Bonded assembly including an insulating member, in particular having at least partially crystallized glass, its use, crystallizable glass and at least partially crystallized glass, and its use

Abstract

To provide a crystallizable glass which has high heat resistance, such as resistance to temperature equal to or higher than 900°C, which wets materials and / or components to be joined when fused, and has a high coefficient of thermal expansion.SOLUTION: The invention provides a crystallizable or at least partially crystallized glass, comprising: La2O3 of more than 0.3 mol% to less than 5 mol%; Nb2O5 of 0 mol% to 9 mol%; Ta2O5 of 0 mol% to 7 mol%; Σ(A2O5) of more than 0.2 mol% to 9 mol %. In the formula, A is an element that, in oxides, has a normal oxidation number V+, and particularly includes Nb, Ta or P, and / or a mixture thereof.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a bonded assembly comprising an insulating member, in particular having at least partially crystallized glass, its uses, crystallizable glass and at least partially crystallized glass, and its uses.

[0002] There are a variety of applications for bonded joints where temperature resistance, mechanical stability, and resistance can all be important.

[0003] When such a mating assembly is part of an exhaust gas system of an internal combustion engine, for example, for transmitting electrical or electronic signals, such as in a motor vehicle in which exhaust gas cleaning is controlled, the ambient conditions frequently change significantly. For example, during cold start operations, particularly in relatively cold regions or when the air humidity is high, such a mating assembly may become covered with a water film from condensed atmospheric components. This condensation may manifest itself as the formation of droplets or even as a coating on the entire surface of the mating assembly. This may undesirably change the electrical resistance between the mating partners, and the corresponding control of the exhaust gas cleaning may be impaired in its control behavior.

[0004] Although highly resistive insulating materials can be used, as will be exemplarily explained in more detail below for crystallizable or at least partially crystallized glasses, they are often not reliable enough in such environments to withstand the above losses so that the control behavior is not impaired.

[0005] Document DE 102008045816 A1 proposes an elastomeric material surrounding the conductor in order to increase the creepage distance, which in the context of the present disclosure is the distance over which creepage currents can occur between the mating partners. The drawback of this solution is that the elastomeric material often does not have the thermal stability and long-term operational durability required for the high-temperature areas of exhaust gas installations.

[0006] One aspect of the present invention addresses better protecting the electrical or electronic properties, particularly the high resistivity properties, of the insulating materials disclosed herein, particularly the crystallizable or partially crystallized glasses disclosed herein, from environmental influences.

[0007] This aspect of the problem to be solved by the present invention is solved by a bonded assembly comprising an electrically insulating member and at least two bonded partners, wherein at least one of the bonded partners 51, 52 is kept electrically insulated from at least the other of the bonded partners 51, 52 by an electrically insulating member 53, and the surface of the electrically insulating member 53 extending between the bonded partners forms a structure S, in particular a bump or depression, which structure S extends, in particular, a direct path along the surface from at least one of the bonded partners to at least the other bonded partner compared to a surface not having this structure S, and the structure preferably completely surrounds at least one of the bonded partners, and the insulating member or structure comprises or consists of a crystallizable glass or an at least partially crystallized glass, as well as by the use of the bonded assembly.

[0008] In the context of the present disclosure, "maintained electrically isolated" refers to a DC resistance of greater than 100 MΩ between bonded partners in a dry atmosphere of a bonded assembly as described herein that is free from deposits that could impair this resistance, and this electrical resistance value is measured at a voltage of less than 100 V.

[0009] The structure S mentioned above can be formed integrally with and of the same material as a portion of the insulating member, which portion extends between and is respectively joined to and preferably glass-fused to the joining partners, preferably the material of the insulating member comprising at least partially crystallized glass and the use thereof.

[0010] In the case of the bonded joints of the present disclosure, the transition area between the surface of the bonded partner and the surface of the at least partially crystallized glass is preferably 1 cm 3 An at least largely amorphous glass layer may be arranged which contains fewer than 10 pores per 1000 sieve and / or has a thickness of preferably 5 μm or less, particularly preferably 2 μm or less, very particularly preferably 1 μm or less.

[0011] In the case of the bonded assembly described herein, the structure S may comprise a crystallizable glass or at least partially crystallized glass, and the surface of the structure S may have at least a predominantly amorphous glass layer, in particular substantially free of open pores, in particular less than 10 pores / cm. 3 It may be formed as a glass layer having a thickness of 5 μm or less, preferably 2 μm or less, very particularly preferably 1 μm or less, including less than 5 μm.

[0012] Also disclosed below are embodiments of bonded assemblies in which the structure S is not made of the same material as the portions of the insulating members to which it extends, each bonded and preferably glass-fused to the bonded assemblies.

[0013] In such a bonded assembly, the structure S is not made of the same material as the portions of the insulating members extending between and preferably glass-fused to the bonded partners, but rather comprises a high-temperature stable ceramic material, such as forsterite, an aluminum oxide-based ceramic, or a zirconium oxide-based ceramic, such as a ceramic containing Y-stabilized zirconium oxide.

[0014] In the case of a joint assembly in which the structure S is not of the same material as the portion of the insulating member to which it extends, connected respectively between the joint partners and preferably glass-fused to them, the structure S may be positioned approximately radially centrally in this portion of the insulating member, preferably at least partially recessed therein.

[0015] In the case of an advantageous bonded assembly in which the structure S includes a reinforcement, the reinforcement includes a metal sheet, a metal foil, or a scrim, mesh or knit that includes a metal, and preferably the metal includes or consists of steel.

[0016] In embodiments of the present disclosure, the structure S may have an edge with a radius of curvature Rv of less than one tenth of a millimeter, preferably less than one twentieth of a millimeter, and greater than 10 μm.

[0017] Using crystallizable or at least partially crystallized glass corresponding to the embodiments described herein, the structure S described herein can enlarge the surface of the insulating material disposed between the joining partners to be separated from each other, thus increasing the creepage distance across the surface of the insulating member.

[0018] The crystallizable or at least partially crystallized glasses according to the embodiments described herein allow for the formation of high-temperature stable and / or mechanically strong bonded joints. As explained above, the crystallizable or at least partially crystallized glasses according to the described embodiments allow for the formation of particularly stable structures in the at least partially crystallized glasses, in particular structures that are mechanically stable even at high temperatures up to 1000° C. or higher.

[0019] A further aspect therefore relates to crystallizable glasses and glasses that exist at least partially crystallized and are used in particular in the field of solder glasses. Solder glasses (also called glass solders or "sealing glasses" in English) are used to create tight bonds between components to be joined. These bonds are also called bonded composites or bonded bonds.

[0020] To produce stable joints that are exposed to very high temperatures during operation, for example temperatures above 900° C., for example even around 1000° C., solder glasses are always required that on the one hand can withstand these high temperatures and, on the other hand, are adapted in terms of their expansion behavior to the materials to be joined, for example high-temperature resistant metals and / or metal alloys or high-temperature resistant non-metallic materials such as yttrium-stabilized ZrO2.

[0021] Furthermore, the bonded assembly must be gas-tight and, particularly when used in electrical components such as sensor technology and / or fuel cells, must have an electrically insulating effect, i.e., have very low electrical conductivity.

[0022] However, commercially available glass solders with high thermal expansion generally have low melting temperatures, limiting their thermal stability and therefore preventing their use at high temperatures. Conversely, glass solders have thermal expansion coefficients in the high temperature range that are much lower than those of their high-temperature-resistant joining partners.

[0023] The prior art has proposed various glass solders for producing bonded joints.

[0024] German patent application DE 10016416 A1 describes a glass-ceramic fusion seal in which the starting glass used consists of 38-48 wt% SiO2, 15-19 wt% Al2IO3, 4.5-11 wt% TiO2, 0-1.5 wt% Na2O, 0-1.5 wt% K2O, and 23-30 wt% CaO, with up to 1.5 wt% Li2O added. These compositions allow for a maximum melting point of 8.8°C in the temperature range of 100°C to 500°C. * 10 -6 A thermal expansion coefficient of 1 / K can be achieved.

[0025] German patent DE 102012206266 describes a barium- and strontium-free glass or glass-ceramic joining material and its use. To ensure sufficient wetting of the components to be joined, the joining material contains B2O3.

[0026] German published patent application DE 10 2014 218 983 A1 describes a feedthrough element for harsh operating conditions, where the joining material again contains B2O3.

[0027] The published patent application DE 102010035251 A1 describes a high-temperature glass solder and its use. This glass solder contains at least 10% by weight of BaO. However, BaO is disadvantageous because barium reacts with Cr contained in high-temperature-resistant steels.

[0028] Published patent application DE 10 2015 207 285 A1 describes a vitreous or at least partially crystallized melt sealing material, which contains at least 5 mol % B2O3.

[0029] DE 102011080352 A1 describes a high-temperature glass solder and its use. The high-temperature glass solder described contains 13% to 50% by weight of Al2O3, with SiO2 only optionally being included in the glass solder.

[0030] U.S. Patent Application Publication No. 2007 / 0238599 describes a highly crystalline sintered glass-ceramic containing cyclosilicate. According to one embodiment, the glass-ceramic of U.S. Patent Application Publication No. 2007 / 0238599 contains, as necessary components, 30% to 55% by weight of SiO, 5% to 40% by weight of CaO, and 0.1% to 10% by weight of AlO, with the total oxides BaO, CaO, and SrO contained in the glass-ceramic being 40% to 65% by weight. In other words, the glass-ceramic of U.S. Patent Application Publication No. 2007 / 0238599 always further contains BaO and / or SrO in addition to CaO.

[0031] U.S. Patent Application Publication No. 2010 / 0129726 describes a lead-free glass having a low B2O3 content, where the content of the oxides SiO2, MgO, CaO, SrO, BaO, ZnO, and Al2O3 in the glass is at least 97 mol%.

[0032] Glass-ceramic compositions for sealing materials are further described in U.S. Patent Application Publication No. 2013 / 0108946. These compositions consist of either SiO, AlO, and CaO, or SiO, AlO, CaO, and SrO, or SiO, AlO, and LaO, as well as other selected additional components.

[0033] Reddy et al., in RSC Advances, 2012, 2, 10955-10967, describe melilite-based glasses and glass-ceramics for functional applications such as sealing materials, where Bi2O3 in particular acts as a crystallizing agent.

[0034] International patent application WO 2017 / 220700 describes a bond made with at least partially crystallized glass and a method for making such a bond, wherein the at least partially crystallized glass has at least one crystalline phase and pores arranged in a structured distribution in the at least partially crystallized glass.

[0035] Finally, the international patent application WO 2018 / 066635 describes a glass composition for joining or bonding, which contains 43 mol% to 53 mol% SiO2, 12 mol% to 33 mol% CaO, 12 mol% to 33 mol% MgO, and 1 mol% to 7 mol% La2O3, and 0 mol% to 4.5 mol% ZnO.

[0036] All of the above-mentioned materials of the prior art have drawbacks.

[0037] For example, the compositions according to German Patent Application Nos. 102012206266, 102014218983, and 102015207285 necessarily contain B2O3. The glasses described in International Patent Application WO 2017 / 220700 also preferably contain B2O3. However, since B2O3 is a material that melts at a relatively low temperature, as already mentioned above, it is often used to sufficiently wet the components to be joined during melting. However, this approach does not allow for high heat resistance of the jointed assembly.

[0038] When the joining material contains BaO and / or SrO, adverse contact reactions occur with high temperature resistant steels, which generally contain Cr.

[0039] When cyclosilicates are produced as a crystalline phase, they are approximately 8 * 10 -6 / K, which is too low a thermal expansion coefficient.

[0040] Furthermore, a high content of nucleating materials, such as TiO2, is undesirable as it can lead to uncontrolled crystallization of the crystallizable glass and, in the most unfavorable cases for the applications considered here, TiO2 can even lead to the formation of low-expansion crystalline phases.

[0041] For example, as described in US Patent Application Publication No. 2010 / 0129726, if the content of components incorporated into the crystalline phase is too high, the wetting of the materials to be joined and therefore its suitability as a joining material may be questionable.

[0042] Therefore, there is a need for crystallizable glasses that have high heat resistance, preferably capable of withstanding temperatures of 900°C or higher, that wet the materials and / or components to be joined when melted, and that preferably have a high coefficient of thermal expansion.

[0043] Therefore, a further aspect of the object of the present invention is also to provide a crystallizable glass which overcomes or at least alleviates the aforementioned drawbacks of the prior art.

[0044] This further aspect of the problem of the invention is solved by the subject matter of the independent claims. Further configurations and special embodiments can be found in the dependent claims as well as in the figures and description.

[0045] This further aspect of the present invention relates to a bonded assembly, particularly a bonded assembly that is stable at high temperatures and / or can withstand high mechanical loads, comprising at least partially crystallized glass and a bonding partner, wherein the at least partially crystallized glass contains less than 10%, preferably less than 5%, of residual glass by volume. The at least partially crystallized glass comprises crystalline aggregates. The crystalline aggregates are formed from a large number of crystallites. Preferably, the crystallites are formed in the form of needles and / or platelets. Preferably, the crystallites are distributed throughout the at least partially crystallized glass and can be arranged radially, for example, in the form of spherulites, fans, rods, and / or platelets.

[0046] Such a construction of the bonded joint has many advantages.

[0047] In particular, a high dimensional stability of the bonded joint is achieved with a low proportion of residual glass, less than 10% by volume, preferably even less than 5% by volume.

[0048] Furthermore, the high dimensional stability of the bonded bonded body is advantageously ensured by the agglomeration of the crystallites contained in the crystallized glass. Here, it is particularly advantageous for the crystallites to be formed in a needle-like and / or platelet-like shape. The inventors have found that the needle-like and / or platelet-like shape of the crystallites in the crystal agglomerates results in the formation of mechanically stable at least partially crystallized glass. This is particularly true when the crystallites, preferably formed in a needle-like and / or platelet-like shape, are distributed throughout the at least partially crystallized glass, for example, in a spherulitic and / or fan-like and / or rod-like or platelet-like arrangement. The inventors believe that the crystallites, preferably formed in a needle-like and / or platelet-like shape, distributed throughout the at least partially crystallized glass, and their arrangement, for example, in a spherulitic, radial, or random rod-like arrangement, interlock with each other, thereby advantageously improving the mechanical stability of the at least partially crystallized glass, for example, against shear, compressive, or tensile forces. This interlocking can also occur in the form of a kind of "house of cards."

[0049] Crystallites can also be formed in platelet form, i.e., distributed as small platelets in the crystallized glass. In cross-sectional views, such formations appear as rods, making it difficult to distinguish them from one another. In the context of this disclosure, platelets are understood to be geometric shapes whose lateral dimension (thickness) in one spatial direction of the Cartesian coordinate system is an order of magnitude smaller than the lateral dimensions (length, width) in the other two directions perpendicular to the first direction.

[0050] The present disclosure further provides a bonded assembly, in particular a bonded assembly that is stable at high temperatures and / or capable of withstanding high mechanical loads, comprising an at least partially crystallized glass and a bonded partner, wherein the glass: La2O3: more than 0.3 mol% to less than 5 mol%, preferably 4.5 mol% or less, particularly preferably 4 mol% or less; Nb2O50mol%~9mol%, Ta2O50mol%~7mol%, where Σ(A2O5) 0.2 mol% to 9 mol%, wherein A is an element which in its oxide normally has the oxidation state V+, and which may include or contain, for example, Nb, and / or Ta, or P, and / or mixtures thereof. The present invention relates to a conjugate comprising:

[0051] It has been shown that strong bonded joints, for example bonded joints that are stable at high temperatures and / or can withstand high mechanical loads, can be obtained by adding the oxides La2O3, Ta2O5, and / or Nb2O5, and optionally further oxides of composition A2O5, in sufficient amounts, i.e. in the ranges mentioned above.

[0052] Here, A represents an element that in its oxide normally has the oxidation state V+. Thus, not all of the atoms "A" contained in a crystallizable or at least partially crystallized glass may be in the same oxidation state.

[0053] Here, in the context of the present disclosure, the oxides La2O3, Nb2O5, and Ta2O5, as well as the optional additional oxide A2O5 contained in the glass, are also referred to as "glass matrix-forming oxides." In the context of the present disclosure, this term refers to those oxides that initially remain in the glass matrix after heat treatment of a crystallizable glass, i.e., when the glass exists as an at least partially crystallized glass. Therefore, the term "glass matrix-forming oxides" differs from the more general term "glass-forming oxides." In particular, in the context of the present disclosure, oxides such as MgO and CaO are not glass matrix-forming oxides, even though, for example, CaO is a common component of conventional glasses, such as soda-lime glass. In glasses according to embodiments of the present disclosure, oxides such as CaO and MgO are incorporated into the crystalline phase, i.e., do not remain in the glass matrix, and therefore are not glass matrix-forming oxides.

[0054] However, it is entirely possible that at least a portion of the glass matrix-forming oxides, e.g., La2O3, may be at least partially incorporated into the crystalline phase in the further course of ceramming, but a small residual content of the glassy phase, formed in particular by the glass matrix-forming oxides, usually remains.

[0055] The formation of a bonded assembly according to the present disclosure with the oxides La2O3, Nb2O5, and / or Ta2O5 in the above-mentioned ranges, and optionally further oxides A2O5, is advantageous because the at least partially crystallized glass is thus particularly advantageously configured so that glass welding occurs during the temperature treatment for producing the assembly. That is, particularly advantageously, strong bonds are thus generated between the individual parts of the bonded assembly, and in particular strong bonding of the at least partially crystallized glass to the bonding partners is possible. However, limiting the glass matrix-forming oxides to the aforementioned ranges advantageously ensures that the bonded assembly simultaneously exhibits high temperature stability and / or high mechanical strength.

[0056] In the context of this disclosure, the following definitions apply: In the context of the present disclosure, a crystallizable glass is understood to be a glass capable of crystallization, in particular, controlled or at least controllable crystallization. Controlled crystallization is understood here to mean that a crystallizable glass can be brought into a state in which the glass is at least partially crystallized by a targeted temperature treatment, and the crystallographic composition of the at least partially crystallized glass and / or its structure, i.e., the spatial arrangement and / or size of the crystals and / or crystallites contained in the at least partially crystallized glass, can be preferably targeted and adjusted. Preferably, by controlling the crystallization, a structure can be obtained in which the crystallites have a substantially uniform size, for example, in the single-digit micrometer range, i.e., for example, all crystallites have an equivalent diameter of about 1 μm to 3 μm.

[0057] Of course, other textures with larger or smaller crystallites are possible.

[0058] When an at least partially crystallized glass contains multiple different crystalline phases, the average crystal size or average crystallite size within the crystalline phases will be relatively similar, although there may be significant differences in crystallite size between the individual crystalline phases.

[0059] In contrast to the preferred controlled or controllable crystallization, spontaneous crystallization of glasses is observed, which can result in unexpected, often undesired, crystalline phases, especially complete devitrification.

[0060] In the context of the present disclosure, a crystalline aggregate or crystal aggregate is understood to mean an intergrowth of at least two crystals or crystallites, where the crystals or crystallites may intergrow in a particularly random manner, meaning that the individual crystallites or crystals of the aggregate may not intergrow along a preferred direction or specific crystallographic plane.

[0061] By "crystals or crystallites formed in an acicular shape," it is understood that the crystals or crystallites have a dimension in one direction that is at least one order of magnitude larger than the dimensions in the other two spatial directions. In other words, crystals or crystallites formed in an acicular shape can be formed in a needle or rod shape, or in a prismatic shape, with the lateral dimension of the prismatic basic shape being at least one order of magnitude smaller than the length of the crystal or crystallite. Such crystals or crystallites are also referred to as "prismatically formed."

[0062] Crystallites can also be formed in platelet form, i.e., distributed as small platelets in the crystallized glass. In cross-sectional views, such formations appear as rods, making it difficult to distinguish them from one another. In the context of this disclosure, platelets are understood to be geometric shapes whose lateral dimension (thickness) in one spatial direction of the Cartesian coordinate system is an order of magnitude smaller than the lateral dimensions (length, width) in the other two directions perpendicular to the first direction.

[0063] In the context of the present disclosure, "radially arranged crystals or crystallites" is understood to mean that needle- or platelet-shaped crystals, e.g., needle- or prismatic crystals or crystallites, are arranged around a center, with one end pointing toward this point and the other ends pointing radially outward in different spatial directions. For example, the ends pointing toward the center may be tangent to the center point. However, this is not required. Such crystalline aggregates oriented radially outward from the center exist, for example, in the form of spherulitically formed crystal aggregates. Such spherulitically formed crystal aggregates are crystalline aggregates with an approximately spherical or ellipsoidal configuration, and in a two-dimensional representation, may appear approximately circular. However, in reality, due to the intergrowth of crystals and crystalline aggregates in the structure, they often differ from ideally spherical or circularly formed spherulites. In particular, the crystals or crystallites forming spherulites may have different lengths and / or thicknesses.

[0064] A further example of a radial arrangement is the formation of a fan shape in a two-dimensional cross section. For example, it may not be possible for crystals or crystallites to form in a specific spatial direction in the tissue. Again, the crystallites or crystals extend from the center outward, but only within a specific solid angle.

[0065] By "distributed rod-like or platelet-like arrangement" is understood that the individual crystals or crystallites do not extend outward in different spatial directions from a common center, but are arranged randomly, e.g., without a particular preferred direction. In particular, the crystallites or crystals may be arranged interlocking with one another. Such a structure can be likened, for example, to that of a "house of cards," in which individual platelets (such as cards in a house of cards) are arranged one above the other to form a stable structure.

[0066] In the context of the present disclosure, a crystallization nucleus is understood to be the starting point of crystallization. A crystallization nucleus promotes the accumulation of atoms to build a crystal lattice, for example, thermodynamically or kinetically. In particular, a crystallization nucleus may be a lattice defect and / or an aggregate of atoms. In many cases, an interface may be the starting point of crystallization, or the interface may include such a starting point of crystallization.

[0067] According to one embodiment of the bonded assembly, the crystallites comprise crystallization nuclei at least partially at their grain boundaries and / or deposits comprising lanthanum, in particular comprising lanthanum compounds, are at least partially located at the grain boundaries of the crystallites.

[0068] Such a configuration of the bonded joint is advantageous in that it allows a particularly strong bond to be formed between the at least partially crystallized glass and the bonded partner. If the crystallites contain crystallization nuclei at least partially at the grain boundaries, this promotes the formation of a structure of the at least partially crystallized glass with crystalline aggregates that are distributed, for example, radially, rod-like, or platelet-like, like a house of cards.

[0069] This is also true when the deposits containing lanthanum, particularly lanthanum compounds, are at least partially located at the grain boundaries of the crystallites, and the inventors believe that the deposits of lanthanum, e.g., lanthanum compounds, can act as effective crystallization nuclei.

[0070] According to a further embodiment of the bonded assembly, the difference in the thermal expansion coefficients of the bonded partners and the at least partially crystallized glass has a value of 5. * 10 -6 / K or less, preferably 3 * 10 -6 / K or less, particularly preferably 1×10 -6 / K or less. Such a configuration of the bonded assembly, in particular the matching of the thermal expansion coefficients of the glass and the bonded partner, has the advantageous effect that the heat resistance and / or mechanical durability of the bonded assembly thus obtained can be further improved.

[0071] The bonded assembly can be subjected to high operating temperatures, particularly temperatures of 1000°C or higher. It is believed that the presence of the crystalline aggregates and the described structure mechanically stabilize the material, for example, by the crystalline aggregates interlocking with one another. If a residual glass phase is present, the crystalline aggregates and / or their structure can also stabilize the residual glass phase, even if the residual glass phase would soften under the influence of temperature.

[0072] Equally advantageously, the bonded joint is mechanically stable, especially against vibration loads, as measured as a function of temperature in shake and vibration tests according to ISO 16750-3 (ed. 2007-08-01). It is believed that the crystalline aggregates inhibit the propagation of initial cracks in the material, preventing the component from failing even in the event of localized damage.

[0073] According to one embodiment of the present disclosure, the bonded combination withstands an operating temperature of at least 1000° C., and preferably the bonded combination is vibration and vibration resistant as measured in accordance with ISO 16750-3.

[0074] In other words, the crystalline aggregates appear to mutually restrict the displacement of at least partially crystallized glass volume elements in an operating state. This can be assumed when considering any two adjacent volume elements that comprise a crystalline aggregate. In an operating state under mechanical load, forces that tend to displace the volume elements relative to one another, such as shear forces, can act on the volume elements. If the crystalline aggregates have a suitable structure, particularly the mentioned structures, they can interlock with one another and thus already mechanically restrict the volume elements from displacing one another.

[0075] That is, according to yet another embodiment of the bonded assembly, the crystalline aggregates prevent the volume elements of the at least partially crystallized glass from being displaced relative to one another in the operating state.

[0076] The measures mentioned here can also be particularly advantageously combined.

[0077] Advantageously, the bonded assembly is configured so that there is no meniscus or there is a neutral meniscus on the surface of the at least partially crystallized glass.

[0078] Here, "forming a meniscus-free surface" is understood to mean that the surface is not curved. A curved surface of at least partially crystallized glass can occur, for example, when glass is heated to produce a bonded joint and at least partially melts (so-called glass welding), and the bonded partner wets it particularly well, so that the glass rises due to capillary forces at the interface with the bonded partner. In this case, the meniscus is concave. Conversely, if there is only slight wetting, for example, in the presence of a very viscous glass, a convex meniscus can form. However, optimally, the bonded joint is configured so that the surface of the at least partially crystallized glass is formed without a meniscus, i.e., without any upward or downward curvature. In this case, it is also called a neutral meniscus.

[0079] According to a further embodiment of the bonded joint, in the transition area between the surface of the bonded partner and the surface of the at least partially crystallized glass, preferably 1 cm 3 An at least largely amorphous glass layer is arranged which contains fewer than 10 pores per 100 μm and / or has a thickness of preferably 5 μm or less, particularly preferably 2 μm or less, very particularly preferably 1 μm or less.

[0080] A bonded joint of such a configuration is advantageous because a particularly strong bond can be achieved in this way. In particular, the low porosity at the interface between the at least partially crystallized glass and the bonded partner advantageously further improves the mechanical durability and / or heat resistance of the joint. That is, pores at or near the interface can be the starting point for mechanical failure, especially when the bonded joint is exposed to high temperatures.

[0081] Furthermore, a thin amorphous glass layer at the interface advantageously supports the formation of a bonded bond that can withstand high thermal and / or mechanical loads, for example. "Forming a glass layer" means that there is a chemical bond between the bonded partner and the glass. However, according to the present disclosure, it is particularly advantageous if the at least partially crystallized glass has a residual glass content of less than 10% by volume, preferably less than 5% by volume. In other words, the at least partially crystallized glass should only have a small residual glass content. This is because the thermal and / or mechanical stability of the bonded bond is achieved, in particular, by the formation of one or more crystalline phases. Therefore, advantageously, high thermal resistance and / or mechanical durability are ensured, especially when the amorphous glass layer has a thin thickness of at most 5 μm or less, preferably 2 μm or less, and particularly preferably 1 μm or less.

[0082] According to one embodiment of the joining combination, the joining partners are metals, in particular steels, such as plain steel, stainless steel, stainless steel, and high-temperature stable ferritic steels also known as Thermax, for example under the trade names Thermax 4016, Thermax 4742 or Thermax 4762, or under the trade names Crofer22 APU or Crofer22 H, or NiFe-based materials, for example NiFe45, NiFe47 or nickel-plated pins, or Inconel, for example under the trade names Inconel 718 or X-750, or for example CF25, Alloy 600, Alloy 601, Alloy 625, Alloy 626, Alloy 627, Alloy 628, Alloy 629, Alloy 630, Alloy 631, Alloy 632, Alloy 633, Alloy 634, Alloy 635, Alloy 636, Alloy 637, Alloy 638, Alloy 639, Alloy 640, Alloy 641, Alloy 642, Alloy 643, Alloy 644, Alloy 645, Alloy 646, Alloy 647, Alloy 648, Alloy 649, Alloy 650, Alloy 651, Alloy 652, Alloy 653, Alloy 654, Alloy 655, Alloy 656, Alloy 657, Alloy 658, Alloy 659 ... These include the steels known under the names 690, SUS310S, SUS430, SUH446 or SUS316, or austenitic steels such as 1.4762, 1.4828 or 1.4841, metals from the Kanthal heating wire group, or high-temperature stable ceramic compounds such as forsterite, aluminum oxide-based ceramics or zirconium oxide-based ceramics, for example ceramics containing Y-stabilized zirconium oxide.

[0083] According to one embodiment, the conjugate is 10 -8 mbar * The composite exhibits a helium leak rate of less than 1 / s and / or comprises, according to one embodiment, at least partially crystallized glass having an elastic modulus of 80 GPa to 200 GPa, preferably 100 GPa to 125 GPa. This configuration is advantageous because, while sufficient mechanical rigidity is achieved in this way, the composite is still more elastic than, for example, conventional ceramics. This is advantageous when subjected to temperature changes and therefore advantageously results in a particularly temperature-stable bonded composite.

[0084] The present disclosure further provides: La2O3: more than 0.3 mol% to less than 5 mol%, preferably 4.5 mol% or less, particularly preferably 4 mol% or less; Nb2O50mol%~9mol%, Ta2O50mol%~7mol%, where Σ(A2O5) 0.2 mol% to 9 mol%, where A is an element that in its oxide normally has the oxidation state V+, and may include, for example, Nb, and / or Ta, or P, and / or mixtures thereof. The present invention relates to a crystallizable or at least partially crystallized glass comprising:

[0085] It has been shown that a strong bond between the glass and the joining partner can be obtained by adding the oxides La2O3, Ta2O5, and / or Nb2O5, and optionally further oxides of composition A2O5, in sufficient amounts, i.e. in the ranges mentioned above.

[0086] Here, A represents an element that in its oxide normally has the oxidation state V+. Thus, not all of the atoms "A" contained in a crystallizable or at least partially crystallized glass may be in the same oxidation state.

[0087] Here, in the context of the present disclosure, the oxides La2O3, Nb2O5, and Ta2O5, as well as the optional additional oxide A2O5 contained in the glass, are also referred to as "glass matrix-forming oxides." In the context of the present disclosure, this term refers to those oxides that initially remain in the glass matrix after heat treatment of a crystallizable glass, i.e., when the glass exists as an at least partially crystallized glass. Therefore, the term "glass matrix-forming oxides" differs from the more general term "glass-forming oxides." In particular, in the context of the present disclosure, oxides such as MgO and CaO are not glass matrix-forming oxides, even though, for example, CaO is a common component of conventional glasses, such as soda-lime glass. In glasses according to embodiments of the present disclosure, oxides such as CaO and MgO are incorporated into the crystalline phase, i.e., do not remain in the glass matrix, and therefore are not glass matrix-forming oxides.

[0088] However, it is entirely possible that one or more glass matrix-forming oxides, such as La2O3, are at least partially incorporated into the crystalline phase during subsequent ceramization, but essentially a residual glass fraction remains, formed by the so-called glass matrix-forming oxides.

[0089] The addition of the components La2O3, Ta2O5, and / or Nb2O5, and possibly further oxides A2O5, primarily contributes to the high glass stability of the starting material. As explained above, these oxides are the oxides that remain, at least initially, in the crystallites and / or the glass matrix surrounding the crystals after a heat treatment, i.e., a heat treatment that can convert a crystallizable glass into an at least partially crystallized glass.

[0090] The inventors envision that these elements are converted into and / or incorporated into the crystalline structure components, if at all, only during subsequent heat treatments. In particular, at least the element La2O3 may be at least partially incorporated into the crystalline phase.

[0091] It has now surprisingly been shown that this vitreous structure, which may in particular comprise the oxides mentioned above, such as La2O3, Ta2O5 and / or Nb2O5, and optionally further oxides A2O5, ensures a strong bond with the joining partners, i.e. the materials and / or components to be joined, without nevertheless inhibiting the high dimensional stability of the resulting joint at high temperatures, such as temperatures of 900°C or even 950°C or 1000°C or higher.

[0092] In the context of the present disclosure, a material and / or component is said to be high-temperature resistant or high-temperature stable if it can be used at temperatures of 900° C. or higher, preferably 950° C. or higher, particularly preferably 1000° C. or higher, in particular if it can be used at temperatures of 900° C. or higher, preferably 950° C. or higher, particularly preferably 1000° C. or higher for 100 hours or more, preferably 500 hours or more, particularly preferably 1000 hours. In particular, the material and / or component can be formed such that it is stable against deformation at these temperatures for the stated periods.

[0093] This high dimensional stability is also due to the relatively early onset of crystallization. However, due to the glass matrix, this does not inhibit the strong bonding of the joining partners. This is particularly surprising, since it was previously assumed that crystallization only occurred after sintering was complete, allowing a strong and dense bond to be obtained (see, for example, Tulyaganov et al., Journal of Power Sources 242 (2013), 486-502).

[0094] Further components that may be included in the glass and that remain at least partially in the glass matrix after heat treatment are Bi2O3 and / or P2O5. However, these components are disadvantageous in terms of the high-temperature stability of the glass considered here and the bonded joints produced with this glass. Therefore, according to one embodiment, the glass advantageously does not contain oxides of Bi and / or P, except for unavoidable trace amounts.

[0095] In the context of this disclosure, a content of 500 ppm or less of this component is referred to as an unavoidable trace component, where the unit "ppm" is based on weight.

[0096] According to yet another embodiment, the glass does not contain alkali metal and / or boron oxides, except for unavoidable trace amounts. In particular, this means that, according to a particularly preferred embodiment of the present invention, the glass contains a maximum of 500 ppm of B2O3. The absence of alkali metal oxides and / or B2O3 in glasses according to these embodiments is advantageous, since these components reduce the temperature resistance of crystallizable or at least partially crystallized glasses. Furthermore, these components, such as certain alkali metals, can form low-expansion crystalline phases that are undesirable for the applications discussed herein. Furthermore, alkali metal content is disadvantageous because it reduces electrical resistance.

[0097] According to one embodiment, the glass comprises the oxide RO, and Σ(RO) ≦55mol% wherein R is an element which in its oxide normally has the oxidation state II+, and includes in particular Ca, Mg, or Zn, and / or mixtures thereof. holds true.

[0098] In other words, RO contains alkaline earth metal oxides and ZnO. According to a preferred embodiment of the present disclosure, the glass does not contain alkaline earth metal oxides BaO and / or SrO, except for unavoidable trace amounts, in order to avoid adverse contact reactions between the glass and chromium-containing joining materials, such as chromium-containing steel.

[0099] According to a further embodiment, the glass comprises: SiO2 30mol%~40mol%, Al2O3 3mol%~12mol%, CaO 32mol%~46mol%, MgO 5mol% to 15mol%, ZnO 0 mol% to 10 mol%, and optionally, 20 mol% to 4 mol%, preferably up to 3 mol%, of ZrO, and / or 20 mol % to 4 mol %, preferably up to 3 mol %, of TiO, and / or MnO20mol%~5mol% Includes:

[0100] According to one embodiment, TiO2, ZrO2, and / or MnO2 may optionally be included in the glass. However, the content of these components in the glass is limited. In particular, in crystallizable glasses, TiO2 and ZrO2, which are known nucleating agents, are not required as nucleating agents. Moreover, their presence can be disruptive, since they can lead to undesirable crystalline phases with low expansion, which is most unfavorable for the present application.

[0101] According to a further embodiment, the CaO content of the glass is at least 35 mol % and at most 46 mol %, preferably at least 35 mol % and less than 43.5 mol %, and / or the MgO content of the glass is 5 mol % and less than 13 mol %.

[0102] The CaO and / or MgO content of the glass, which is limited according to one embodiment, is attributed to the fact that this further improves the stability of the crystallizable glass against spontaneous crystallization. CaO and MgO are components that are incorporated into the crystalline phases produced by heat-treating the crystallizable glass. As explained above, obtaining a crystalline phase with a high thermal expansion coefficient is particularly important for the intended application. Therefore, the CaO and MgO contents of the glass are preferably further limited as explained above, so that the desired crystalline phase with a high thermal expansion coefficient is predominantly obtained. This limitation serves, in particular, to prevent, at least as far as possible, or even completely, the formation of wollastonite, enstatite, diopside, or mixed crystals of these crystalline phases.

[0103] According to a further embodiment, the glass is present as a crystallizable glass and has a transformation temperature above 720°C.

[0104] The transformation temperature of a glass is an important characteristic parameter that reflects both the processing properties of the glass and its heat resistance. In particular, a high transformation temperature of a glass is also accompanied by a high dimensional stability of the glass.

[0105] Thus, preferably, according to one embodiment, the crystallizable glass has a particularly high dimensional stability, which is indicated by the high transformation or glass transition temperature T ≥ 720 ° C. g This is reflected in the

[0106] According to a further embodiment, the crystallizable glass has a linear thermal expansion coefficient of 8×10 in the temperature range from 20° C. to 300° C. -6 / K, and preferably 9 × 10 -6 / K. In this way, it is advantageously possible with the crystallizable glass to better match the vitreous material to the linear thermal expansion coefficient of the materials to be joined, for example highly refractory materials such as Y-stabilized ZrO and / or alloys, even before the end of the heat treatment to produce a preferably hermetic bond.

[0107] Transformation temperature T g is determined by the intersection of the tangents to the two branches of the expansion curve when measured at a heating rate of 5 K / min. This corresponds to measurements according to ISO 7884-8 or DIN 52324.

[0108] The softening temperature of glass, also abbreviated as "Ew", is the temperature range in which the viscosity of the glass is 10 7.6 dPa * The value of s represents the temperature.

[0109] In the context of the present disclosure, the coefficient of linear thermal expansion is referred to. When the coefficient of linear thermal expansion of a crystallizable glass is described, this is the nominal mean coefficient of linear thermal expansion according to ISO 7991, determined by static measurement (using a push rod dilatometer). The coefficient of linear thermal expansion of an at least partially crystallized glass is determined by dilatometry.

[0110] In the context of this disclosure, the coefficient of linear thermal expansion is also referred to as α, e.g., α(20-700) or α 20-700 represents the coefficient of linear thermal expansion in the temperature range of 20°C to 700°C.

[0111] According to yet another embodiment of the present disclosure, the glass exists as an at least partially crystallized glass, and has a temperature range of 20°C to 700°C. * 10 -6 / K, preferably above 10 × 10 -6 / K, and particularly preferably the linear thermal expansion coefficient of the at least partially crystallized glass is greater than 9 / K in the temperature range of 20°C to 1000°C. * 10 -6 / K above, preferably 9.5 * 10 -6 / K or more.

[0112] According to embodiments of the present disclosure, the glass is not only formed such that a preferably gas-tight and / or electrically insulating bond can be produced, but in particular, according to embodiments, a preferably gas-tight and / or electrically insulating bond can also be produced that continues to ensure sufficient electrical insulation even at high temperatures.

[0113] Such a combination, for example a metal-glass combination, is said to be fluid-tight if it is sealed, i.e., in this case, sealed against the escape or passage of a fluid medium, and preferably substantially completely (hermetically) sealed. Here, the sealing property can usually be determined by a leak test using a helium leak tester. At room temperature, 1 * 10 -8 mbar * A helium leak rate of less than 1 / s indicates that a substantially perfectly gas-tight seal has occurred. This measurement may preferably be carried out at an applied pressure of 1 bar.

[0114] According to these embodiments, the glass is present as a crystallizable glass, and the temperature of the crystallizable glass is 10 8 Ω * The specific electrical resistivity of 10 ... k It's 100.

[0115] According to one embodiment, the crystallizable or at least partially crystallized glass comprises, in particular, SiO 2 , and CaO, and MgO, and Al 2 O 3 , and optionally ZnO.

[0116] In the SiO2-Al2O3-CaO-MgO system, crystalline phases with high thermal expansion coefficients can be realized. These include, for example, mixed crystals from the CaO-rich calcium-magnesium silicate family, such as akermanite and / or merwinite, which also form gehlenite and / or augite, for example, with Al2O3. If the glass also contains ZnO, hardystonite may also be formed as a mixed crystal.

[0117] According to one embodiment, the glass is present as an at least partially crystallized glass, preferably comprising crystallites of a CaO-rich calcium-magnesium silicate, in particular CaO-rich calcium-magnesium island silicates and / or sorosilicates. Here, island silicates are silicates in which the SiO tetrahedra contained therein are present individually, i.e., not bonded to each other. Sorosilicates are silicates in which two SiO tetrahedra are bonded to each other via a common bridging oxygen, resulting in a SiO aggregate as a silicate structural unit. Preferably, the at least partially crystallized glass may comprise marwinite CaMg(SiO) and / or a mixed crystal having a marwinite structure as the island silicate. Furthermore, the at least partially crystallized glass may alternatively or additionally comprise a crystalline phase having a melilite structure, such as akermanite CaMgSiO or gehlenite CaAl[AlSiO], or a mixed crystal thereof, as the sorosilicate. Additionally, the at least partially crystallized glass may also include a crystalline phase having an augite structure, according to one embodiment.

[0118] When mixed crystals are mentioned in the context of the present disclosure, these are crystals that do not correspond to the stoichiometric compound. For example, when "akermanite mixed crystals" are mentioned, these are understood to be crystals that do not have the stoichiometric composition Ca2MgSi2O7. For example, it is possible for the mixed crystal to contain more Ca than the stoichiometric composition, or for Zn to be incorporated instead of Ca. However, the mixed crystals crystallize in a crystal structure that corresponds approximately to the crystal structure of akermanite, i.e., except for small deviations, for example, in the lattice parameters.

[0119] According to one embodiment, the glass is present as an at least partially crystallized glass, preferably comprising crystallites of CaO-rich calcium-magnesium silicates, in particular CaO-rich calcium-magnesium island silicates and / or sorosilicates, e.g. merwinite and / or mixed crystals with a merwinite structure, and alternatively or additionally crystalline phases with a melilite structure such as akermanite CaMgSiO and / or gehlenite CaAl[AlSiO] and / or mixed crystals thereof, and / or crystalline phases with an augite structure.

[0120] The present disclosure also relates to a bonded bond comprising at least partially crystallized glass, wherein the glass is at least partially crystallized glass according to embodiments of the present disclosure or is made or producible from a crystallizable glass according to embodiments of the present disclosure.

[0121] In the context of the present disclosure, a joining partner is understood to be a material or element that is or is to be assembled or joined together with other materials or elements, preferably into a hermetically assembled element. If there are several joining partners to be joined, these may be of the same or different composition.

[0122] In the context of the present disclosure, a conjugate is also referred to as a junction complex or junction conjugate.

[0123] The present disclosure also relates to articles of manufacture, particularly retaining and / or insulating elements and / or additional structures that include at least partially crystallized glass according to embodiments of the present disclosure.

[0124] Preferably, the product can be produced from a sintered body comprising a crystallizable glass according to an embodiment of the present disclosure. Preferably, the sintered body comprises a crystallizable glass as a glass powder. Very particularly preferably, the glass powder comprises powder particles having a particle surface.

[0125] Furthermore, the present disclosure relates to the use of a bonded combination according to an embodiment of the present disclosure. In particular, the combination may be used in conjunction with an exhaust gas sensor, a pressure sensor, a particle sensor, e.g., a soot particle sensor, and / or a temperature sensor, such as in an automotive exhaust gas system. x It can be used in sensors such as oxygen sensors, and / or in feedthroughs for compressors and / or electric compressors, and / or as current feedthroughs in exhaust gas elements and / or fuel cells, and / or in feedthroughs for chemical reactors.

[0126] Example The crystallizable or at least partially crystallized glasses disclosed herein, as well as their uses, are described in more detail below with reference to examples.

[0127] The following table shows exemplary compositions of crystallizable or at least partially crystallized glasses. These compositions are in each case listed in mol %. Characteristic temperatures are those temperatures usually used to describe the melting behavior of ash, such as the softening temperature (abbreviated as softening), sintering temperature (abbreviated as sintering), sphere temperature (abbreviated as sphere), hemisphere temperature (abbreviated as hemisphere) and flow temperature, which are determined using a hot spot microscope (abbreviated as HSM). These temperatures are determined in accordance with or on the basis of DIN 51730. The thermal expansion coefficient α is in each case 10 -6 It is shown in units of / K.

[0128] [Table 1-1]

[0129] [Table 1-2]

[0130] [Table 2-1]

[0131] [Table 2-2]

[0132] [Table 3-1]

[0133] [Table 3-2]

[0134] Table 2 below lists comparative examples of crystallizable or at least partially crystallized glasses.

[0135] [Table 4-1]

[0136] [Table 4-2]

[0137] In Comparative Examples 1, 5, and 6, the glasses began to flow specifically at flow temperatures of 1128°C (Comparative Example 1), 1166°C (Comparative Example 5), and 1147°C (Comparative Example 6).

[0138] In Comparative Examples 2, 3, and 4, glasses were no longer obtainable, rather, these compositions crystallized in an uncontrolled manner upon cooling after melting.

[0139] Glasses according to embodiments of the present disclosure are obtained in a vitreous state from a melting process. Rapid cooling rates are not required during casting. In particular, a cooling rate of at least 30 cm 3This is all the more surprising since the specialist literature states that vitreous solidification is only possible on a small scale in the case of ribbons.

[0140] The crystallized or at least partially crystallized glass according to the present disclosure has particularly advantageous dimensional stability. This is demonstrated, for example, by the very small shape deviation between a sintered body containing a crystallizable glass according to an embodiment of the present disclosure and a molded body containing at least partially crystallized glass obtained by crystallizing the sintered body through a temperature treatment, i.e., the length deviation is only in the single-digit percentage range, as shown, for example, in the measurement data in the table below. To determine these data, compacts having average transverse dimensions (here, average diameter) of approximately 10-12 mm were prepared. After sintering, the resulting sintered molded body was heated to 1200°C in a muffle furnace at a heating rate of 4 K / min. The temperature at 1200°C was kept constant for 10 minutes. Cooling was then performed. After cooling, the average transverse dimensions (here, average diameter) were again determined. The relative deviation of the average transverse dimensions before and after the heat treatment at 1200°C was then determined.

[0141] [Table 5]

[0142] The described high dimensional stability of compacts, such as pressed or sintered bodies, that initially contain a crystallizable glass and are then converted during temperature treatment into compacts at least partially containing at least partially crystallized glass, now makes it particularly advantageous to reliably extend creepage distances, for example, in feedthroughs. In particular, the compacts do not curl during temperature treatment. The excellent resistance to urea and its derivatives, particularly in concentrations such as those used in certain AdBlue for SCR catalysts, allows the bonded assemblies described herein to be used in exhaust gas installations with exhaust gas cleaning systems for extended operational life. [Brief explanation of the drawings]

[0143] Hereinafter, embodiments of the present disclosure will be further described with reference to the drawings. [Figure 1] 1 is a cross-sectional view of a first embodiment of a bonded combination disclosed herein, the cross-section being taken along plane AA from FIG. 1a and passing approximately through the center of the bonded combination. [Figure 1a] FIG. 2 is a plan view of the first embodiment illustrated in cross section in FIG. 1; [Figure 2] FIG. 1 is a cross-sectional view of a second embodiment of a bonded combination disclosed herein, the cross-section being taken through approximately the center of the bonded combination as illustrated in FIGS. 1 and 1a. [Figure 2a] FIG. 1 is a plan view of a creepage distance extension of the first disclosed embodiment, on which graphite pen or pencil marks are visible. [Figure 2b] FIG. 1 is a plan view of a creepage distance extension of the first disclosed embodiment, on which graphite pen or pencil marks are visible after being at least partially removed with a cellulose cloth using a lateral wiping motion. [Figure 2c] FIG. 1 is a plan view of a creepage distance extension of the first disclosed embodiment, on which graphite pen or pencil marks are visible after being at least partially removed with a cellulose cloth using a lateral wiping motion. [Figure 3] FIG. 1 is a cross-sectional view of a third embodiment of a bonded combination disclosed herein, the cross-section being taken through approximately the center of the bonded combination as illustrated in FIGS. 1 and 1a. [Figure 4] FIG. 1 is a cross-sectional view of a fourth embodiment of a bonded combination disclosed herein, the cross-section being taken through approximately the center of the bonded combination as illustrated in FIGS. 1 and 1a. [Figure 5] FIG. 1 is a cross-sectional view of a fifth embodiment of a bonded combination disclosed herein, the cross-section being taken through approximately the center of the bonded combination as illustrated in FIGS. 1 and 1a. [Figure 6] FIG. 10 is a cross-sectional view of a sixth embodiment of a bonded joint disclosed herein, the cross-section being taken approximately through the center of the bonded joint. [Figure 7] 1 is a scanning micrograph of an at least partially crystallized glass according to an embodiment of the present disclosure. [Figure 8] 1 is a scanning micrograph of an at least partially crystallized glass according to an embodiment of the present disclosure. [Figure 9] 1 is a scanning micrograph of an at least partially crystallized glass according to an embodiment of the present disclosure. [Figure 10] 1 is a scanning micrograph of an at least partially crystallized glass according to an embodiment of the present disclosure. [Figure 11] 1 is a scanning micrograph of a bonded assembly according to one embodiment of the present disclosure.

[0144] Detailed Description of the Preferred Embodiments In the following detailed description of the embodiments disclosed herein, the components are not drawn to scale for ease of understanding, and like reference symbols represent like or functionally corresponding components in each embodiment.

[0145] FIG. 1 is a cross-sectional view of a first embodiment of a bonded joint 5 disclosed herein, the cross-section being taken along plane AA from FIG. 1 a through approximately the center of the bonded joint 5 and including centerline M.

[0146] The bonded assembly 5 includes an electrically insulating member 53 and at least two bond mates 51, 52. In the embodiment disclosed herein, the bond mate 51 is, without limitation of generality, formed in a hollow cylindrical shape and comprises a metal or ceramic material as described in further detail below. The bond mate 52 may likewise be made of a metal as described in further detail below and may be part of, for example, an electrical or electronic feedthrough and thus part of an electrical or electronic assembly in its intended use.

[0147] At least one of the joining partners 51 , 52 is kept electrically insulated from at least the other of the joining partners 51 , 52 by an electrically insulating member 53 .

[0148] This member 53 may include or consist of the crystallizable or partially crystallized glasses disclosed herein.

[0149] The insulating member 53 has a portion 54 extending between and bonded to the joining partners 51, 52, preferably glass-fused thereto. In the context of the present disclosure, "glass-fused" means that the crystallizable glasses or partially crystallized glasses disclosed herein form, upon heat treatment, an amorphous or glassy layer on their surface that can be melt-bonded to the material of each joining partner, and in this melt-bonded state, they are referred to as "glass-fused."

[0150] 1, the upper surface O of the insulating element is shown separated from portion 54 by dotted line L, which merely schematically illustrates the profile of the upper surface O without structures S, and therefore without creepage extensions, compared to a bonded combination with structures S, and therefore with creepage extensions. Without structures S, the upper surface forms a planar surface on which a meniscus may possibly be formed with respect to the respective bonded partner.

[0151] However, in the embodiment disclosed herein, a protuberance formed by the structure S, in this case the portion 55, is located on this surface of the portion 54 of the electrically insulating member 53 that extends between the joining partners.

[0152] This portion 55 forming the structure S allows the distance on the surface of the insulating member 53 from the inner mating partner 52 to the outer mating partner 51 to be extended, and therefore the presence of the structure S allows the creepage distance extension to be increased by up to seven times or more.

[0153] Thereby, the low resistance deposits on each surface can contribute to a much lesser extent to the reduction of the electrical resistance between the joining partners 51 and 52 .

[0154] In the case of deposits forming droplets and / or surface films, it can be very advantageous if the structure S has an edge with a radius of curvature Rv of less than one tenth of a millimeter, preferably less than one twentieth of a millimeter, and more than 10 μm, such that in most cases, even under the influence of gravity, the surface film or coating by the droplets will not extend over this edge with radius of curvature Rv, so that a closed surface coating cannot occur.

[0155] Instead of the protuberances shown in this embodiment, the structures S may also form recessed depressions in the insulating element 53. In any case, however, in particular the direct path from at least one joining partner to at least the other joining partner along the surface is extended compared to a surface that does not have this structure S. A direct path is here understood to be the shortest path from one joining partner to the other joining partner along a surface that does not have the structure S on the one hand and has the structure S according to the invention on the other hand.

[0156] Preferably, the structure S completely surrounds at least one of the joining partners, here the joining partner 52 as an annular structure, as can be clearly seen in FIG. 1a by way of example. In the context of the present disclosure, the expression "completely surrounded" does not mean that a complete three-dimensional surrounding is required, although this may in principle be the case. In the context of the present disclosure, a complete surrounding is already achieved, in particular if a complete annular surrounding is achieved, such that a complete seal can already be achieved by this surrounding.

[0157] The structure S may be formed integrally with and of the same material as a portion 54 of an insulating member 53 extending between and connected to the joining partners 51, 52, respectively, and preferably glass-fused thereto.

[0158] Preferably here, the material of the insulating member 53 comprises an at least partially crystallized glass as described in further and more detail elsewhere in the context of this disclosure.

[0159] In this case, the insulating parts 53 can be formed together with the structure S in a single heat treatment step, and in particular their crystallinity can be adjusted.

[0160] Advantageously, the crystallizable glass disclosed herein allows for the formation of a glass fusing joint during the heat treatment, particularly in the transition area between the surface of the joining partner and the surface of the at least partially crystallized glass, preferably 1 cm 2 , arranged in such a way that it subsequently provides a long-term operational durability at this point. 3 An at least largely amorphous glass layer is formed which contains fewer than 10 pores per layer and / or has a thickness of preferably 5 μm or less, particularly preferably 2 μm or less, very particularly preferably 1 μm or less, whereby a gas-tight bond is achieved between the joining partners 51, 52 and the insulating element 53.

[0161] In a preferred embodiment, the structure comprises a crystallizable or at least partially crystallized glass, and has at least a predominantly amorphous boundary layer at the surface of the structure, in particular substantially free of open pores, in particular less than 10 pores / cm. 3 A glass layer is formed having a thickness of 5 μm or less, preferably 2 μm or less, very particularly preferably 1 μm or less, including less than 5 μm.

[0162] Depending on the embodiment, in this at least predominantly amorphous boundary layer, which has a thickness of 5 μm or less, preferably 2 μm or less, and very particularly preferably 1 μm or less, the proportion of the amorphous phase or the glassy phase, each measured in weight percent, is higher than the proportion of all the respective crystalline phases as a whole, also measured in weight percent.

[0163] However, it is entirely possible that at least a portion of the glass matrix-forming oxides, for example La2O3, can be at least partially incorporated into the crystalline phase in the further course of ceramming, but there usually remains a small residual content of the glassy phase, which is formed in particular by the glass matrix-forming oxides and forms the amorphous boundary layer mentioned above.

[0164] To determine whether the embodiments disclosed herein are present, the inventors developed a test.

[0165] When a pen, for example a graphite pen with a hardness of HB, is used to draw a line St on the surface of the structure S or on the surface O of the structure S by pressing the pen perpendicularly to the surface of the structure S with a force of about 100 mN, as shown in Figures 2a to 2c, the line St is obtained as shown in Figure 2a.

[0166] Because the graphite of a graphite pen or pencil cannot be retained within the pores of an otherwise smooth surface, wiping parallel to the surface of the structure S or surface O, e.g., with a Zewa brand cellulose cloth, also with a contact pressure of about 100 mN, results in significant removal for members disclosed herein that include crystallizable or partially crystallized glass. Typically, the contrast between the line St and the surface of the structure S or surface O is now significantly reduced, e.g., to values ​​less than 50% or, depending on the notation of contrast, less than 0.5.

[0167] However, the graphite of the graphite pen or pencil can be retained in the pores of the ceramic surface, so that wiping parallel to the surface or surface O of the structure S, for example with a cellulose cloth under the brand name Zewa, also with a contact pressure of about 100 mN, results in only a small amount of removal, for example in the case of a component made of zirconium oxide. In general, the contrast between the line St and the surface or surface O of the structure S is then only slightly reduced, for example to a value of more than 50% or, depending on the expression of contrast, to a value of more than 0.5.

[0168] 3 and 4, the structure S is not made of the same material as the portion 54 of the insulating member 53 extending between and preferably glass-fused to the joining partners 51 and 52, respectively. Here, the structure S may comprise or consist of a high-temperature stable ceramic material, such as forsterite, an aluminum oxide-based ceramic, or a zirconium oxide-based ceramic, e.g., a ceramic containing Y-stabilized zirconium oxide. If the structure S is not made of a material according to the invention, the pencil test cannot be performed positively.

[0169] FIG. 2 shows a cross-sectional view of a second embodiment of the bonded combination disclosed herein, the cross-section being taken through approximately the center of the bonded combination as illustrated in FIGS. 1 and 1a.

[0170] In this embodiment, structure S includes a reinforcing member 56 that includes or consists of a metal foil, metal sheet, or metal-containing scrim, mesh, or knit, preferably consisting of or including steel. This substantially annular reinforcing member 56 is preferably held within further insulating members 57, 58, 59 that are formed as sintered bodies and can house reinforcing member 56, and that can be glass-fused to it after heat treatment. Here, the material of substantially annular members 57, 58, and 59 can be made of the crystallizable glass of the present disclosure.

[0171] FIG. 3 shows a cross-sectional view of a third embodiment of the bonded combination disclosed herein, the cross-section being taken through approximately the center of the bonded combination as illustrated in FIGS. 1 and 1a.

[0172] In this embodiment, the structure S is not of the same material as the portion 54 of the insulating member 53 that extends between, and is bonded to, and preferably glass-fused to, the joining partners 51, 52. The structure S comprises or consists of a high-temperature stable ceramic material, such as a ceramic containing forsterite, an aluminum oxide-based ceramic, or a zirconium oxide-based ceramic, such as Y-stabilized zirconium oxide.

[0173] As best seen in Figure 3, structure S is recessed within insulating member 53 and is surrounded by insulating member 53 so that glass welding occurs during heat treatment, preferably in the recessed region of structure S. Here, structure S is approximately radially centered within, and preferably at least partially recessed within, portion 54 of insulating member 53. This radial direction is illustrated by arrow R in Figure 3.

[0174] FIG. 4 shows a cross-sectional view of a fourth embodiment of the bonded combination disclosed herein, the cross-section being taken through approximately the center of the bonded combination as illustrated in FIGS. 1 and 1a.

[0175] This further, not-to-scale, schematic illustration of the bonded assembly 5 differs from the bonded assembly 5 illustrated in FIGS. 1-8 in that the structure S forming the creepage distance extension 55 is configured to include not only the material of the portion 54 but also a second material. This second material is also an insulating material, but is different from the material of the portion 54. In this embodiment, the material of the portion 54 is formed as a crystallizable or at least partially crystallized glass, as will be described in greater detail below, and the second material has a different chemical and / or crystallographic composition. That is, the second material differs from the material of the portion 54 in that it has a different chemical composition and / or a different crystalline content. In particular, the second material can be formed from or include ZrO2. It has been shown that a particularly dimensionally and temperature-stable structure S is possible as a creepage distance extension when 5% to 25% by weight of the second material, preferably ZrO2, is added as the second material. A content of 10 to 15% by weight is particularly preferred.

[0176] FIG. 5 shows very diagrammatically the configuration of a bonded assembly 5 according to a fifth embodiment. Here, an outer sidewall 552 of a portion 55 has a slightly curved or bent shape and is therefore not perfectly planar. In contrast, an inner sidewall 553 of the portion 55 is now planar. As can be seen from FIG. 5, the flatness of sidewall 552 differs from the flatness of sidewall 553. Here, sidewall 552 is shown somewhat distorted, since in reality it would not deviate so greatly from a planar sidewall.

[0177] 6 shows a sixth further embodiment of a bonded assembly 5 in which both the inner sidewall 552 and the outer sidewall 553 are not perfectly flat or planar. However, here the flatness is made approximately the same for both sidewalls 552 and 553. Again, strong distortion was introduced so that the effect of the sidewalls not being perfectly flat can be shown. Essentially, the deviation from flat sidewalls is much smaller.

[0178] Figure 7 shows a first scanning electron microscope photograph of an at least partially crystallized glass according to one embodiment of the present disclosure. The at least partially crystallized glass includes a crystalline aggregate 1 formed from numerous crystallites, which are preferably needle-shaped. Crystal aggregate 1 is shown in Figure 1 as an example. Additionally, crystallites 21 are visible at the grain boundaries and are shown as an example, as are crystallites 22, which are needle-shaped.

[0179] Figure 8 shows a second scanning microscope photograph of an at least partially crystallized glass according to a further embodiment of the present disclosure. Again, the at least partially crystallized glass comprises a crystalline aggregate formed from a large number of crystallites, preferably formed in a needle-like shape. Furthermore, pores are partially disposed between the individual crystallites, and the at least partially crystallized glass further comprises a residual glass phase disposed between the crystallites. Exemplarily shown here is a crystallite 2 forming a crystalline aggregate formed in a star shape. The residual glass phase 3, which is gray in the scanning microscope view, and the exemplarily shown pores 4 (black) can also be seen.

[0180] Figure 9 is a third scanning micrograph of an at least partially crystallized glass according to yet another embodiment of the present disclosure. Crystal aggregates are again visible. Here, the crystallites are so finely formed that they are barely perceptible at the selected resolution. In this way, a very dense and fine structure is obtained. Here, by way of example, one can see very fine crystals 22 shown.

[0181] Figure 10 is a scanning micrograph of yet another at least partially crystallized glass according to an embodiment of the present disclosure. In contrast to the crystallites of the at least partially crystallized glass shown in Figure 9, the crystallites 23 included in the crystalline aggregates of the at least partially crystallized glass are not as finely formed; rather, their rod-like or perhaps platelet-like morphology is discernible. Here, the crystallites 23 are arranged interlocking with one another, similar to a "house of cards" structure.

[0182] 11 shows a scanning micrograph of a bonded assembly according to one embodiment of the present disclosure, with 10 pores / cm at the interface between the bonded partner and the at least partially crystallized glass, located on the left side of the photograph. 3 A very thin boundary layer is formed, which is an at least largely amorphous glass layer having a thickness of 5 μm or less, preferably 2 μm or less, very particularly preferably 1 μm or less.

[0183] The following statements apply to all embodiments disclosed above.

[0184] The above embodiments have been described with respect to only two mating partners, however, it is within the scope of this disclosure that three or more mating partners can be held together in a mating combination by insulating members, similar to those disclosed herein.

[0185] The bonded combinations of the present disclosure allow for many-fold increases in creepage distance, with over seven times increase achieved here.

[0186] The combination of water resistance in environments prone to galvanic corrosion and high dimensional stability of the bonded joints disclosed herein is also advantageous.

[0187] A sufficiently high electrical resistance allows the use of crystallizable glasses as creepage distance extenders (e.g., as feedthroughs in electric compressors) even under (typically) water condensation or even under refrigerant condensation.

[0188] The advantage over ceramics is that the pores of the structure S, i.e. the protruding material, are closed.

[0189] Here, long-term operational durability applications include feedthroughs for electrical or power supplies for heating elements (mainly for use in heatable catalytic elements, for example), for sensors in exhaust gas systems, and also generally for electric compressors, mainly for automotive applications.

[0190] In the previously disclosed embodiments, the crystallites may contain crystallization nuclei at least partially at their grain boundaries and / or have deposits comprising lanthanum, particularly comprising lanthanum compounds, at least partially located at the grain boundaries of the crystallites.

[0191] In operation, the crystalline aggregates of the crystallizable or partially crystallized glasses disclosed herein inhibit volume elements of the at least partially crystallized glasses from displacing one another.

[0192] In the bonded joints of the present disclosure, the surface of the at least partially crystallized glass is free of a meniscus.

[0193] In the case of the bonded joints of the present disclosure, the bonded partners are metals, in particular steels, such as plain steel, stainless steel, stainless steel, and high temperature stable ferritic steels also known as Thermax, for example under the trade names Thermax 4016, Thermax 4742 or Thermax 4762, or under the trade names Crofer22 APU or Crofer22 H, or NiFe based materials, for example NiFe45, NiFe47 or nickel plated pins, or Inconel, for example under the trade names Inconel 718 or X-750, or for example CF25, Alloy 600, Alloy 601, Alloy 625, Alloy 630, Alloy 640, Alloy 650, Alloy 660, Alloy 670, Alloy 680, Alloy 690, Alloy 701, Alloy 712, Alloy 720, Alloy 730, Alloy 740, Alloy 751, Alloy 760, Alloy 770, Alloy 781, Alloy 790, Alloy 801, Alloy 810, Alloy 820, Alloy 830, Alloy 840, Alloy 851, Alloy 860, Alloy 870, Alloy 881, Alloy 890, Alloy 901, Alloy 910, Alloy 920, Alloy 930, Alloy 940, Alloy 951, Alloy 960, Alloy 970, Alloy 981, Alloy 991, Alloy 992, Alloy 993, Alloy 994, Alloy The steels may include those known under the names 690, SUS310S, SUS430, SUH446 or SUS316, or austenitic steels such as 1.4762, 1.4828 or 1.4841, metals from the Kanthal heating wire group, or high-temperature stable ceramic compounds such as forsterite, aluminum oxide-based ceramics or zirconium oxide-based ceramics, for example ceramics containing Y-stabilized zirconium oxide.

[0194] The conjugates of the present disclosure are -8 mbar * It comprises an at least partially crystallized glass having a helium leak rate of less than 1 / s and / or an elastic modulus of 80 GPa to 200 GPa, preferably 100 GPa to 125 GPa.

[0195] For the crystallizable or at least partially crystallized glasses of the present disclosure, the CaO content of the crystallizable or at least partially crystallized glass may be at least 35 mol% and at most 46 mol%, preferably at least 35 mol% and less than 43.5 mol%, and / or the MgO content of the crystallizable or at least partially crystallized glass may be 5 mol% and less than 13 mol%.

[0196] In the case of crystallizable or at least partially crystallized glasses of the present disclosure, the glasses can exist as at least partially crystallized glasses and can be used in a temperature range of 20°C to 700°C. * 10 -6 / K, preferably above 10 * 10 -6 / K, and particularly preferably, the linear thermal expansion coefficient of the at least partially crystallized glass is greater than 9 / K in the temperature range of 20°C to 1000°C. * 10 -6 / K above, preferably 9.5 * 10 -6 / Super.

[0197] In the case of crystallizable or at least partially crystallized glasses of the present disclosure, the glass exists as a crystallizable glass and has a transformation temperature T above 720°C. g may have:

[0198] For crystallizable or at least partially crystallized glasses of the present disclosure, the temperature of the crystallizable glass is 10 8 Ω * The specific electrical resistivity of 10 ... k It's 100.

[0199] In the case of the crystallizable or at least partially crystallized glasses of the present disclosure, the at least partially crystallized glass comprises crystallites of calcium-magnesium silicate, preferably a CaO-rich calcium-magnesium silicate, in particular a CaO-rich calcium-magnesium island silicate and / or sorosilicate, e.g., merwinite and / or mixed crystals having a merwinite structure, and alternatively or additionally, crystalline phases having a melilite structure and / or mixed crystals thereof, such as akermanite CaMgSiO and / or gehlenite CaAl[AlSiO], and / or crystalline phases having an augite structure. [Explanation of symbols]

[0200] 1. Crystalline aggregates 2 Crystallites 21 Crystallites at grain boundaries 22 Needle-shaped crystallites 23 Crystallites formed in rod or platelet shapes 3 Residual glass 4 pores 5 conjugate 51 First joining partner 511 Upper end of first joining partner 52 Second joining partner 521 Upper end of second joining partner 53 Insulating materials 54 Part of an insulating part placed between mating members 55 A part of the insulating member protruding from the mating member 51, i.e., a creepage distance extension 56 Reinforcement 57 Substantially annular members 58 Substantially annular members 59 Substantially annular members M center line S Structure forming creepage distance extension O Upper surface of insulating member 53 Rv Radius of curvature at the end St: A line drawn with a pen on the surface of structure S or on surface O R Radial direction

Claims

1. La ２ O ３ More than 0.3 mol% to less than 5 mol%, preferably 4.5 mol% or less, particularly preferably 4 mol% or less; Nb ２ O ５ 0mol%~9mol%、 That ２ Oh ５ 0mm%~7mm%、 where Σ(A ２ 9 ５ ) 0.02mllee~molle、 wherein A is an element which in its oxide normally has the oxidation state V+, and includes in particular Nb, Ta, or P, and / or mixtures thereof; SiO 2 30 mol% to 40 mol%, Al 2 O 3 3 mol% to 12 mol%, CaO 32 mol% to 46 mol%, MgO 5 mol% to 15 mol%, ZnO 0 mol% to 10 mol%, A crystallizable or at least partially crystallized glass comprising:

2. oxide RO, and Σ(RO) ≦55mol% wherein R is an element that normally has the oxidation state II+ in the oxide, and includes in particular Ca, Mg, or Zn, and / or mixtures thereof.

2. The crystallizable or at least partially crystallized glass of claim 1, wherein:

3. ZrO ２ 0 mol % to 4 mol %, preferably up to 3 mol %, and / or TiO ２ 0 mol % to 4 mol %, preferably up to 3 mol %, and / or MnO ２ 0mol%~5mol% 3. The crystallizable or at least partially crystallized glass of claim 1 or 2, further comprising:

4. the CaO content of said crystallizable or at least partially crystallized glass is at least 35 mol % and at most 46 mol %, preferably at least 35 mol % and less than 43.5 mol %, and / or the MgO content of the crystallizable or at least partially crystallized glass is between 5 mol% and less than 13 mol%, 4. Crystallizable or at least partially crystallized glass according to claim 1.

5. The glass is present as a crystallizable glass and has a transformation temperature T above 720°C. ｇ 5. The crystallizable or at least partially crystallized glass according to claim 1, wherein

6. The crystallizable glass has a linear thermal expansion coefficient of 8 or less in the temperature range of 20°C to 300°C. ＊ 10 －６ / K, and preferably in the temperature range of 20°C to 700°C ＊ 10 －６ 6. The crystallizable or at least partially crystallized glass according to claim 1, wherein the crystallization temperature is greater than 1000 K.

7. the glass is present as an at least partially crystallized glass, In the temperature range of 20°C to 700°C, 9 ＊ 10 －６ / K, preferably 10 ＊ 10 －６ / K, Particularly preferably, the linear thermal expansion coefficient of the at least partially crystallized glass is 9 or less in the temperature range of 20°C to 1000°C. ＊ 10 －６ / K, preferably 9.5 ＊ 10 －６ / K over, 7. Crystallizable or at least partially crystallized glass according to any one of claims 1 to 6.

8. The temperature of the crystallizable glass is 10 ８ Ω ＊ The specific electrical resistivity of t ｋ 8. The crystallizable or at least partially crystallized glass according to claim 1, wherein the crystallization temperature is 100°C.

9. The at least partially crystallized glass is preferably composed of crystallites of calcium-magnesium silicates, preferably CaO-rich calcium-magnesium silicates, in particular CaO-rich calcium-magnesium island silicates and / or sorosilicates, such as merwinite and / or mixed crystals having a merwinite structure, and alternatively or additionally akermanite Ca ２ MgSi ２ O ７ and / or gehlenite Ca ２ Al[AlSiO ７ 9. The crystallizable glass or at least partially crystallized glass according to claim 1, comprising a crystalline phase having a melilite structure such as ] and / or a mixed crystal thereof, and / or a crystalline phase having an augite structure.

10. comprising an at least partially crystallized glass and a joining partner; The glass is an at least partially crystallized glass according to any one of claims 1 to 9 or is made or can be made from an at least partially crystallizable glass according to any one of claims 1 to 9. conjugate.

11. 10. An article of manufacture, in particular a holding element and / or an insulating element and / or an additional structure, comprising an at least partially crystallized glass according to any one of claims 1 to 9.

12. 12. The product according to claim 11, which can be produced from a sintered body comprising at least partly the crystallizable glass according to any one of claims 1 to 9, wherein the sintered body comprises the crystallizable glass, preferably as a glass powder, and particularly preferably the glass powder comprises powder particles with a particle surface.

13. 10. An article of manufacture, the article being a bonded assembly, comprising an at least partially crystallized glass according to any one of claims 1 to 9 and a bond partner.

14. the at least partially crystallized glass comprises, by volume, less than 10%, preferably less than 5%, of residual glass; the at least partially crystallized glass comprises crystalline aggregates; the crystalline aggregate is formed from a large number of crystallites, the crystallites are preferably formed in the form of needles and / or platelets, The crystallites are particularly preferably distributed throughout the at least partially crystallized glass and arranged radially, for example in the form of spherulites and / or fans and / or rods and / or platelets, in particular comprising one insulating element.

15. the crystallites contain crystallization nuclei at least partially at grain boundaries, and / or accumulations comprising lanthanum, in particular lanthanum compounds, at least partially located at the grain boundaries of the crystallites; 15. The product of claim 13 or 14.

16. The absolute value of the difference between the thermal expansion coefficients of the joining partners and the at least partially crystallized glass is 5 ＊ 10 －６ / K or less, preferably 3 ＊ 10 －６ / K or less, particularly preferably 1×10 －６ 16. The product of any one of claims 13 to 15, wherein the viscosity is less than or equal to 1 / K.

17. A product according to any one of claims 13 to 16, which is vibration and vibration resistant as measured in accordance with ISO 16750-3.

18. 18. The article of manufacture according to any one of claims 13 to 17, wherein the surface of the at least partially crystallized glass is free of a meniscus.

19. In the transition area between the surface of the joining partner and the surface of the at least partially crystallized glass, preferably 1 cm ３ 19. The product according to claim 13, wherein an at least predominantly amorphous glass layer is arranged, the glass layer having fewer than 10 pores per pore and preferably having a thickness of 5 μm or less, particularly preferably 2 μm or less, very particularly preferably 1 μm or less.

20. The joining partners are metals, in particular steels, such as mild steel, stainless steel, stainless steel, and high-temperature stable ferritic steels also known as Thermax, for example under the trade names Thermax 4016, Thermax 4742 or Thermax 4762, or Crofer 22 APU or Crofer 22 H, or NiFe-based materials, for example NiFe45, NiFe47 or nickel-plated pins, or Inconel, for example under the trade names Inconel 718 or X-750, or for example CF25, Alloy 600, Alloy 625, Alloy 630, Alloy 640, Alloy 650, Alloy 660, Alloy 670, Alloy 680, Alloy 690, Alloy 700, Alloy 710, Alloy 720, Alloy 730, Alloy 740, Alloy 750, Alloy 760, Alloy 770, Alloy 780, Alloy 790, Alloy 800, Alloy 810, Alloy 820, Alloy 830, Alloy 840, Alloy 850, Alloy 860, Alloy 870, Alloy 880, Alloy 890, Alloy 900, Alloy 910, Alloy 920, Alloy 930, Alloy 940, Alloy 950, Alloy 960, Alloy 970, Alloy 980, Alloy 9 ...

20. The article of manufacture according to any one of claims 13 to 19, comprising a metal from the group of austenitic steels such as SUS690, SUS310S, SUS430, SUH446 or SUS316, or austenitic steels such as 1.4828 or 1.4841, or a high-temperature stable ceramic compound, such as an aluminum oxide-based ceramic or a zirconium oxide-based ceramic, for example a ceramic containing Y-stabilized zirconium oxide.

21. 10 －８ mbar ＊ and / or has a helium leak rate of less than 1 / s; comprising an at least partially crystallized glass having an elastic modulus of 80 GPa to 200 GPa, preferably 100 GPa to 125 GPa; 21. The product of any one of claims 13 to 20.

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