JP2009533310A - Glass ceramic seals for use in solid oxide fuel cells - Google Patents

Abstract

The present invention relates to high crystalline frit sintered glass ceramic materials and seals made therewith suitable for solid oxide fuel cell applications. This seal is in the range of 70 to 130 × 10 ^-7 / ° C., and preferably has a thermal expansion coefficient in the range of 85~115 × 10 ^-7 / ℃. The glass ceramic material has a crystalline component and a glass component, the crystalline component being greater than 50% of the glass ceramic and the glass component being less than 50%. In certain preferred embodiments, the crystalline component is greater than 75%. In terms of the crystalline component alone, more than 50% of the crystalline component of the glass ceramic is composed of Walstromite, cyclowollastonite, μ- (Ca, Sr) SiO ₃ , calcilite, caryophyllite and wollast. It has a structure selected from a structure group represented by knight (main crystal phase), and the remaining less than 50% of the crystalline component contains at least one sub-crystal phase. In general, the glass ceramics of the present invention are useful as metal-to-metal, metal-to-ceramic and ceramic-to-ceramic sealants.

Description

Explanation of related applications

  This application claims priority to copending application US patent application Ser. No. 11 / 40,2761, filed Apr. 11, 2006, entitled “HIGH THERMAL EXPANSION CYCLOSILICATE GLASS-CERAMICS”. Co-pending US patent application Ser. No. 11 / 40,2761 and this application include a co-pending US patent application entitled “Glass Ceramic Seals For Use In Solid Oxide Fuel Cells” filed Oct. 11, 2006. Along with 11/546237, there is a common co-inventor, Linda R. Pinckney, which is co-assigned to Corning Incorporated.

  The present invention relates to highly crystallized frit sintered glass ceramics in which the main crystalline phase has a selected crystal structure as shown here, in particular the glass ceramic material described herein as a sealant. The present invention relates to a seal for a solid oxide fuel cell (“SOFC”) manufactured using the same. In addition to SOFC applications, this material can be used as a sealant for metal-to-metal, metal-to-ceramic and ceramic-to-ceramic seals.

  A glass ceramic is a polycrystalline material formed by controlled crystallization of a precursor glass article. The glass ceramic is prepared by subjecting a glass monolith to a heat treatment for conversion to a crystalline state. This is referred to as a “bulk” or “monolith glass ceramic formation process”. In Stookey, US Pat. No. 6,057,049 describes a monolithic glass ceramic forming technique. In general, a raw material usually containing a nucleating agent is melted and cooled at the same time to form a glass monolith of a desired shape. Thereafter, the glass monolith is subjected to a crystallization heat treatment referred to in the art as “ceramicization”. Appropriate heat treatment typically involves holding at a low temperature about the transformation range to induce nucleation, followed by one or more temperatures above the softening point of the glass to promote crystal growth. Retention is performed. In the monolith formation process, nucleation occurs internally. The production of glass ceramics by a bulk forming process is comparable to the high speed automated manufacturing process used to form and manufacture glass articles. Moreover, one advantage of internal nucleation is that it can provide a wide range of polycrystalline microstructures. As a result, the properties of the final glass ceramic material can be changed by adjusting the temperature treatment form.

  Glass ceramics are also prepared by firing a glass frit called a powder processing method. The glass is ground into a powder state (frit) and then fired and crystallized into a glass ceramic state. In this process, the surface of the glass particles serves as a nucleation site for the crystalline phase. The glass composition, particle size, and processing conditions are selected such that the glass softens before crystallization and undergoes viscous sintering to maximum density just before the crystallization process is complete. Shape-forming methods may include, but are not limited to, extrusion, casting, tape casting, spray drying, and isostatic pressing.

  Glass ceramic materials have properties that make them suitable for many other applications. A recent and increasingly important use of glass-ceramic materials is as a sealant for solid oxide fuel cells (“SOFC”). The SOFC is basically an energy reactor system in which chemical energy is converted into electrical energy. SOFCs are similar to storage batteries, but differ in that they do not run out as the storage battery runs out. This is because the fuel is continuously supplied to the SOFC, and therefore electricity can be supplied continuously. Therefore, the SOFC is limited only by the amount of fuel that can be supplied in the same way as any ordinary power generator. While SOFCs operate at high temperatures in the range of 600-1000 ° C., current research seeks to lower this temperature range and use ceramic materials for the functional elements of fuel cells.

As a general description, an SOFC consists of a negative electrode and a positive electrode separated by a solid impermeable electrolyte that conducts oxygen ions from the positive electrode to the negative electrode, where they chemically react with the fuel. The charge induced by the passage of ions through the electrolyte is collected and conducted from the fuel cell to the source of use. Each cell produces only a limited voltage, but many cells can be configured in series to increase the voltage to a useful output level. Small SOFC units of 5-10 kW are commercially available from various companies, and large units of 25-125 kW are being developed and tested around the world.
US Patent No. 2900971

When designing an SOFC, keep fuel (H ₂ , CH ₄ , C ₂ H ₈ , CO, etc.) and air (O ₂ ) flows separately and maintain thermal equilibrium so that the operating temperature of the unit remains within an acceptable range. It is important to maintain. Ceramic materials have been widely used in SOFC designs to ensure both. However, in order to produce a unit that produces a usable amount of output, it is necessary to place a large number of single cells in series, so that not only the operating components for the single cells are kept separate (no leakage), There must be no leakage from cell-to-cell in series cells. Various materials have been used as sealants, such as, among others, epoxies and cements, but improvements in this area are needed.

  The present invention discloses a glass ceramic material that can be used as a sealing material.

  The present invention relates to novel compositions suitable for forming seals for solid oxide fuel cells and glass-ceramic sealants for such applications.

In one aspect, the present invention relates to a boron-free glass ceramic seal for a solid oxide fuel cell comprising a glass ceramic having less than 50% glass component and greater than 50% crystalline component. With respect to the crystalline component alone, more than 50% by weight of the crystals in the crystalline component of the glass ceramic are walstromite, cyclowollastonite and μ- (Ca, Sr) SiO ₃ (cyclosilicate material), and the tip Having a structure selected from the group of structures represented by a mixture (main crystalline phase) of In addition to the crystalline phase described above, one or more crystalline phases (less than 50%) can be present in the ceramic portion of the glass ceramic, and such crystalline phase is the remainder of the ceramic (crystalline) portion of the glass ceramic. (Sub-crystal phase) is formed. Examples of such additional crystalline phases include, but are not limited to, crystals having a structure represented by wollastonite, dolomite, dolomite, and bituminous meteorite, or mixtures thereof. It is done. These glass-ceramic CTE (25 ℃ ~800 ℃) is in the range of 70 to 130 × 10 ^-7 / ° C., preferably in the range of 85~115 × 10 ^-7 / ℃.

In one aspect, the present invention relates to a highly crystalline, boron-free glass ceramic seal that can be used in a solid oxide fuel cell having a crystal component greater than 75% and a glass component less than 25%. In preferred embodiments, the crystalline component is greater than 90% and the glass component is less than 10%. CTE of these glass-ceramics, the range of 70~130 × 10 ^-7 / ℃, preferably in the range of 85~115 × 10 ^-7 / ℃.

Another aspect of the present invention is a boron-free glass-ceramic seal, wherein the glass-ceramic contains SiO ₂ , Al ₂ O ₃ , and at least one MO component, where MO is Mg, Ca, Alkaline earth oxides of Ba and Sr, more than 50% of the crystalline components of the glass ceramic are composed of walstromite, cyclowollastonite and μ- (Ca, Sr) SiO ₃ (cyclosilicic acid). Salt material) as well as a glass ceramic seal having a structure selected from the group of structures represented by a mixture of the foregoing (main crystalline phase). In addition, the glass-ceramic seals described above may contain ZnO, Nb ₂ O ₅ , Ta ₂ O ₅ , La ₂ O ₃ , Y ₂ O ₃ , Sb ₂ O ₃ , and transition metal and rare earth oxides as required. A small amount of other oxides may be contained. Furthermore, there may be one or more additional crystalline phases in the ceramic portion of the glass ceramic, such crystalline phases constituting the remainder of the ceramic portion of the glass ceramic. Examples of such additional crystalline phases include, but are not limited to, crystals having a structure represented by wollastonite, dolomite, dolomite, and bituminous meteorite, or mixtures thereof. It is done. The CTE (25 ° C. to 800 ° C.) of these glass ceramics is in the range of 85 to 115 × 10 ⁻⁷ / ° C.

In another aspect, the present invention is, SiO ₂ of 30 to 50 wt%, 2-8 wt% of Al ₂ O _3, 10 to 40 wt% of CaO, and at least one 0-40 wt% of SrO, A boron-free glass-ceramic seal having a composition containing 0 to 35% by weight of BaO and 0 to 10% by weight of MgO, wherein the total of alkaline earth oxides (Σ _MO , where M is Mg, Ca , Ba and Sr) are in the range of 40 to 60% by mass. If necessary, said Nb ₂ O ₅ up to ZnO, 10 wt% to 8 _{wt%, Ta 2 O 5, La} 2 O 3, Y 2 O 3 or Sb ₂ O _3, (or mixtures thereof) It may be included in the composition. The CTE of these glass ceramics is in the range of 85 to 115 × 10 ⁻⁷ / ° C. Expressed for ranges when optional oxides are included in the composition, the amount of oxide selected is> 0-8 wt% for ZnO, Nb ₂ O ₅ , Ta ₂ O ₅ , for _{la 2 O 3, Y 2 O} 3, Sb 2 O 3 is> 0 to 10%.

In another aspect, the present invention is a boron-free and zinc-free glass-ceramic seal having a crystalline component greater than 50% and a glass component less than 50%, wherein only 50% of the glass ceramic is crystalline with respect to the crystalline component. It relates to a glass-ceramic seal in which the crystalline component in excess of% is a crystalline phase (main crystalline phase) selected from the group consisting of potassium aluminosilicates calcilite and caryophyllite, and wollastonite. In addition to the crystalline phases described above, there can be one or more additional crystalline phases such as gehlenite, anorthite, kirkoanite, and corundum, and such crystalline phase is the remainder of the crystalline component of the glass ceramic ( Sub-crystalline phase). CTE of these glass-ceramics, the range of 70~130 × 10 ^-7 / ℃, preferably in the range of 85~115 × 10 ^-7 / ℃. In certain embodiments, the glass-ceramic seal boron-free and zinc-free is 5 to 25 wt% of Al ₂ O _3, 25 to 45 wt% of CaO, SiO ₂ of 25 to 45 wt%, 1 to 10 mass% Of K ₂ O and 0 to 25% by weight of GeO ₂ . In another embodiment, the glass-ceramic seal-free boron-free and zinc, 10 to 20 wt% of Al ₂ O _3, 30 to 40 wt% of CaO, 30 to 40 wt% of SiO _2, 2 to 8 mass having a% of K ₂ O and the composition of GeO ₂ 5 to 20 wt%.

Selection of (a) boron-free and zinc-free glass ceramic, (b) boron-free glass ceramic, and (c) boron-free glass ceramic containing SiO ₂ , Al ₂ O ₃ and at least one MO component In a given embodiment, the main crystalline phase of the crystalline component is greater than 75% of the crystalline component and the subcrystalline phase, if present, is less than 25%. In yet another embodiment, the main crystalline phase of the crystalline component is greater than 90% of the crystalline component and the subcrystalline phase, if present, is less than 10%.

  As used herein, all compositions containing the specified crystalline component or phase and percentage of glass component are expressed in bulk percent by mass (% by weight). For clarity, the term “glass ceramic” as understood in the art means that the material has a glass phase or component and a crystalline phase or component that is homogeneously dispersed throughout the glass. It should be understood that the compositions of the present invention may contain minor components, where trace means less than 0.4% by weight, preferably less than 0.1% by weight.

As understood herein by way of example, “greater than 50% of the crystalline component of the glass ceramic is selected from the group represented by Walstromite, cyclowollastonite and μ- (Ca, Sr) SiO ₃ Reference to “having a structure as defined” relates to the structure rather than the chemical formula of the crystalline material represented by the “name” of Walstromite, cyclowollastonite and μ- (Ca, Sr) SiO ₃ . For example, the traditional (end-component) chemical formulas of wolstromite and cyclowollastonite are Ca ₂ BaSi ₃ O ₉ and α-CaSiO ₃ , respectively. The sealing materials described herein may contain additional components in the structure in solid solution (see Examples 1-7 in Table 1), but more than 50% of the crystals in the crystalline phase are It has the structure of walstromite and cyclowollastonite and may contain such additional ingredients. The remainder of the crystals (ie, less than 50%) in the crystalline component constitutes a subcrystalline phase if such a phase is present. The traditional (edge) chemical formulas for the various structures listed here are: Walstromite [Ca ₂ BaSi ₃ O ₉ ], cyclowollastonite [α-CaSiO ₃ ], wollastonite [β-CaSiO ₃ ], Dolomite [CaMgSi ₂ O ₆ ], ochermanite [Ca ₂ MgSi ₂ O ₇ ], Herstone stone [Ca ₂ MgSi ₂ O ₇ ], dolomite [MgSiO ₃ ], and dolomite [Mg ₂ SiO] ₄ ], gehlenite [Ca ₂ Al ₂ SiO ₇ ], anorthite [Ca ₂ Al ₂ Si ₂ O ₈ ], kircoanite [Ca ₆ (SiO ₄ ) (Si ₃ O ₁₀ )], and corundum [Al ₂ O ₃ ].

  The present invention relates to a boron-free glass ceramic seal for a solid oxide fuel cell comprising a glass ceramic having a glass component and a crystalline component. In some embodiments, the crystalline component of the glass ceramic is greater than 50% by weight and the glass component is less than 50%. In another embodiment, the crystalline component of the glass ceramic is greater than 75% by weight and the glass component is less than 25%. In another embodiment, the crystalline component of the glass ceramic is greater than 90% by weight and the glass component is less than 10%. In yet another embodiment, the present invention is a boron-free and zinc-free glass-ceramic seal for a solid oxide fuel cell, comprising a glass-ceramic having a glass component and a crystalline component, wherein the glass or ceramic The percentage of each component relates to the seal as described above in this paragraph in the embodiment of the boron-free glass-ceramic seal.

With respect to only the crystalline component of the glass ceramic, the crystalline component of 50% by mass or more, sometimes referred to as the main crystalline phase, is composed of the above-mentioned crystal structure of walstromite, cyclowollastonite and μ- (Ca, Sr). It has a structure selected from the group consisting of SiO ₃ and solid solutions and mixtures thereof, or a group consisting of potassium aluminosilicate calcilite and caryophyllite [KAlSiO ₄ ], wollastonite, and mixtures thereof. In addition to the main crystalline phase described above, there may also be one or more additional or subcrystalline phases (less than the remaining 50% of the crystalline component) in the crystalline component of the glass ceramic, It constitutes the remainder of the crystalline component of the glass ceramic. Examples of such sub-crystalline phases include, but are not limited to, ochermanite, Herstone stone, wollastonite, peridotite, dolomite, and dolomite meteorite. For example, when the main crystalline phase in the crystalline component is 75% cyclowollastonite, the remaining subcrystalline phase is ochermanite in the presence of magnesium, or Herstone stone in the presence of zinc. It may be. One skilled in the art will appreciate that the exact nature and amount of the subcrystalline phase depends on the composition of the glass.

  The seal is an integral part of the solid oxide fuel cell (SOFC) flat plate design. The seal avoids fuel and air mixing and prevents fuel from leaking from the stack or individual cells. The requirements for the seal (and hence the sealant or material used to form it) are severe. For example, the seal must be able to withstand exposure to high temperatures up to 1000 ° C. and exposure to both oxidizing and reducing environments. In addition, the seal must have a low vapor pressure and must maintain hermeticity and insulation over the life of the stack, which can exceed 50,000 hours. Furthermore, the seal must not degrade due to thermal cycling of the stack or due to changes in viscosity and chemical composition over time. These latter changes can result from certain types of volatility and from reactions with other cell components such as electrodes and stainless steel interconnectors. Finally, the seal itself should not be a source of contaminants that adversely affect the operation of other stack components, particularly the cell electrodes.

  The most commonly used sealants are cement, glass, and glass ceramic. Cement seals usually do not form hermetic seals and glass seals can provide the required hermeticity, but the upper temperature at which they can be used is generally limited. By using glass ceramic as a sealant, most if not all of these problems can be avoided.

  Powder processed (frit sintered) glass-ceramics are well known as metal-to-metal, metal-to-ceramic, and ceramic-to-ceramic sealing materials, and high performance coatings for metals and ceramics. Compared to glass, glass-ceramics provide high service temperatures, excellent mechanical and corrosion resistance, and a very wide range of coefficients of thermal expansion (CTE), because of these properties, for many different alloys Glass ceramic can be used as an expansion compatible seal. Glass ceramic materials are particularly suitable for applications where high-strength systems are important due to the ability to fill concave angles and complex internal shapes with the viscous flow of the crystallizing molten glass forming the glass ceramic.

  Nevertheless, more glass-ceramic seals, especially glass-ceramic seals containing significant glassy constituents and / or easily diffusing cations such as small alkali ions, can cause excessive reaction with SOFC components. Susceptible and subsequent degradation of the device may occur over time. In certain embodiments, the present invention relates to highly crystalline glass-ceramic seals that are particularly well suited for SOFC applications and have a residual glass of less than 25% (ratio of crystalline component to glass component of> 75 / <25). . In another embodiment, the present invention relates to a highly crystalline glass-ceramic seal that is particularly well suited for SOFC applications, with a residual glass of less than 20% (> 80 / <20 ratio of crystalline component to glass component). . In yet another embodiment, the present invention relates to a highly crystalline glass-ceramic seal having less than 10% residual glass (> 90 / <10 ratio of crystalline component to glass component). The overall glass-ceramic seal has a thermal expansion that closely matches the thermal expansion of the fuel cell electrolyte and interconnector, and the vitreous component remaining in the final microstructure is bounded by gaps and some particle boundaries. The continuous path is not formed by the seal.

Advantages of the highly crystalline glass-ceramic sealing material of the present invention include:
The sealing material provides a path to a low stress hermetic seal due to the advantageous sintering characteristics of the temporary glass phase.
• Nearly zero porosity and discontinuous glass phase: any residual glass occupies gaps and does not form a continuous path over most of the material. This minimizes cation migration through the glass phase at high temperatures, thereby inhibiting any continuous reaction between the substrate and the frit.
• Residual glass is minimal so that no softening or permanent dimensional changes of the glass-ceramic seal occur during thermal cycling.
• The seal is mechanically and thermally stable.
The thermal expansion of the crystallization seal is compatible with the thermal expansion of the SOFC component.

The requirement for highly crystalline glass ceramic SOFC seals is that they have an almost stoichiometric composition that undergoes almost complete crystallization and thus provides the high thermal expansion required for SOFC applications. As a glass ceramic that satisfies these criteria, the crystal in the crystal phase has a structure selected from the structure represented by the structure of Walstromite, cyclowollastonite and μ- (Ca, Sr) SiO ₃ , Glass ceramics whose subcrystalline phase structure is based on structures including, but not limited to, the structures of wollastonite, dolomite, ochermanite, hergestone, dolomite, and dolomite Is mentioned.

In another aspect of the present invention, the crystalline component of the glass ceramic in excess of 50% by mass is selected from the group consisting of potassium aluminosilicate calcilite and caryophyllite, and the subcrystalline phase is not limited to the following: , Wollastonite, gelenite, anorthite, kirkoanite and corundum. CTE of these glass-ceramics, the range of 70~130 × 10 ^-7 / ℃, preferably in the range of 85~115 × 10 ^-7 / ℃.

Tables 1 and 2 below illustrate some of the compositions expressed in weight percent that can be used as seals for SOFC applications. Seals made from the glass ceramic materials illustrated in Table 1 contain SiO ₂ , Al ₂ O ₃ and MO, where MO is an alkaline earth oxide of Mg, Ca, Ba and Sr. is there. The main (> 50%) crystalline phase of the glass ceramic exemplified in Table 1 is at least one of Walstromite, cyclowollastonite and μ- (Ca, Sr) SiO ₃ , and minor (<50%) ) The crystalline phase is wollastonite, dolomite, ochermanite, dolomite, dolomite, and Herstone stone, and solid solutions or mixtures thereof.

The composition of the glass-ceramic material useful as SOFC illustrated in Table 1 contains SiO ₂ , Al ₂ O ₃ and MO, where MO is an alkaline earth oxide of Mg, Ca, Ba and Sr And when M is two or more of Mg, Ca, Ba and Sr, the total of the alkaline earth oxides (ΣMO) is in the range of 40 to 60% by mass, and Al ₂ O ₃ is 2 to 2. In the range of 4% by mass, SiO ₂ is in the range of 36-58% by mass.

Boron-free and zinc-free seals made from the glass ceramic materials exemplified in Table 2 contain SiO ₂ , Al ₂ O ₃ and CaO, and R ₂ O, where R is an alkali ion, preferably Potassium (K). The crystalline component of the glass ceramic exemplified in Table 2 has a main crystal phase whose structure is selected from the group consisting of caryophyllite and calcilite structures, and is not limited to the following. It may have a subcrystalline phase including knight, gehlenite, and corundum. The boron-free and zinc-free glass-ceramic seals of Table 2 are 5-25% by weight Al ₂ O ₃ , 25-45% by weight CaO, 25-45% by weight SiO ₂ , 1-10% by weight K _2. having O and composition range of GeO ₂ 0 to 25 wt%. In a preferred embodiment, the boron-free and the composition range of the glass-ceramic seal-free zinc, 10 to 20 wt% of Al ₂ O _3, 30-40 wt% of CaO, SiO ₂ of 30 to 40 wt%, 2 ˜8 mass% K ₂ O and 5-20 mass% GeO ₂ .

  The glass composition used to prepare the glass ceramic according to the present invention melts the component materials in a container, such as a platinum crucible, at a temperature in the range of 1450-1650 ° C. for a period in the range of 2-5 hours. It was prepared by. The starting material may be in the form of oxides, carbonates, nitrates, hydroxides and other forms of metals described herein that are known in the art to be useful for the preparation of glasses. In one embodiment, melting was performed at a temperature of 1600 ± 50 ° C. for a period ranging from 2.5 to 4 hours. For each composition, a small ˜5 cm piece was molded from the molten glass composition and annealed at a temperature of 750 ± 40 ° C. These samples served as visual indicators of overall glass stability. The remaining glass in each crucible was poured into water and granulated, and crushed to an average particle size in the range of 10 to 20 μm (325 mesh). The resulting frit (frit = powder glass) powder was formed into articles (pellets, rods, rods, etc.) using techniques known in the art. For example, for the test purposes described herein, the frit may be 0.5 inch diameter pellets and / or 10 × 0.6 × 0.6 cm (4 × 0.25 × 0.25). Inch) CTE bars and then fired (sintered) at temperatures ranging from 850 ° C. to 1000 ° C. for periods ranging from 1 to 2 hours.

Glass-ceramic composition of the present invention is in the range of 70 to 130 × 10 ^-7 / ° C., and preferably has a thermal expansion coefficient in the range of 85~115 × 10 ^-7 / ℃. For use as a SOFC seal, in certain preferred embodiments, the highly crystallized glass ceramic seal has a crystal phase of greater than 75 wt% and a glass phase of less than 25 wt%. In yet another embodiment, the crystalline phase is greater than 90% by weight and the glass phase is less than 10% by weight.

  Phase and structural information regarding the crystalline forms described herein can be obtained from Phase Diagrams for Ceramists and other literature known to those skilled in the art. For example, XRD information can be found in the JCPDS database and can be used to identify the crystalline morphology present in the glass ceramic.

  Although the invention has been described with respect to a limited number of embodiments, those skilled in the art having the benefit of this disclosure may devise other embodiments that do not depart from the scope of the invention disclosed herein. It will be understood. Accordingly, the scope of the invention should be limited only by the attached claims.

Claims (13)

A glass ceramic seal comprising a glass ceramic having a glass component and a crystalline component,
The glass ceramic does not contain boron,
The crystalline component of the glass ceramic is greater than 50% of the glass ceramic seal and the glass component is less than 50%;
Speaking only of the crystalline component, more than 50% by mass of the crystalline component is composed of a main crystalline phase, where the crystals of the main crystalline phase are composed of walstromite, cyclowollastonite, μ- (Ca , Sr) SiO _3, having a structure selected from structures represented Karushiraito by the group consisting of potash office light and wollastonite,
The remaining less than 50% of the crystalline component comprises at least one subcrystalline phase;
A glass-ceramic seal, wherein the glass-ceramic has a CTE in the range of 70 to 130 × 10 ⁻⁷ / ° C. The glass ceramic is expressed in terms of mass percent, 30-50 mass% SiO ₂ , 2-8 mass% Al ₂ O ₃ , 10-40 mass% CaO, and at least one kind of 0-40 mass%. 2. SrO, 0 to 35% by mass of BaO or 0 to 10% by mass of MgO, wherein the total of alkaline earth metal oxides (ΣMO) is in the range of 40 to 60% by mass. Glass ceramic seal. The glass ceramic is> 0-8 wt% ZnO,> 0-10 wt% Nb ₂ O ₅ , Ta ₂ O ₅ , La ₂ O ₃ , Y ₂ O ₃ , or Sb ₂ O ₃ , or their The glass-ceramic seal according to claim 2, comprising a mixture.   4. The glass-ceramic seal according to claim 3, comprising zinc oxide in an amount in the range of> 0 to 6% by weight.   The crystalline component of the glass ceramic is more than 75% by mass, the glass component is less than 25% by mass, and the main crystalline phase is more than 75% by mass of the crystalline component. Glass ceramic seal.   2. The glass ceramic seal according to claim 1, wherein the crystalline component of the glass ceramic is more than 90% by mass and the glass component is less than 10% by mass. The glass-ceramic seal according to claim 1, wherein the glass-ceramic has a CTE in the range of 85 to 115 x ^10-7 / ° C. The crystalline component has a main crystalline phase of more than 50%, having a structure selected from the group consisting of wolstromite, cyclowollastonite and μ- (Ca, Sr) SiO ₃ ;
The glass ceramic seal according to claim 1, wherein the remaining less than 50% of the crystalline component contains at least one subcrystalline phase.   The said sub-crystalline phase has a structure selected from the group of structures consisting of wollastonite, dolomite, dolomite, dolomite and their solid solutions or mixtures. Glass ceramic seal. A glass ceramic seal comprising a boron-free and zinc-free glass ceramic having a glass component of less than 50% and a crystalline component of greater than 50%,
Speaking only of the crystalline component, more than 50% by mass of the crystalline component consists of more than 50% of the main crystalline phase, wherein the crystals of the main crystalline phase are calcilite, caryophyllite and wollast Having a structure selected from the structure represented by the group consisting of knights and their solid solutions or mixtures;
The remaining less than 50% of the crystalline component is a group consisting of Okermanite, Hergistone, Corundum, Gehlenite, Anorthite, Wollastonite, Peridotite, Peridotite, and Blastite meteorite, and mixtures thereof Comprising a subcrystalline phase selected from the structure represented by
The glass ceramic has a CTE in the range of 70-130 × 10 ⁻⁷ / ° C .;
5-25 wt% of Al ₂ O _3, 25 to 45 wt% of CaO, SiO ₂ of 25 to 45 wt%, that it contains 1 to 10 wt% of K ₂ O and 0 to 25 wt% of GeO ₂ A boron-free and zinc-free glass-ceramic seal. 10-20 wt% Al ₂ O _3, 30 to 40 wt% CaO, SiO ₂ of 30 to 40 wt%, to include 2-8 wt% K ₂ O and 5-20 wt% of GeO ₂ The glass ceramic seal according to claim 10, wherein 11. A glass ceramic seal according to claim 10, having a CTE in the range of 85-115 × 10 ⁻⁷ / ° C.   The main crystalline phase of the crystalline component is selected from the group consisting of caryophyllite and wollastonite, and the sub-crystalline phase is selected from the group consisting of wollastonite, gehlenite and corundum. 10. The glass ceramic seal according to 10.