Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
  • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C14/00—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix
  • C03C14/004—Glass compositions containing a non-glass component, e.g. compositions containing fibres, filaments, whiskers, platelets, or the like, dispersed in a glass matrix the non-glass component being in the form of particles or flakes

Definitions

• the invention relates to a glass ceramic composition with at least one oxide ceramic that has barium, titanium and at least one rare earth metal Rek, and at least one glass material that has at least one oxide with boron.
• the invention relates to a glass ceramic composition with at least one oxide ceramic that has barium, titanium and at least one rare earth metal Rek, and at least one glass material that has at least one oxide with boron and at least one oxide with at least one tetravalent metal Me4 +.
• the use of the glass ceramic materials is also specified.
• the glass ceramic compositions mentioned are known from US Pat. No. 5,264,403.
• the oxide ceramic of the glass ceramic mass is made from barium oxide (BaO), titanium dioxide (Ti0 2 ), a trioxide of a rare earth metal (Rek 2 0 3 ) and possibly bismuth trioxide (Bi 2 0 3 ).
• the rare earth metal Rek is, for example, neodymium.
• the oxide ceramic of the composition mentioned is referred to as microwave ceramic, since its dielectric material properties permittivity ( ⁇ r ), quality (Q) and temperature response of the frequency (Tkf value) are very well suited for use in microwave technology.
• the glass material of the glass ceramic mass consists of boron trioxide (B 2 0 3 ), silicon dioxide (Si0 2 ) and zinc oxide (ZnO).
• a ceramic portion of the oxide ceramic in the glass ceramic mass is, for example, 90% and a glass portion of the glass material is 10%.
• the glass ceramic mass is compacted at a sintering temperature of approximately 950 ° C.
• a glass ceramic mass which mainly consists of a glass portion of a glass material.
• the glass material has different combinations of silicon dioxide, an anthanid trioxide (Ln 2 0 3 ), Titanium dioxide, an alkaline earth metal oxide and zirconium dioxide (Zr0 2 ).
• LTCC technology is a ceramic multilayer process in which a passive electrical component can be integrated in the volume of a ceramic multilayer body.
• the passive electrical component is, for example, an electrical conductor track, a coil, an induction or a capacitor. Integration is achieved, for example, by printing a metal structure corresponding to the component on one or more ceramic green foils, stacking the printed ceramic green foils on top of one another to form a composite, and sintering the composite. Since ceramic green foils with a low-sintering glass ceramic mass are used, low-melting, electrically highly conductive elemental metal MeO such as silver or copper can be sintered in combination with the ceramic green foils.
• An LTCC method is known from WO 00/04577, in which, in order to avoid lateral shrinkage (zero xy shrinkage) during sintering, the composite of ceramic green foils is built up with a first and at least one further glass ceramic mass. The first and the further glass ceramic mass compact at different temperatures. In a two-stage sintering process, the
• the first glass ceramic mass condenses.
• the non-compacting further glass-ceramic mass prevents the lateral shrinkage of the compacting first glass-ceramic mass.
• the already compacted first glass ceramic mass now prevents the lateral shrinkage of the further glass-ceramic mass that is compacting at the higher temperature.
• the first glass ceramic mass that compacts at a lower temperature consists mainly of a glass portion with a glass material that contains barium, aluminum and silicon (barium aluminum silicate glass).
• the further glass ceramic mass which compacts at a higher temperature consists mainly of an oxide ceramic of the formal composition Ba 6 - ⁇ ek8 + ⁇ Ti ⁇ 8 ⁇ 54 (0 ⁇ x ⁇ 1), where Rek of a rare earth metal is lanthanum, neodymium or samarium.
• the ceramic multilayer body obtained by the two-stage sintering process is characterized by a lateral shrinkage (lateral offset) of ⁇ 2%.
• the glass ceramic mass is primarily compacted by reactive liquid phase sintering.
• the glass material forms a liquid glass phase (glass melt).
• the oxide ceramic dissolves in the glass melt until a saturation concentration is reached and the oxide ceramic re-precipitates.
• a component of the oxide ceramic remains in the glass phase after the glass ceramic mass has cooled.
• the object of the present invention is to provide a glass ceramic mass which compresses at a temperature of below 850 ° C. and is nevertheless suitable for use in microwave technology.
• a glass ceramic mass is specified with at least one oxide ceramic which has barium, titanium and at least one rare earth metal Rek, and at least one glass material which has at least one oxide with boron and at least one oxide with at least one tetravalent metal Me4 +.
• the glass ceramic mass is characterized in that the glass material has at least one oxide with at least one rare earth metal Reg.
• the glass material has at least one oxide with at least one pentavalent metal Me5 +.
• a glass ceramic mass is also specified with at least one oxide ceramic that has barium, titanium and at least one rare earth metal Rek, and at least one glass material that has at least one oxide with boron.
• This glass ceramic mass is characterized in that the glass material has at least one oxide with at least one pentavalent metal Me5 + and at least one oxide with at least one rare earth metal Reg.
• the glass material has at least one oxide with at least one tetravalent metal Me4 +.
• the glass ceramic mass is a glass ceramic composition and regardless of its condition.
• the glass ceramic mass can be present as a ceramic green body.
• a powder of the oxide ceramic and a powder of the glass material can be produced using a organic binder.
• the glass ceramic mass is present as a powder mixture of the oxide ceramic and the glass material.
• the glass ceramic mass can be present as a sintered ceramic body.
• a ceramic multilayer body produced in a sintering process consists of the glass ceramic mass. This ceramic multilayer body can be fed to a further sintering process or firing process at a higher firing temperature.
• the oxide ceramic can be present as a single phase. But it can also consist of several phases. It is conceivable, for example, that the oxide ceramic consists of phases with a different composition in each case. The oxide ceramic is therefore a mixture of different ones
• Oxide ceramics It is also conceivable that one or more starting compounds of an oxide ceramic are present, which are only converted to the actual oxide ceramic during sintering.
• the glass material can also be a single phase.
• the phase is a glass melt made of boron trioxide, titanium dioxide and lanthanum trioxide. It is also conceivable that the glass material consists of several phases. For example, the glass material consists of a
• a common glass melt forms from the oxides during sintering.
• a softening temperature of the glass material is preferably below 800 ° C. in order to enable the viscous flow to be carried out at the lowest possible temperature.
• the glass material has a crystalline phase.
• the crystalline phase is formed, for example, by a crystallization product of the glass melt. This means that the glass material after sintering is not only in the glass phase, but also in crystalline form.
• Such a crystallization product is, for example, lanthanum borate (LaB0 3 ).
• the Crystallization product or another crystalline component is added to the glass material before sintering.
• the crystallization product and the crystalline constituent can serve as crystallization nuclei.
• the composition of the glass ceramic mass is preferably chosen so that the compression takes place primarily by viscous flow.
• the viscous flow causes compaction at a relatively low temperature.
• a viscosity-temperature characteristic that is decisive for the compression process which is expressed, for example, in the glass transition point Tg and in the softening temperature T SO ft of the glass material, can be set, for example, by a ratio of the boron trioxide to the oxide of the tetravalent metal Me4 + or to the oxide of the pentavalent metal Me5 + ,
• the dielectric material properties of the glass ceramic mass can be varied almost independently of the compression temperature.
• the oxide of the rare earth metal it is possible to match the dielectric material properties of the glass material to the dielectric material properties of the oxide ceramic.
• the higher the proportion of lanthanum trioxide in the glass material the higher the permittivity of the glass material.
• the composition of the oxide ceramic and that of the glass material is selected such that crystallization products are formed during the compression (for example by reactive liquid phase sintering) and in particular after the compression (at higher temperatures). This
• the oxide ceramic has a formal composition BaRek 2 Ti0 ⁇ .
• the rare earth metal Rek is, for example, lanthanum.
• the oxide ceramic of this composition is particularly suitable as a microwave ceramic.
• the Tkf value of the oxide ceramic is in the range between - 20 ppm / K and + 200 ppm / K.
• a suitable composition and combination of oxide ceramics and glass material makes it possible to achieve a low absolute Tkf value.
• Tkf value of an underlying glass ceramic mass is negative, countermeasures are taken, for example, with BaLa 2 Ti 4 0 ⁇ 2 , titanium dioxide and / or strontium titanate (SrTi0 3 ) in the direction + 0 ppm / K of the glass ceramic mass. If, on the other hand, the Tkf value of the underlying glass ceramic mass is positive, the Tkf value can be compensated, for example, with BaSm 2 Ti0 ⁇ 2 , aluminum oxide and lanthanum borate (LaB0 3 ).
• the additional oxides, with the aid of which countermeasures are taken, can be added to the glass ceramic mass before sintering. However, these oxides can also be crystallization products mentioned above.
• the rare earth metal Reg is present, for example, as trioxide Reg 2 0 3 .
• the permittivity of the glass material which contributes to the permittivity of the entire glass ceramic mass, can be adapted to the permittivity of the oxide ceramic. This makes a glass ceramic mass accessible that has a permittivity of 15 to 80 or even higher.
• the rare earth metal Rek and / or the rare earth metal Reg are selected from the group consisting of lanthanum and / or neodymium and / or samarium. Other lanthanides or actinides are also conceivable.
• the rare earth metals Rek and Reg can be identical, but they can also be different rare earth metals.
• the tetravalent metal is Me4 ' + from the group silicon and / or germanium and / or tin and / or titanium and / or zirconium and / or hafnium selected.
• the oxides of the sub-group elements titanium, zirconium and hafnium themselves influence the dielectric material properties of the glass ceramic mass. In particular, these oxides influence the formation of the
• the oxides of the main group elements silicon, germanium and tin primarily support a glassiness of the glass material. With the help of these oxides, the viscosity-temperature characteristics of the glass material are controlled.
• the pentavalent metal Me5 + is selected from the group bismuth and / or vanadium and / or niobium and / or tantalum.
• the oxides of the sub-group elements vanadium, niobium and tantalum apply
• niobium pentoxide Nb 2 Os or tantalum pentoxide Ta 2 Os directly influence the dielectric material properties.
• these oxides influence the formation of the crystallization products and thus indirectly the material properties.
• Main group element primarily supports the glassiness of the glass material.
• the glass material has at least one oxide with at least one further metal Mex, which is selected from the group aluminum and / or magnesium and / or calcium and / or strontium and / or barium and / or copper and / or zinc ,
• the other metal Mex can exist as its own oxidic phase.
• the oxides aluminum trioxide (Al 2 0 3 ), magnesium oxide (MgO),
• Calcium oxide (CaO), strontium oxide (SrO) and barium oxide (BaO) can stabilize the glassiness of the glass material.
• the oxide ceramic has, in addition to barium as a divalent metal, a doping of at least one further divalent metal Me2 +.
• the further divalent metal Me2 + is from the group Copper and / or zinc selected.
• the oxide ceramic of the composition BaRek 2 Ti 4 0 ⁇ 2 is doped with zinc.
• the divalent metal Me2 + controls the dielectric material properties of the oxide ceramic.
• the oxide ceramic can partially dissolve in the glass melt of the glass material with subsequent crystallization. It has been shown that it is particularly favorable if the glass material or an oxide of the glass material is doped with the divalent metal Me2 +, which also occurs in the oxide ceramic. This also applies to other crystalline additives in the glass material.
• An oxide of an alkaline earth metal as a divalent metal Me2 + increases the basicity of the glass material and thus the reactivity of the glass material with a basic oxide ceramic.
• the composition of the oxide ceramic is thus largely retained during the compression. It has been shown that it is particularly advantageous if the oxide ceramic is doped with a divalent metal Me2 +, which also occurs in the glass material. Zinc is particularly worth mentioning as the divalent metal Me2 +.
• 100 vol% of the glass ceramic mass is composed of a ceramic portion of the oxide ceramic, which is selected from the range between 20 vol% up to and including 60 vol%, and a glass portion of the glass material, which is selected from the range between 80 vol% up to and including 40 vol%.
• the ceramic portion is selected from the range between 30 vol% to 50 vol% inclusive and the glass portion from the range between 70 vol% to 50 vol% inclusive.
• densification takes place primarily through viscous flow.
• the oxide ceramic and / or the glass material have a powder with an average particle size (D 50 value), which is selected from the range between 0.8 ⁇ m and 3.0 ⁇ m inclusive.
• the average particle size is also referred to as the half-value particle size.
• the oxide ceramic and the glass material are each in the form of such a powder.
• the average particle size is in particular between 1.5 ⁇ m and 2.0 ⁇ m. It has been shown that with a particle size from the range mentioned, a possible reactive removal of individual components of the oxide ceramic or crystalline additives of the glass material can be controlled well.
• the particle size is advantageously not more than 3 ⁇ m, so that the glass ceramic mass can be sealing-sintered.
• a lead oxide content and / or a cadmium oxide content in the glass ceramic mass and / or the oxide ceramic and / or the glass material is at most 0.1%, in particular at most 1 pp. It is preferably off
• the glass ceramic mass has a sealing firing temperature of at most 850 ° C. and in particular of at most 800 ° C.
• a glass ceramic mass is accessible with a permittivity selected from the range from 20 to 80 inclusive, a quality selected from the range from 300 to 5000 inclusive, and a Tkf value from the range from including - 20 ppm / K up to and including + 20 ppm / K is selected.
• the glass ceramic mass is ideally suited for use in microwave technology.
• a ceramic body with a previously described glass ceramic mass is specified.
• the ceramic body has at least one elemental metal MeO, which is selected from the group gold and / or silver and / or copper.
• the ceramic body is preferably a ceramic multilayer body.
• the glass ceramic mass described above is used to produce the ceramic body.
• Multi-layer body can be produced.
• the glass ceramic mass is used in particular in ceramic green foils using LTCC technology. This means that LTCC technology is provided with glass ceramic materials with excellent material properties for the production of microwave technology components.
• the glass ceramic mass sintering at low temperature can be used to suppress the lateral shrinkage when producing a ceramic multilayer body.
• the invention has the following advantages:
• composition of the glass ceramic mass with oxide ceramic and glass material is selected so that the compression is predominantly carried out by viscous flow and crystallization products are formed during and / or after the compression.
• the composition of the oxide ceramic remains essentially constant during the sintering of the glass ceramic mass.
• the material properties of the glass ceramic mass can thus be preset very easily.
• the invention is described below using an exemplary embodiment and the associated figure.
• the figure shows a schematic cross section, not to scale, of a ceramic body with the glass ceramic mass in a multilayer construction.
• the glass ceramic mass 11 is a powder made of an oxide ceramic and a powder of one
• the oxide ceramic has the formal composition Ba ek2 i4 ⁇ i2 ⁇
• the rare earth metal Rek is neodymium.
• the oxide ceramic has a divalent metal Me2 + in the form of zinc as doping.
• appropriate amounts of barium oxide, titanium dioxide and neodymium trioxide are mixed with about 1% by weight of zinc oxide, calcined or sintered and then ground to the corresponding powder.
• the glass material has the following composition: 35.0% mol% boron trioxide, 23.0 mol% lanthanum trioxide and 42 mol% titanium dioxide.
• the glass material Alkaline earth metal oxides zirconium dioxide mixed in with less than 5% by weight, a ratio between boron trioxide and the sum of the oxides of the tetravalent metals titanium and zirconium being approximately 0.75.
• 100 vol% of the glass ceramic mass is composed of 35 vol% of the ceramic material and 65 vol% of the glass material. Ceramic material and glass material have a D 50 value of 1.0 ⁇ m.
• the sealing firing temperature of the glass ceramic mass is 760 ° C.
• the glass ceramic mass compresses.
• the crystallization product titanium dioxide forms, which serves as one for adjusting the Tkf value
• Component acts. Crystalline titanium dioxide is obtained with 15% by weight.
• a firing process which leads to the specified values, consists in a first heating phase with a heating rate of 2 K / min to a temperature of 500 ° C, a first holding time of the temperature of 30 min, a second heating phase with a heating rate of 10 K / min, a second holding time of 5 K / min and a cooling phase of 5 K / min to room temperature.
• the presented glass ceramic mass 11 is used in order to use the LTCC technology in the volume of a ceramic multilayer body 1 to form a passive electrical component 6, 7 to integrate.
• the passive electrical component 6, 7 consists of the elemental metal MeO silver.
• the ceramic layers 3 and 4 of the ceramic multilayer body 1 are formed from the ceramic green foils with the glass ceramic mass 11 by sintering.
• the ceramic layers 2 and 5 result from the Heratape® green foils.
• the glass ceramic mass has a permittivity of 30, a quality of over 1000 and a Tkf value of + 8 ppm / K.
• a permittivity of 28 a quality of over 1000 and a Tkf value of + 142 are obtained.

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• 2000
  • 2000-09-01 DE DE10043194A patent/DE10043194A1/de not_active Withdrawn
• 2001
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