calculated in the same manner as the barium percent described herein in reference to Equation 6.
In some embodiments having x values <0.667 in, for example Formula 4, there may be conditions where rutile TiO2 can be added as a second crystallographic phase. Examples of such additions are described herein in greater detail. Further, some embodiments can include small amounts of acceptor dopants such as MnO2 or CeO2 added to the composition to, for example, prevent or reduce thermal reduction of the titanium from Ti4+ to Ti3+.
Table 1 lists various samples having various combinations of aluminum percent (Al %, as described in Equation 5), barium percent (Ba %, as described in Equation 6), strontium percent (Sr %, similar to the barium percent), lanthanum percent (La %, mole percent), cerium oxide weight percent (CeO2 w %), and titanium oxide or rutile weight percent (TiO2 w %). Table 1 also lists density values of selected ones of the samples. Empty cells, if any, correspond to values that are either not applicable or not available. It will be understood that each of the samples listed in Table 1 is based on Formula 9 (Ba4+xβ²Sm(2/3)[14+0.5yβxβ²]Ti18βyAlyO54), with the various percent values corresponding to substitutions of Ba or Sm, or introduction of second phase materials (e.g., TiO2).
Table 2 lists Q values for the same samples of Table 1, at or near f=1 GHz. Corresponding Qf values are also listed. Table 2 also lists dielectric constant values (ββ²) corresponding to the listed approximately 1 GHz frequency values for selected ones of the samples. Table 2 also lists values of temperature coefficient of resonant frequency (Οf) for selected ones of the samples. Empty cells, if any, correspond to values that are either not applicable or not available.
Table 3 lists Q values for some of the samples of Table 1, at or near f=3 GHz. Corresponding Qf values are also listed. Table 3 also lists dielectric constant values (ββ²) corresponding to the listed approximately 3 GHz frequency values. Empty cells, if any, correspond to values that are either not applicable or not available.
| TABLE 1 | |||||||
| Den- | |||||||
| Sam- | sity | ||||||
| ple | Al | Ba | Sr | La | CeO2 | TiO2 | (g/ |
| No. | % | % | % | % | w % | w % | cm3) |
| 1 | 100 | 0 | 0 | 2.75 | 0 | 0 | |
| 2 | 100 | 0 | 0 | 2.75 | 0 | 0 | |
| 3 | 100 | 0 | 0 | 2.75 | 0 | 0 | |
| 4 | 100 | 0 | 0 | 2.75 | 0 | 0 | |
| 5 | 100 | 0 | 0 | 2.75 | 0 | 0 | |
| 6 | 100 | 0 | 0 | 2.75 | 0 | 0 | |
| 7 | 100 | 0 | 0 | 2.75 | 0 | 0 | |
| 8 | 75 | 0 | 0 | 0 | 0 | 0 | |
| 9 | 75.1 | 24.8 | 0 | 0 | 0 | 0 | |
| 10 | 50 | 0 | 0 | 0 | 0 | 0 | |
| 11 | 50 | 25 | 0 | 0 | 0 | 0 | |
| 12 | 25 | 0 | 0 | 0 | 0 | 0 | |
| 13 | 24.9 | 24.9 | 0 | 0 | 0 | 0 | |
| 14 | 0 | 0 | 0 | 0 | 0 | 25 | |
| 15 | 0 | 25.1 | 0 | 0 | 0 | 25 | |
| 16 | 75 | 25 | 0 | 0 | 0 | 25 | |
| 17 | 50 | 0 | 0 | 0 | 0 | 25 | |
| 18 | 50 | 25 | 0 | 0 | 0 | 25 | |
| 19 | 25 | 0 | 0 | 0 | 0 | 25 | |
| 20 | 25 | 25 | 0 | 0 | 0 | 25 | |
| 21 | 25 | 0 | 0 | 0 | 0 | 12.5 | |
| 22 | 25 | 25 | 0 | 0 | 0 | 12.5 | |
| 23 | 75.1 | 24.8 | 0 | 0 | 0.25 | 0 | 5.453 |
| 24 | 50 | 25 | 0 | 0 | 0.5 | 0 | |
| 25 | 24.9 | 24.9 | 0 | 0 | 0.75 | 0 | |
| 26 | 0 | 25.1 | 0 | 0 | 0.75 | 25 | |
| 27 | 0 | 25.1 | 0 | 0 | 0.875 | 12.5 | |
| 28 | 24.9 | 24.9 | 0 | 0 | 0.558 | 25 | |
| 29 | 24.9 | 24.9 | 0 | 0 | 0.658 | 12.5 | |
| 30 | 74.2 | 48.06 | 0 | 2.8 | 0.25 | 0 | 5.896 |
| 31 | 49.85 | 25.09 | 0 | 5.78 | 0.5 | 0 | |
| 32 | 24.98 | 24.91 | 0 | 8.89 | 0.75 | 0 | |
| 33 | 0 | 24.92 | 0 | 12.14 | 0.875 | 0 | |
| 34 | 24.98 | 24.91 | 0 | 8.89 | 0.75 | 25 | |
| 35 | 24.98 | 24.91 | 0 | 8.89 | 0.75 | 12.5 | |
| 36 | 74.75 | 25.34 | 0 | 2.84 | 0 | 0 | 5.916 |
| 37 | 49.68 | 24.91 | 0 | 5.82 | 0 | 0 | |
| 38 | 24.67 | 24.8 | 0 | 8.92 | 0 | 0 | |
| 39 | 0 | 24.92 | 0 | 12.14 | 0 | 25 | |
| 40 | 0 | 24.92 | 0 | 12.14 | 0 | 12.5 | |
| 41 | 24.67 | 24.8 | 0 | 8.92 | 0 | 25 | |
| 42 | 24.67 | 24.8 | 0 | 8.92 | 0 | 12.5 | |
| 43 | 9.93 | 24.9 | 0 | 5 | 0 | 0 | |
| 44 | 9.93 | 25.1 | 0 | 10 | 0 | 0 | |
| 45 | 31.28 | 24.88 | 0 | 5 | 0 | 0 | |
| 46 | 31.28 | 24.88 | 0 | 10 | 0 | 0 | |
| 47 | 50.02 | 24.84 | 0 | 5 | 0 | 0 | |
| 48 | 50.02 | 24.84 | 0 | 10 | 0 | 0 | |
| 49 | 70.07 | 25 | 0 | 5 | 0 | 0 | 5.74β |
| 50 | 70.07 | 25 | 0 | 10 | 0 | 0 | |
| 51 | 89.95 | 25.87 | 0 | 5 | 0 | 0 | |
| 52 | 89.95 | 25.87 | 0 | 10 | 0 | 0 | |
| 53 | 9.93 | 24.9 | 0 | 2.5 | 0 | 0 | |
| 54 | 31.28 | 24.88 | 0 | 2.5 | 0 | 0 | |
| 55 | 50.02 | 24.84 | 0 | 2.5 | 0 | 0 | 5.76β |
| 56 | 70.07 | 25 | 0 | 2.5 | 0 | 0 | 5.74β |
| 57 | 89.95 | 25.87 | 0 | 2.5 | 0 | 0 | |
| 58 | 10 | 31.99 | 0 | 5 | 0 | 0 | |
| 59 | 10 | 31.99 | 0 | 10 | 0 | 0 | |
| 60 | 29.8 | 33.8 | 0 | 5 | 0 | 0 | |
| 61 | 29.8 | 33.8 | 0 | 10 | 0 | 0 | |
| 62 | 49.6 | 37.06 | 0 | 5 | 0 | 0 | |
| 63 | 49.6 | 37.06 | 0 | 10 | 0 | 0 | |
| 64 | 69.4 | 45.02 | 0 | 5 | 0 | 0 | 5.7β |
| 65 | 69.4 | 45.02 | 0 | 10 | 0 | 0 | 5.7β |
| 66 | 89.23 | 82.2 | 0 | 5 | 0 | 0 | 5.64β |
| 67 | 89.23 | 82.2 | 0 | 10 | 0 | 0 | 5.66β |
| 68 | 10 | 31.99 | 0 | 2.5 | 0 | 0 | |
| 69 | 29.8 | 33.8 | 0 | 2.5 | 0 | 0 | |
| 70 | 49.6 | 37.06 | 0 | 2.5 | 0 | 0 | |
| 71 | 69.4 | 45.02 | 0 | 2.5 | 0 | 0 | 5.75β |
| 72 | 89.23 | 82.2 | 0 | 2.5 | 0 | 0 | 5.67β |
| 73 | 74.2 | 48 | 0 | 10 | 0 | 0 | 5.77β |
| 74 | 74.2 | 48 | 0 | 10 | 0 | 10 | |
| 75 | 74.2 | 0 | 48 | 10 | 0 | 0 | 5.81β |
| 76 | 74.2 | 48 | 0 | 20 | 0 | 0 | 5.78β |
| 77 | 74.2 | 48 | 0 | 30 | 0 | 0 | 5.77β |
| 78 | 74.2 | 48 | 0 | 40 | 0 | 0 | 5.67β |
| 79 | 74.75 | 25.35 | 0 | 10 | 0 | 0 | 5.8β |
| 80 | 74.75 | 25.35 | 0 | 10 | 0 | 10 | |
| 81 | 74.75 | 0 | 25.35 | 10 | 0 | 0 | 5.8β |
| 82 | 74.75 | 25.35 | 0 | 20 | 0 | 0 | 5.79β |
| 83 | 74.75 | 25.35 | 0 | 30 | 0 | 0 | 5.77β |
| 84 | 74.75 | 25.35 | 0 | 40 | 0 | 0 | 5.71β |
| 85 | 70.06 | 25 | 0 | 10 | 0 | 0 | 5.76β |
| 86 | 70.06 | 25 | 0 | 10 | 0 | 10 | |
| 87 | 70.06 | 0 | 25 | 10 | 0 | 0 | 5.82β |
| 88 | 70.06 | 25 | 0 | 20 | 0 | 0 | 5.66β |
| 89 | 70.06 | 25 | 0 | 30 | 0 | 0 | 5.73β |
| 90 | 70.06 | 25 | 0 | 40 | 0 | 0 | 5.73β |
| 91 | 89.25 | 82.3 | 0 | 10 | 0 | 0 | |
| 92 | 89.25 | 82.3 | 0 | 10 | 0 | 10 | |
| 93 | 89.25 | 0 | 82.3 | 10 | 0 | 0 | |
| 94 | 89.25 | 82.3 | 0 | 20 | 0 | 0 | |
| 95 | 89.25 | 82.3 | 0 | 30 | 0 | 0 | |
| 96 | 89.25 | 82.3 | 0 | 40 | 0 | 0 | |
| 97 | 69.35 | 45 | 0 | 10 | 0 | 0 | 5.76β |
| 98 | 69.35 | 45 | 0 | 10 | 0 | 10 | |
| 99 | 69.35 | 0 | 45 | 10 | 0 | 0 | 5.79β |
| 100 | 69.35 | 45 | 0 | 20 | 0 | 0 | 5.73β |
| 101 | 69.35 | 45 | 0 | 30 | 0 | 0 | 5.76β |
| 102 | 69.35 | 45 | 0 | 40 | 0 | 0 | 5.64β |
| 103 | 50 | 0 | 0 | 5 | 0 | 0 | |
| 104 | 50 | 0 | 0 | 5 | 0 | 10 | |
| 105 | 50 | 12.5 | 0 | 5 | 0 | 0 | |
| 106 | 50 | 12.5 | 0 | 5 | 0 | 10 | |
| 107 | 50 | 25 | 0 | 5 | 0 | 0 | |
| 108 | 50 | 25 | 0 | 5 | 0 | 10 | |
| 109 | 50 | 37.5 | 0 | 5 | 0 | 0 | |
| 110 | 50 | 37.5 | 0 | 5 | 0 | 10 | |
| 111 | 50 | 50 | 0 | 5 | 0 | 0 | |
| 112 | 50 | 50 | 0 | 5 | 0 | 10 | |
| 113 | 50 | 75 | 0 | 5 | 0 | 0 | |
| 114 | 50 | 75 | 0 | 5 | 0 | 10 | |
| 115 | 50 | 100 | 0 | 5 | 0 | 0 | |
| 116 | 50 | 100 | 0 | 5 | 0 | 10 | |
| 117 | 66.67 | 0 | 0 | 5 | 0 | 0 | |
| 118 | 66.67 | 0 | 0 | 5 | 0 | 10 | |
| 119 | 66.67 | 25 | 0 | 5 | 0 | 0 | |
| 120 | 66.67 | 25 | 0 | 5 | 0 | 10 | |
| 121 | 66.67 | 50 | 0 | 5 | 0 | 0 | |
| 122 | 66.67 | 50 | 0 | 5 | 0 | 10 | |
| 123 | 66.67 | 75 | 0 | 5 | 0 | 0 | |
| 124 | 66.67 | 75 | 0 | 5 | 0 | 10 | |
| 125 | 66.67 | 100 | 0 | 5 | 0 | 0 | |
| 126 | 66.67 | 100 | 0 | 5 | 0 | 10 | |
| 127 | 83.33 | 50 | 0 | 5 | 0 | 10 | |
| 128 | 83.33 | 100 | 0 | 5 | 0 | 0 | |
| 129 | 83.33 | 100 | 0 | 5 | 0 | 10 | |
| 130 | 70.06 | 25 | 0 | 40 | 0 | 0 | |
| 131 | 70.06 | 25 | 0 | 40 | 0.067 | 0 | |
| 132 | 70.06 | 25 | 0 | 40 | 0.033 | 0 | |
| 133 | 70.06 | 25 | 0 | 40 | 0.067 | 0 | |
| 134 | 70.06 | 25 | 0 | 40 | 0 | 0 | |
| 135 | 70.06 | 25 | 0 | 40 | 0.133 | 0 | |
| 136 | 50 | 20 | 0 | 0 | 0 | 8.333 | |
| 137 | 50 | 20 | 0 | 0 | 0.067 | 8.333 | |
| 138 | 50 | 20 | 0 | 0 | 0.067 | 8.333 | |
| 139 | 25 | 25 | 0 | 0 | 0 | 8.333 | |
| 140 | 25 | 25 | 0 | 0 | 0.067 | 8.333 | 5.61β |
| 141 | 25 | 25 | 0 | 0 | 0.033 | 8.333 | 5.61β |
| 142 | 25 | 25 | 0 | 0 | 0.067 | 8.333 | |
| 143 | 25 | 25 | 0 | 10 | 0 | 8.333 | |
| 144 | 25 | 25 | 0 | 10 | 0.067 | 8.333 | |
| 145 | 25 | 25 | 0 | 10 | 0.033 | 8.333 | |
| 146 | 25 | 25 | 0 | 10 | 0.067 | 8.333 | |
| 147 | 50 | 27 | 0 | 0 | 0.067 | 10 | |
| 148 | 50 | 29 | 0 | 0 | 0.067 | 10 | |
| 149 | 50 | 31 | 0 | 0 | 0.067 | 10 | |
| 150 | 50 | 33 | 0 | 0 | 0.067 | 10 | |
| 151 | 50 | 35 | 0 | 0 | 0.067 | 10 | |
| 152 | 50 | 37 | 0 | 0 | 0.067 | 10 | |
| 153 | 50 | 39 | 0 | 0 | 0.067 | 10 | |
| 154 | 50 | 41 | 0 | 0 | 0.067 | 10 | |
| 155 | 50 | 43 | 0 | 0 | 0.067 | 10 | |
| 156 | 50 | 45 | 0 | 0 | 0.067 | 10 | |
| 157 | 70.06 | 25 | .3GeO2 | 0 | .067MnO2 | 0 | |
| 158 | 70.06 | 25 | .3GeO2 | 0 | 0.067 | 0 | |
| 159 | 70.06 | 25 | .3GeO2 | 40 | .067MnO2 | 0 | |
| 160 | 70.06 | 25 | .3GeO2 | 40 | 0.067 | 0 | |
| 161 | 70.06 | 25 | 0 | 50Nd2O3 | 0.067 | 0 | |
| 162 | 70.06 | 25 | 0 | 50Nd2O3 | .067MnO2 | 0 | |
| 163 | 70.06 | 25 | .3GeO2 | 50Nd2O3 | 0.067 | 0 | |
| 164 | 70.06 | 25 | .3GeO2 | 50Nd2O3 | .067MnO2 | 0 | |
| 165 | 25 | 25 | .3GeO2 | 0 | 0.067 | 10 | |
| 166 | 25 | 25 | .3GeO2 | 10 | 0.067 | 10 | |
| 167 | 25 | 25 | 0 | 10Nd2O3 | 0.067 | 0 | |
| 168 | 25 | 25 | .3GeO2 | 10Nd2O3 | 0.067 | 0 | |
| 169 | 25 | 25 | 0 | 50Nd2O3 | 0.067 | 0 | |
| 170 | 25 | 25 | .3GeO2 | 50Nd2O3 | 0.067 | 0 | |
| TABLE 2 | |||||
| Sample No. | Q (1 GHz) | f | Qf (1 GHz) | Ξ΅β² (1 GHz) | ΟF |
| 1 | 2170 | 1.156 | 2508.52 | ||
| 2 | 3170 | 1.172 | 3715.24 | ||
| 3 | 3420 | 1.111 | 3799.62 | ||
| 4 | 6580 | 1.089 | 7165.62 | ||
| 5 | 4770 | 1.045 | 4984.65 | ||
| 6 | 7300 | 1.013 | 7394.9 | ||
| 7 | 7830 | 0.949 | 7430.67 | ||
| 8 | 2620 | 1.092 | 2861.04 | ||
| 9 | 9510 | 1.104 | 10499.04 | ||
| 10 | 3600 | 1.054 | 3794.4 | ||
| 11 | 6720 | 1.052 | 7069.44 | ||
| 12 | 4410 | 1.016 | 4480.56 | ||
| 13 | 3600 | 1.0528 | 3790.08 | 81.8 | |
| 14 | |||||
| 15 | |||||
| 16 | 1000 | 0.98 | 980 | 82 | |
| 17 | 1500 | 0.9543 | 1431.45 | 81.9 | |
| 18 | 4780 | 0.974 | 4655.72 | ||
| 19 | 1400 | 0.9484 | 1327.76 | 84.2 | |
| 20 | 1500 | 0.9805 | 1470.75 | 79.7 | |
| 21 | 1000 | 0.9929 | 992.9 | 78.4 | |
| 22 | 1400 | 1.026 | 1436.4 | 73.8 | |
| 23 | 9700 | 1.1895 | 11538.15 | β41.61 | |
| 24 | 8000 | 1.0859 | 8687.2 | 68.3 | |
| 25 | 2500 | 1.0306 | 2576.5 | 76.6 | |
| 26 | 3900 | 1.0723 | 4181.97 | 76.7 | |
| 27 | |||||
| 28 | 1000 | 0.9966 | 996.6 | 77.1 | |
| 29 | |||||
| 30 | 12000 | 1.0818 | 12981.6 | 63.1 | β62.53 |
| 31 | 9400 | 1.0363 | 9741.22 | ||
| 32 | 9900 | 1.0109 | 10007.91 | ||
| 33 | 5200 | 1.0903 | 5669.56 | ||
| 34 | 5000 | 1.2524 | 6262 | ||
| 35 | 3800 | 1.3473 | 5119.74 | ||
| 36 | 11000 | 1.0839 | 11922.9 | 66 | β61.19 |
| 37 | 9600 | 1.0446 | 10028.16 | ||
| 38 | 8000 | 0.9915 | 7932 | ||
| 39 | 6000 | 1.0312 | 6187.2 | ||
| 40 | 6300 | 1.0055 | 6334.65 | ||
| 41 | 8000 | 1.1036 | 8828.8 | ||
| 42 | 8000 | 1.0685 | 8548 | ||
| 43 | 7680 | 0.9718 | 7463.424 | ||
| 44 | 7668 | 0.9669 | 7414.1892 | ||
| 45 | 8742 | 1.0128 | 8853.8976 | ||
| 46 | 8734 | 1.0081 | 8804.7454 | ||
| 47 | 9910 | 1.0601 | 10505.591 | ||
| 48 | 9696 | 1.0502 | 10182.739 | ||
| 49 | 10923 | 1.0876 | 11879.855 | β55.32 | |
| 50 | 10580 | 1.0904 | 11536.432 | β48.21 | |
| 51 | 4352 | 1.1621 | 5057.4592 | ||
| 52 | 7031 | 1.2009 | 8443.5279 | ||
| 53 | 7079 | 1.0114 | 7159.7006 | ||
| 54 | 7885 | 1.1273 | 8888.7605 | ||
| 55 | 10224 | 1.0482 | 10716.797 | β46.15 | |
| 56 | 10780 | 1.1261 | 12139.358 | β57.93 | |
| 57 | 3674 | 1.1532 | 4236.8568 | ||
| 58 | 3556 | 0.9687 | 3444.6972 | ||
| 59 | 4647 | 0.9609 | 4465.3023 | ||
| 60 | 7770 | 1.0052 | 7810.404 | ||
| 61 | 7948 | 1.0043 | 7982.1764 | ||
| 62 | 9417 | 1.0411 | 9804.0387 | ||
| 63 | 9302 | 1.0517 | 9782.9134 | ||
| 64 | 10341 | 1.0823 | 11192.064 | β54.1 | |
| 65 | 10018 | 1.0909 | 10928.636 | β46.83 | |
| 66 | 10860 | 1.1288 | 12258.768 | β62.16 | |
| 67 | 10445 | 1.1151 | 11647.22 | β55.87 | |
| 68 | 2653 | 0.9673 | 2566.2469 | ||
| 69 | 6935 | 1.0049 | 6968.9815 | ||
| 70 | 9223 | 1.0384 | 9577.1632 | ||
| 71 | 10003 | 1.1293 | 11296.388 | β58.02 | |
| 72 | 11197 | 1.1336 | 12692.919 | β65.23 | |
| 73 | 9700 | 1.0987 | 10657.39 | 65.5 | β50.34 |
| 74 | 4500 | 1.1571 | 5206.95 | 69.8 | |
| 75 | 9300 | 1.0991 | 10221.63 | 66.3 | β51.46 |
| 76 | 9400 | 1.1015 | 10354.1 | 67.8 | β32.96 |
| 77 | 8200 | 1.0835 | 8884.7 | 69.5 | β12.82 |
| 78 | 6600 | 1.1135 | 7349.1 | 70.5 | 15.09 |
| 79 | 10600 | 1.1003 | 11663.18 | 66 | β52.13 |
| 80 | 3600 | 1.0643 | 3831.48 | 67.1 | |
| 81 | 8800 | 1.1149 | 9811.12 | 65.8 | β53.34 |
| 82 | 9800 | 1.09 | 10682 | 67.5 | β36.93 |
| 83 | 8800 | 1.0905 | 9596.4 | 68.8 | β16.24 |
| 84 | 7400 | 1.0616 | 7855.84 | 69.9 | 7.33 |
| 85 | 10300 | 1.1232 | 11568.96 | 65.8 | β48.71 |
| 86 | 4300 | 1.0486 | 4508.98 | 69.3 | |
| 87 | 8700 | 1.1725 | 10200.75 | 67 | β51.36 |
| 88 | 10400 | 1.0536 | 10957.44 | 65.5 | β32.12 |
| 89 | 9000 | 1.045 | 9405 | 68.9 | β14.01 |
| 90 | 7600 | 1.0537 | 8008.12 | 71.9 | 9.81 |
| 91 | 9200 | 1.2902 | 11869.84 | 61.2 | |
| 92 | 2600 | 1.088 | 2828.8 | 64.1 | |
| 93 | 8000 | 1.1366 | 9092.8 | 61.5 | |
| 94 | 9200 | 1.1044 | 10160.48 | 61.9 | |
| 95 | 7500 | 1.1018 | 8263.5 | 62.8 | |
| 96 | 6000 | 1.1165 | 6699 | 62.8 | |
| 97 | 10000 | 1.0912 | 10912 | 66.9 | β47.17 |
| 98 | 4800 | 1.0472 | 5026.56 | 71.9 | |
| 99 | 9400 | 1.0952 | 10294.88 | 67.8 | β49.31 |
| 100 | 9500 | 1.0742 | 10204.9 | 68.1 | β29.03 |
| 101 | 8400 | 1.0607 | 8909.88 | 70.9 | β8.75 |
| 102 | 6800 | 1.0476 | 7123.68 | 71.2 | 20.57 |
| 103 | 4300 | 1.0483 | 4507.69 | 70.8 | |
| 104 | 2500 | 1.0174 | 2543.5 | 73.9 | |
| 105 | 10300 | 1.0656 | 10975.68 | 68.7 | |
| 106 | 2700 | 1.0132 | 2735.64 | 75.6 | |
| 107 | 9850 | 1.0651 | 10491.235 | 69.2 | |
| 108 | 7000 | 1.0099 | 7069.3 | 75.7 | |
| 109 | 9000 | 1.0788 | 9709.2 | 70.1 | |
| 110 | 6800 | 1.0302 | 7005.36 | 73.6 | |
| 111 | 2000 | 1.0491 | 2098.2 | 71.9 | |
| 112 | 4800 | 1.1632 | 5583.36 | 55 | |
| 113 | |||||
| 114 | 5700 | 1.0687 | 6091.59 | 66 | |
| 115 | |||||
| 116 | |||||
| 117 | 4200 | 1.0897 | 4576.74 | 67.4 | |
| 118 | 5600 | 1.0445 | 5849.2 | 67.3 | |
| 119 | 10600 | 1.102 | 11681.2 | 65.5 | |
| 120 | 1600 | 1.0285 | 1645.6 | 71.4 | |
| 121 | 9700 | 1.102 | 10689.4 | 66.5 | |
| 122 | 3200 | 1.0222 | 3271.04 | 72.5 | |
| 123 | 1000 | 1.0881 | 1088.1 | 68.4 | |
| 124 | 5100 | 1.0373 | 5290.23 | 68.2 | |
| 125 | |||||
| 126 | 4900 | 1.0799 | 5291.51 | 63.4 | |
| 127 | 1600 | 1.0603 | 1696.48 | 66.7 | |
| 128 | 1600 | 1.1628 | 1860.48 | 61.7 | |
| 129 | 3700 | 1.0604 | 3923.48 | 67.4 | |
| 130 | 6600 | 1.0502 | 6931.32 | 71.1 | |
| 131 | 6900 | 1.0722 | 7398.18 | 71.1 | |
| 132 | 6900 | 1.0661 | 7356.09 | 71.2 | |
| 133 | 6800 | 1.0789 | 7336.52 | 71.4 | |
| 134 | 6100 | 1.0704 | 6529.44 | 71.5 | |
| 135 | 7000 | 1.0816 | 7571.2 | 69.6 | |
| 136 | 6900 | 1.0419 | 7189.11 | 73.4 | |
| 137 | 7300 | 1.037 | 7570.1 | 73.4 | |
| 138 | 6900 | 1.0293 | 7102.17 | 72.9 | |
| 139 | 8800 | 1.0313 | 9075.44 | 72.9 | |
| 140 | 9900 | 1.0287 | 10184.13 | 72.9 | β2.6 |
| 141 | 9900 | 1.0244 | 10141.56 | 73 | β1.86 |
| 142 | 9600 | 1.0327 | 9913.92 | 72.7 | |
| 143 | 8000 | 1.0281 | 8224.8 | 74.6 | |
| 144 | 8600 | 1.0266 | 8828.76 | 74.4 | |
| 145 | 8200 | 1.0362 | 8496.84 | 74.4 | |
| 146 | 7900 | 1.0366 | 8189.14 | 74.4 | |
| 147 | 1700 | 1.1102 | 1887.34 | 63.9 | |
| 148 | 2000 | 1.1221 | 2244.2 | 64 | |
| 149 | 2600 | 1.1132 | 2894.32 | 64.2 | |
| 150 | 3000 | 1.1339 | 3401.7 | 62.8 | |
| 151 | 3500 | 1.0861 | 3801.35 | 65.4 | |
| 152 | 4300 | 1.0872 | 4674.96 | 64.3 | |
| 153 | 5600 | 1.0834 | 6067.04 | 65.2 | |
| 154 | 5800 | 1.0893 | 6317.94 | 65.5 | |
| 155 | 5800 | 1.0991 | 6374.78 | 63.6 | |
| 156 | 5000 | 1.0901 | 5450.5 | 63.3 | |
| 157 | 9000 | 1.1791 | 10611.9 | 64.3 | |
| 158 | 9200 | 1.1796 | 10852.32 | 63.8 | |
| 159 | 6200 | 1.1302 | 7007.24 | 71.2 | |
| 160 | 6200 | 1.1229 | 6961.98 | 71.1 | |
| 161 | 10200 | 1.1065 | 11286.3 | 64 | |
| 162 | 10300 | 1.1121 | 11454.63 | 65.3 | |
| 163 | 10400 | 1.1118 | 11562.72 | 64.3 | |
| 164 | 9500 | 1.124 | 10678 | 67 | |
| 165 | 3800 | 1.1339 | 4308.82 | 63.8 | |
| 166 | 6000 | 1.1159 | 6695.4 | 60.3 | |
| 167 | 5600 | 1.0165 | 5692.4 | 77.6 | |
| 168 | 6700 | 1.0823 | 7251.41 | 75.2 | |
| 169 | 8800 | 1.0029 | 8825.52 | 80.4 | |
| 170 | 8500 | 1.0377 | 8820.45 | 79.5 | |
| TABLE 3 | ||||
| Sample No. | Q (3 GHz) | f | Qf (3 GHz) | Ξ΅β² (3 GHz) |
| 23 | 3669 | 3.5075 | 12869.018 | 54.69 |
| 30 | 4104 | 3.301 | 13547.304 | 65.06 |
| 36 | 4080 | 3.283 | 13394.64 | 65.81 |
| 49 | 3981 | 3.3071 | 13165.565 | 64.3 |
| 50 | 3952 | 3.2981 | 13034.091 | |
| 55 | 3619 | 3.1984 | 11575.01 | 68.8 |
| 56 | 3988 | 3.315 | 13220.22 | 63.97 |
| 64 | 3808 | 3.3186 | 12637.229 | 63.85 |
| 65 | 3746 | 3.2934 | 12337.076 | 64.86 |
| 66 | 4175 | 3.4485 | 14397.488 | 59.07 |
| 67 | 3986 | 3.4196 | 13630.526 | 60.08 |
| 71 | 3807 | 3.3019 | 12570.333 | 64.52 |
| 72 | 4161 | 3.4473 | 14344.215 | 59.19 |
| 73 | 3726 | 3.2956 | 12279.406 | 64.89 |
| 75 | 4055 | 3.273 | 13272.015 | 65.84 |
| 76 | 3784 | 3.2418 | 12266.971 | 67.04 |
| 77 | 3548 | 3.1944 | 11333.731 | 69.1 |
| 78 | 3106 | 3.1836 | 9888.2616 | 69.64 |
| 79 | 4152 | 3.2889 | 13655.513 | 65.19 |
| 81 | 3890 | 3.2922 | 12806.658 | 65.06 |
| 82 | 3915 | 3.243 | 12696.345 | 67.01 |
| 83 | 3725 | 3.2149 | 11975.503 | 68.29 |
| 84 | 3319 | 3.1924 | 10595.576 | 69.25 |
| 85 | 4121 | 3.2855 | 13539.546 | 65.33 |
| 87 | 3941 | 3.2575 | 12837.808 | 66.46 |
| 88 | 3864 | 3.2943 | 12729.175 | 65.08 |
| 89 | 3594 | 3.2154 | 11556.148 | 68.36 |
| 90 | 3279 | 3.158 | 10355.082 | 70.9 |
| 97 | 3973 | 3.2739 | 13007.205 | 65.89 |
| 99 | 3955 | 3.2538 | 12868.779 | 66.7 |
| 100 | 3635 | 3.239 | 11773.765 | 67.35 |
| 101 | 3520 | 3.1777 | 11185.504 | 70.03 |
| 102 | 2975 | 3.1723 | 9437.5925 | 70.27 |
| 140 | 3776 | 3.1235 | 11794.336 | 72.7 |
| 141 | 3793 | 3.1231 | 11845.918 | 72.66 |
As described herein, in some radio-frequency (RF) applications such as low-frequency (700 MHz-1 GHz) microwave applications, materials with dielectric constant values greater than 60 and having Qf (product of Q and frequency f) values greater than 10,000 can be desirable. Among the non-limiting examples listed in Tables 1-3, a number of configurations can include such a combination of relatively high dielectric constant (e.g., greater than 60) and relatively high Qf (e.g., greater than 10,000) at or near such a low-frequency range of 700 MHz-1 GHz. Table 4 lists such configurations selected from the list of Tables 1-3.
| TABLE 4 | |||||||||
| Sample | Al | Ba | Sr | La | CeO2 | TiO2 | Qf | ||
| No. | % | % | % | % | w % | w % | (1 GHz) | Ξ΅β² | ΟF |
| 9 | 75.1 | 24.8 | 0 | 0 | 0 | 0 | 10499 | ||
| 23 | 75.1 | 24.8 | 0 | 0 | 0.25 | 0 | 11538 | β41.61 | |
| 30 | 74.2 | 48.06 | 0 | 2.8 | 0.25 | 0 | 12982 | 63.1 | β62.53 |
| 32 | 24.98 | 24.91 | 0 | 8.89 | 0.75 | 0 | 10008 | ||
| 36 | 74.75 | 25.34 | 0 | 2.84 | 0 | 0 | 11923 | 66 | β61.19 |
| 37 | 49.68 | 24.91 | 0 | 5.82 | 0 | 0 | 10028 | ||
| 47 | 50.02 | 24.84 | 0 | 5 | 0 | 0 | 10506 | ||
| 48 | 50.02 | 24.84 | 0 | 10 | 0 | 0 | 10183 | ||
| 49 | 70.07 | 25 | 0 | 5 | 0 | 0 | 11880 | β55.32 | |
| 50 | 70.07 | 25 | 0 | 10 | 0 | 0 | 11536 | β48.21 | |
| 55 | 50.02 | 24.84 | 0 | 2.5 | 0 | 0 | 10717 | β46.15 | |
| 56 | 70.07 | 25 | 0 | 2.5 | 0 | 0 | 12139 | β57.93 | |
| 64 | 69.4 | 45.02 | 0 | 5 | 0 | 0 | 11192 | β54.1 | |
| 65 | 69.4 | 45.02 | 0 | 10 | 0 | 0 | 10929 | β46.83 | |
| 66 | 89.23 | 82.2 | 0 | 5 | 0 | 0 | 12259 | β62.16 | |
| 67 | 89.23 | 82.2 | 0 | 10 | 0 | 0 | 11647 | β55.87 | |
| 71 | 69.4 | 45.02 | 0 | 2.5 | 0 | 0 | 11296 | β58.02 | |
| 72 | 89.23 | 82.2 | 0 | 2.5 | 0 | 0 | 12693 | β65.23 | |
| 73 | 74.2 | 48 | 0 | 10 | 0 | 0 | 10657 | 65.5 | β50.34 |
| 75 | 74.2 | 0 | 48 | 10 | 0 | 0 | 10222 | 66.3 | β51.46 |
| 76 | 74.2 | 48 | 0 | 20 | 0 | 0 | 10354 | 67.8 | β32.96 |
| 79 | 74.75 | 25.35 | 0 | 10 | 0 | 0 | 11663 | 66 | β52.13 |
| 82 | 74.75 | 25.35 | 0 | 20 | 0 | 0 | 10682 | 67.5 | β36.93 |
| 85 | 70.06 | 25 | 0 | 10 | 0 | 0 | 11569 | 65.8 | β48.71 |
| 87 | 70.06 | 0 | 25 | 10 | 0 | 0 | 10201 | 67 | β51.36 |
| 88 | 70.06 | 25 | 0 | 20 | 0 | 0 | 10957 | 65.5 | β32.12 |
| 91 | 89.25 | 82.3 | 0 | 10 | 0 | 0 | 11870 | 61.2 | |
| 94 | 89.25 | 82.3 | 0 | 20 | 0 | 0 | 10160 | 61.9 | |
| 97 | 69.35 | 45 | 0 | 10 | 0 | 0 | 10912 | 66.9 | β47.17 |
| 99 | 69.35 | 0 | 45 | 10 | 0 | 0 | 10295 | 67.8 | β49.31 |
| 100 | 69.35 | 45 | 0 | 20 | 0 | 0 | 10205 | 68.1 | β29.03 |
| 105 | 50 | 12.5 | 0 | 5 | 0 | 0 | 10976 | 68.7 | |
| 107 | 50 | 25 | 0 | 5 | 0 | 0 | 10491 | 69.2 | |
| 119 | 66.67 | 25 | 0 | 5 | 0 | 0 | 11681 | 65.5 | |
| 121 | 66.67 | 50 | 0 | 5 | 0 | 0 | 10689 | 66.5 | |
| 140 | 25 | 25 | 0 | 0 | 0.067 | 8.333 | 10184 | 72.9 | β2.6 |
| 141 | 25 | 25 | 0 | 0 | 0.033 | 8.333 | 10142 | 73 | β1.86 |
| 157 | 70.06 | 25 | .3GeO2 | 0 | .067MnO2 | 0 | 10612 | 64.3 | |
| 158 | 70.06 | 25 | .3GeO2 | 0 | 0.067 | 0 | 10852 | 63.8 | |
| 161 | 70.06 | 25 | 0 | 50Nd2O3 | 0.067 | 0 | 11286 | 64 | |
| 162 | 70.06 | 25 | 0 | 50Nd2O3 | .067MnO2 | 0 | 11455 | 65.3 | |
| 163 | 70.06 | 25 | .3GeO2 | 50Nd2O3 | 0.067 | 0 | 11563 | 64.3 | |
| 164 | 70.06 | 25 | .3GeO2 | 50Nd2O3 | .067MnO2 | 0 | 10678 | 67 | |
In Table 4, some of the listed samples do not have measured dielectric constant (ββ²) values. However, and as described herein in reference to Formula 1, tungsten bronze based materials, including the samples of Table 4, will tend to have dielectric constant values that are greater than 50.
Also in Table 4, some of the measured values of temperature coefficient of resonant frequency (Οf) are not listed. Among the samples whose Οf values are listed, all of them are negative, mainly due to the Sm being the primary lanthanide. As described herein, such negative values of Οf can be compensated by introduction of other lanthanides (e.g., Nd, Pr, Ce and La) having positive Οf values.
For example, in Table 4, samples 56, 49, 50 and 88 all have the same 70% aluminum percent value and 25% barium percent value, but have increasing lanthanum content (La %) of 2.5%, 5%, 10% and 20%, respectively. For the same samples in the same order, one can see that the Οf values (β57.93, β55.32, β48.21 and β32.12) become less negative as La % value increases.
In some embodiments, materials having one or more features as described herein can be implemented as microwave dielectric materials. As described herein, such microwave dielectric materials can be configured to have dielectric constant values greater than 60. When combined with improved Q performance and temperature compensation capability, such microwave dielectric materials can be desirable for RF applications such as LTE applications in which filters can benefit from reduced sizes.
As described herein, substituting aluminum (Al) for at least some of the titanium (Ti) in the octahedral sites of a tungsten bronze material can yield some or all the foregoing desirable properties. Such substitutions can be effectuated in cost-effective manner.
As also described herein, lanthanides such as Sm and/or Nd can be utilized to achieve temperature compensated ceramic bodies. Table 5 lists additional examples of compositions that show, among others, how temperature coefficient of resonant frequency (Οf) can be adjusted by different combinations of Sm and Nd, and/or different substitutions of Ti with Al.
| TABLE 5 | ||||
| Sample | Density (g/cm3) | Dielectric Constant | ΟF | Qf (at 3 GHz) |
| Ba4Sm9.6Ti17.2Al.8O54 | 5.62 | 66.33 | β50.38 | 11641 |
| Ba4Nd9.46667Ti17.6Al.4O54 | 5.69 | 79.5 | 48.17 | 16073 |
| Ba4Nd9.6Ti17.2Al.8O54 | 5.67 | 75.12 | 32.07 | 15298 |
| Ba4Nd9.7333Ti16.8Al1.2O54 | 5.70 | 70.07 | 13.76 | 14635 |
| Ba4Nd9.8666Ti16.4Al1.6O54 | 5.35 | 60.22 | 8.5 | 16028 |
| Ba4Nd9.0667Y.4Ti17.6Al.4O54 | 5.63 | 78.42 | 26.36 | 13936 |
| Ba4Nd8.8Y.8Ti17.2Al.8O54 | 5.57 | 72.3 | 5.85 | 14673 |
| Ba4Sm7.5733Nd1.8933Ti17.6Al.4O54 | 5.77 | 80.27 | 20.23 | 15653 |
| Ba4Sm5.76Nd3.84Y.8Ti17.2Al.8O54 | 5.81 | 74.65 | β7.26 | 16534 |
At least some of the compositions listed in Table 5 are more specific examples of the samarium (Sm) based compositions described herein in reference to Formula 9 (Ba4+xβ²Sm(2/3)[14+0.5yβxβ²]Ti18βyAlyO54). In the example context of some of Sm being replaced with neodymium (Nd), such a formula can be expressed as
Ba4(Nd1-xSmX)28/3+y/3Ti18βyAlyO54.ββ(10)
In Formula 10, x can be referred to as Sm content, and y can be referred to as Al content.
As described in reference to Table 5, temperature coefficient of resonant frequency (Οf) can be tuned by different combinations of Sm and Nd, and/or different substitutions of Ti with Al. Table 6 lists various examples of combinations of the Sm content (x) and the A1 content (y) in reference to Formula 10.
| TABLE 6 | |||
| Sample | Qf (at 1 GHz) | Qf (at 3 GHz) | Ξ΅β² |
| x = 0.2, y = 1.6 | 9796 | 15907 | 65.61 |
| x = 0.4, y = 1.2 | 10210 | 14448 | 70.02 |
| x = 0.6, y = 0.8 | 9436 | 13107 | 73.07 |
| x = 0.8, y = 0.4 | 7688 | 12021 | 76.46 |
| x = 0.6, y = 0.4 | 8824 | 13247 | 77.81 |
| x = 0.4, y = 0.8 | 10302 | 15395 | 73.96 |
| x = 0.2, y = 1.2 | 10151 | 15638 | 71.22 |
| x = 0.4, y = 0.4 | 9068 | 15593 | 70.38 |
| x = 0.2, y = 0.8 | 9154 | 14851 | 75.38 |
| x = 0.355, y = 0.68 | 10500 | 15321 | 75.2 |
For the samples listed in Table 6, their values of Οf are generally in a range of β50 to 0 or 0 to 50. Accordingly, such samples can be utilized to estimate a plane in which Οf is zero or close to zero, if such tuning is desired. For the example described in reference to Formula 10 and Table 6, such a Οf=0 plane can be along an approximate line between points (yβ0, xβ0.77) and (yβ1.8, xβ2) when y (Al content) is on the horizontal axis and x (Sm content) is on the vertical axis. In such a system, one can see that the example configuration of (x=0.355, y=0.68) (last example in Table 6) yields relatively high values of dielectric constant (75.2) and Qf (10500 at 1 GHz), while having Οf that is tuned to a value close to zero. It will be understood that other systems having one or more features as described herein can also be tuned in a similar manner.
In some embodiments, Q value of a system can be adjusted (e.g., enhanced) by adjusting the Sm content (in the example context of the system of Formula 10), adding elements/compounds, and/or substituting elements/compounds. In the context of the example system of Formula 10, a more specific example can be represented by Ba4Nd6.16Sm3.4Ti17.32Al0.68O54. Examples of adjustments to such a system, and the resulting values of Qf, are listed in Table 7. If a Qf value greater than 10000 is desired, one can see that, for example, substituting Ge0.1 for Ti0.1 yields a relatively high Qf value of approximately 12300 (at 1 GHz).
| TABLE 7 |
| Ba4Nd6.16Sm3.4Ti17.32Al0.68O54 |
| x = 0.6 | Qf = 8467 (1 GHz) | |
| x = 0.75 | Qf = 8993 (1 GHz) | |
| 1% Na2O added | Qf = 9943 (1 GHz) | |
| 1% K2O added | Qf = 7597 (1 GHz) | |
| +2% Ba2Ti9O20 | Qf = 9982 (1 GHz) | |
| Sn.05 for Ti.05 | Qf = 10040 (1 GHz) | |
| (Ba3.6Sr0.4) | Qf = 8958 (1 GHz) | |
| Mg.34Ti.34 for Al.68 | Qf = 8101 (1 GHz) | |
| Zn.34Ti.34 for Al.68 | Qf = 6396 (1 GHz) | |
| Ge.1 for Ti.1 | Qf = 12300 (1 GHz) | |
| Fe.68 for Al.68 | Qf = 4610 | |
| Mn.68 for Al.68 | Qf = 8045 | |
| Mg.34Ge.34 for Al.68 | Qf = 8509 | |
| Zn.34Ge.34 for Al.68 | Qf = 10044 | |
FIGS. 1 and 2 show examples of microwave devices that can be formed from materials having one or more features as described herein. FIG. 1 shows that in some embodiments, a ceramic puck 100 can include a material as described herein so as to yield desirable properties such as a high dielectric constant (e.g., greater than 60) and a high Qf value (e.g., greater than 10,000) at relatively low frequencies (e.g., 700 MHz-1 GHz). Such a puck 100 can be implemented in a cylindrical shape having a diameter Dr and a height Lr. Such a puck 100 can be utilized as a microwave resonator.
FIG. 2 shows that in some embodiments, a ceramic puck 100 having one or more features as described herein can include a center aperture dimensioned to allow, for example, tuning of the ceramic puck when utilized as a microwave resonator. The aperture is shown to have a diameter of dr. The overall diameter Dr and the height Lr may or may not be the same as the solid ceramic puck counterpart.
FIG. 3 shows a tunable microwave resonator configuration 110. A ceramic puck 100 similar to the example of FIG. 2 is shown to be supported by a support structure. A ceramic tuning element can be dimensioned to fit within the aperture of the ceramic puck 100; and tuning can be achieved by the extent of insertion of the tuning element into the aperture.
FIG. 4 shows an example of a cavity filter 120 having a plurality of cavities 122 arranged between RF ports 124, 126. Each cavity 122 can be dimensioned to receive a resonator puck (e.g., 100 in FIGS. 1 and 2). Such a resonator puck may or may not be tunable. The resonators in their respective cavities can pass successively filtered RF signal through slots formed between neighboring cavities.
FIG. 5 shows an example of an RF system that can utilize one or more of the filter device 120 of FIG. 4. For example, the filter device of FIG. 4 can be implemented as a dielectric narrowband filter 120 between an antenna and a diplexer. The diplexer can be configured to provide a filtered signal to a low-noise amplifier (LNA) to be further processed by an Rx portion of a baseband subsystem. The diplexer can also be configured to route an amplified RF signal from a power amplifier (PA) to the antenna for transmission.
FIGS. June 2010 show examples of how dielectric materials and/or devices having one or more features as described herein can be fabricated. FIG. 6 shows a process 20 that can be implemented to fabricate a ceramic material having one or more of the foregoing properties. In block 21, powder having one or more features as described herein can be prepared. In block 22, a shaped object can be formed from the prepared powder. In block 23, the formed object can be sintered. In block 24, the sintered object can be finished to yield a finished ceramic object having one or more desirable properties.
In implementations where the finished ceramic object is part of a device, the device can be assembled in block 25. In implementations where the device or the finished ceramic object is part of a product, the product can be assembled in block 26.
FIG. 6 further shows that some or all of the steps of the example process 20 can be based on a design, specification, etc. Similarly, some or all of the steps can include or be subjected to testing, quality control, etc.
In some implementations, powder prepared in the powder preparation step (block 21) of FIG. 6 can be formed into different shapes by different forming techniques. By way of an example, FIG. 7 shows a process 50 that can be implemented to press-form a shaped object from a powder material prepared as described herein. In block 52, a shaped die can be filled with a desired amount of the powder. In FIG. 8, configuration 60 shows the shaped die as 61 that defines a volume 62 dimensioned to receive the powder 63 and allow such power to be pressed. In block 53, the powder in the die can be compressed to form a shaped object. Configuration 64 shows the powder in an intermediate compacted form 67 as a piston 65 is pressed (arrow 66) into the volume 62 defined by the die 61. In block 54, pressure can be removed from the die. In block 55, the piston (65) can be removed from the die (61) so as to open the volume (62). Configuration 68 shows the opened volume (62) of the die (61) thereby allowing the formed object 69 to be removed from the die. In block 56, the formed object (69) can be removed from the die (61). In block 57, the formed object can be stored for further processing.
In some implementations, formed objects fabricated as described herein can be sintered to yield desirable physical properties as ceramic devices. FIG. 9 shows a process 70 that can be implemented to sinter such formed objects. In block 71, formed objects can be provided. In block 72, the formed objects can be introduced into a kiln. In FIG. 10, a plurality of formed objects 69 are shown to be loaded into a sintering tray 80. The example tray 80 is shown to define a recess 81 dimensioned to hold the formed objects 69 on a surface 82 so that the upper edge of the tray is higher than the upper portions of the formed objects 69. Such a configuration allows the loaded trays to be stacked during the sintering process. The example tray 80 is further shown to define cutouts 83 at the side walls to allow improved circulation of hot gas at within the recess 81, even when the trays are stacked together. FIG. 10 further shows a stack 84 of a plurality of loaded trays 80. A top cover 85 can be provided so that the objects loaded in the top tray generally experience similar sintering condition as those in lower trays.
In block 73, heat can be applied to the formed objects so as to yield sintered objects. Such application of heat can be achieved by use of a kiln. In block 74, the sintered objects can be removed from the kiln. In FIG. 10, the stack 84 having a plurality of loaded trays is depicted as being introduced into a kiln 87 (stage 86a). Such a stack can be moved through the kiln (stages 86b, 86c) based on a desired time and temperature profile. In stage 86d, the stack 84 is depicted as being removed from the kiln so as to be cooled.
In block 75, the sintered objects can be cooled. Such cooling can be based on a desired time and temperature profile. In block 76, the cooled objects can undergo one or more finishing operations. In block 77, one or more tests can be performed.
Heat treatment of various forms of powder and various forms of shaped objects are described herein as calcining, firing, annealing, and/or sintering. It will be understood that such terms may be used interchangeably in some appropriate situations, in context-specific manners, or some combination thereof.
Unless the context clearly requires otherwise, throughout the description and the claims, the words βcomprise,β βcomprising,β and the like are to be construed in an inclusive sense, as opposed to an exclusive or exhaustive sense; that is to say, in the sense of βincluding, but not limited to.β The word βcoupledβ, as generally used herein, refers to two or more elements that may be either directly connected, or connected by way of one or more intermediate elements. Additionally, the words βherein,β βabove,β βbelow,β and words of similar import, when used in this application, shall refer to this application as a whole and not to any particular portions of this application. Where the context permits, words in the above Detailed Description using the singular or plural number may also include the plural or singular number respectively. The word βorβ in reference to a list of two or more items, that word covers all of the following interpretations of the word: any of the items in the list, all of the items in the list, and any combination of the items in the list.
The above detailed description of embodiments of the invention is not intended to be exhaustive or to limit the invention to the precise form disclosed above. While specific embodiments of, and examples for, the invention are described above for illustrative purposes, various equivalent modifications are possible within the scope of the invention, as those skilled in the relevant art will recognize. For example, while processes or blocks are presented in a given order, alternative embodiments may perform routines having steps, or employ systems having blocks, in a different order, and some processes or blocks may be deleted, moved, added, subdivided, combined, and/or modified. Each of these processes or blocks may be implemented in a variety of different ways. Also, while processes or blocks are at times shown as being performed in series, these processes or blocks may instead be performed in parallel, or may be performed at different times.
The teachings of the invention provided herein can be applied to other systems, not necessarily the system described above. The elements and acts of the various embodiments described above can be combined to provide further embodiments.
While some embodiments of the inventions have been described, these embodiments have been presented by way of example only, and are not intended to limit the scope of the disclosure. Indeed, the novel methods and systems described herein may be embodied in a variety of other forms; furthermore, various omissions, substitutions and changes in the form of the methods and systems described herein may be made without departing from the spirit of the disclosure. The accompanying claims and their equivalents are intended to cover such forms or modifications as would fall within the scope and spirit of the disclosure.
1. A composition comprising a material with a formula Ba4+xSm(2/3)(14βx+0.5y)Ti18βyAlyO54, the quantity y being in a range 0<y<2, the quantity x being in a range 0<x<2βy.