• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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    • 专利摘要:
    Sodium-resistant joining glass (1) from the system SiO 2 - B 2 O 3 - Na 2 O - Al 2 O 3 for producing a joint with a ceramic or a metal which is substantially free of ZrO 2, as well as joining of a ceramic or a metal with further joining components (2, 3, 4) with the joining glass (1) and electrical feedthrough containing the joining glass (1) as insulation material.
    公开号:CH708728B1
    申请号:CH01580/14
    申请日:2014-10-15
    公开日:2019-05-31
    发明作者:Jens Suffner Dr
    申请人:Schott Ag；
    IPC主号:
    专利说明:

    Description: The invention relates to sodium-resistant joining glasses, with which joining connections with ceramics such as aluminum oxide (also called Al2O3, alumina ceramic or Al 2 O 3 ceramic) and / or metals and / or combinations thereof can be produced and their applications. Sodium-resistant joining glasses are joining materials which can withstand liquid sodium or vaporous sodium in particular and are thus suitable for the production of joining compounds which are exposed to liquid sodium and / or sodium vapor and / or other aggressive sodium compounds and / or media containing sodium.
    Such sodium-resistant joining glasses are of interest, for example, for the production of energy storage and energy generation units in which liquid sodium and / or sodium compounds are used as the electrolyte or cooling medium. Examples of such energy generation units are batteries, but also nuclear reactors, in particular hatchery reactors, in which the joining glass is used in technical components that can come into contact with the sodium. Such technical components are, in particular, electrical feed-through devices with which, for example, sensors and / or actuators and / or electric motors are supplied with electrical current. Another area of application is equipment for the disposal of, in particular, toxic materials, the processing of which produces sodium compounds and / or liquid and / or vaporous sodium.
    [0003] Electrochemical storage and energy generation technology has also gained considerable interest in recent years. It can be used in the field of electromobility, for decentralized power supply, as an emergency power system and mainly due to the increased share of renewable energies to stabilize the network system.
    Various battery technologies are under discussion here, with the Li-ion batteries (LIB) being the most discussed. Another class of batteries are high-temperature sodium batteries (Sodium Beta Battery, SBB). Their advantages over the LIB are the higher energy density and high energy efficiency. SBB uses liquid sodium as a negative electrode at elevated temperatures, usually more than 250 ° C. A distinction is generally made between two variants: one is the sodium-sulfur battery (Na / S), which uses sulfur as the positive electrode. The other is the sodium metal chloride battery, also called the ZEBRA battery, which uses metal chlorides such as nickel or iron chloride as the positive electrode and sodium tetrachloroaluminate (NaAICI 4 ) as the liquid electrolyte. Both types have in common that they use a sodium ion-conducting membrane made of ß- or ß-Al 2 O 3 and a housing part made of a-Al 2 O 3 and this if necessary. can also be connected to a metallic cover. The generic term alumina used in this description or synonym alumina ceramic or synonym AI 2 O 3 or likewise synonym AI 2 O 3 ceramic includes in particular the embodiments a- and / or β- and / or β-alumina. The use of the term aluminum oxide also means no restriction to the degree of purity and thus the content of Al 2 O 3 in the Al 2 O 3 ceramic and / or the component in question.
    In the electrochemical cell, the joining connection between the components made of ceramic, in particular aluminum oxide, or another metal component is a critical component, since it determines the service life. If leaks occur in this area, the liquid sodium can come into contact with the atmosphere and start to burn. The task of the joining glass as joining material is to achieve a hermetically sealed joining that extends over the entire service life of the battery. This can be achieved in particular by a good adaptation of the thermal expansion coefficient of all materials involved, which makes the joining tolerant to the operating conditions, and a very good chemical resistance of the glass to all active components, without impairing their function.
    A distinction is made between two basic types of joining glasses for batteries: silicate-based glasses and borate-based glasses. The advantage of the borate-based glasses is that they usually have very good resistance to the molten sodium, but they have poorer properties in terms of their chemical resistance to the metal chloride. In addition, the frequently used aluminoborates often have little stability against crystallization, which limits them from the point of view of the process. A special form is listed, for example, in US Pat. No. 8,334,053 B2, which describes separate glasses depending on the corrosion resistance of the anode and cathode of an SBB. For example, a high silicon-containing glass with more than 40 wt.% SiO 2 and less than 25 wt.% B 2 O 3 is used on the metal salt side and on the sodium side a borate glass with a very low silicon content of less than 20 wt. % SiO 2 and more than 35% by weight B 2 O 3 .
    [0007] GB 2 207 545 A describes the use of 8245 borosilicate glass from Schott AG as joining glass for a Na / S battery. This glass has a very good chemical stability towards the media of the Na / S battery, but due to the low linear thermal expansion coefficient a 2O - 3 oo ° c of 5.2 · 10 -6 K _1 it is only partially hermetic with aluminum oxide to add.
    US 4 268 313 A describes a borosilicate glass for use in a Na / S battery. However, this contains a total of at least 6% by weight of the alkaline earth metal oxides CaO, SrO and BaO. These components are helpful for glass formation and can improve the flow behavior, but can reduce the performance of the active components by ion transfer with the electrolyte, in particular an SBB.
    CH 708 728 B1 [0009] A joining glass for an energy store is described in US Pat. No. 8,034,457 B2, which contains a maximum of 25% by weight of B 2 O 3 . The limitation of the B 2 O 3 content to the above-mentioned upper limit is explained by the fact that the joining glass would otherwise be attacked too strongly by adsorbed water.
    [0010] US Pat. No. 8,043,986 B2 contains an SBB joining glass with at least 0.1 to 10% by weight of ZrO 2 . Zirconium oxide is used in this document to improve chemical resistance. However, it also leads to a stronger tendency towards phase separation and crystallization and, due to the high raw material costs, to a reduction in the efficiency of the glass production process.
    Against this background, it is an object of this invention to provide a joining glass which is suitable for producing joining compounds which have a very good resistance to sodium and which is used for joining metals and / or ceramics, in particular aluminum oxide and / or NASICON , is suitable, and in particular has both a very good resistance to molten metal salts and to sodium melts. It is also an object of the invention to provide advantageous uses. Another object of the invention is to provide a joining connection of ceramics, in particular aluminum oxide and / or NASICON, by means of the joining glass, the provision of electrochemical / n energy storage / or energy generation units containing the joining glass and the provision of electrical feedthroughs including the joining glass as an electrically insulating sealing material, all of which benefit from the properties of the joining glass and thus have improved properties.
    The object is achieved by the joining glass, the joining connection and the electrochemical energy storage and / or energy generation unit as well as the implementation and use according to the claims. Preferred embodiments result from the claims dependent on the main claim.
    Unless explicitly stated otherwise, all components and / or ingredients are given in weight percent on an oxide basis.
    A joining glass according to the invention contains 40% to 50% SiO 2 and more than 25% up to 30% B 2 O 3 . This combination in particular sets the coefficient of thermal expansion and at the same time controls the flow behavior. The joining glass further contains 5% to 15% Na 2 O and 17% to 25% Al 2 O 3 according to the invention. In particular, the good chemical resistance of the joining glass can be adjusted via these components.
    The joining glasses according to the invention optionally and in total contain less than 2% of alkaline earth metal oxides MO. MO stands for CaO, SrO and / or BaO, which can be contained in the joining glass individually or in any possible combination up to the stated limit of the total content. Alkaline earth metal oxides can have a positive effect on the flow behavior of the glasses. Since they can reduce the performance of one of the active components by diffusion or ion transfer with the sodium ions of the electrolyte, their content is reduced to a minimum according to the invention.
    Furthermore, the joining glass according to the invention is free of ZrO 2 except for at most impurities. Contamination can be introduced into the glass through contamination of the raw materials used for glass production and / or through contamination and / or corrosion of the melting units used. Such impurities generally do not exceed 0.2% by weight, in particular 0.1% by weight. Of course, this also includes the complete freedom of ZrO 2 . Contrary to the teaching of the prior art mentioned, it was found that the joining glasses according to the invention have very good chemical resistance, although ZrO 2 is not used to improve the chemical resistance. It was also found that ZrO 2 can act as a seed that promotes crystallization during processing. Crystallization (including partial crystallization) of the joining glass according to the invention is undesirable since the crystalline regions lead to difficulties in producing the joining connection and / or even cause leaks in the joining connection. The joining glass according to the invention is therefore particularly advantageously an amorphous glass, in particular without crystallized areas.
    Tests of the joining glasses have shown that, contrary to the state of the art mentioned, hydrolytic aging could not be determined at increased contents of B 2 0 3 of more than 25%. Instead, the inventors have found that a higher boron content of more than 25% to 30% surprisingly increases the resistance to sodium melts. Thanks to the composition mentioned, the joining glasses according to the invention can advantageously be melted free of crystallization and segregation.
    In a preferred embodiment, a joining glass according to the invention contains up to 5% ZnO and / or up to 5% TiO 2 and / or up to 5% SnO 2 and / or up to 15% MgO. These optional additional components can be contained in the joining glass individually or in any combination. ZnO, TiO 2 and / or SnO 2 in particular improve the chemical resistance in the alkaline range. MgO can optionally be included and its content can be selected so that the thermal expansion of the joining glass can be adapted to the joining partner. Usually, a higher MgO content increases the thermal expansion coefficient of the joining glass. An MgO content of 0- <2% can also advantageously be provided.
    The composition of the joining glass is particularly preferably selected within the previously specified limits such that the linear thermal expansion coefficient a 2O - 3 oo ° c of the joining glass values between 5.5 · 1CT 6 K _1 up to 10.5 • 10 - 6 K " 1 , preferably from 5.5 · 10 -6 K _1 up to 8.5 · 10 -6 K _1 , very particularly preferably from 6.0 · 10" 6 K _1 up to
    CH 708 728 B1
    8.0 · 10 6 K 1 . In this way, an adaptation of the joining glass to the thermal expansion behavior of aluminum oxide is achieved in particular.
    It may also be preferred that the joining glass additionally contains up to 30% by volume of an oxidic filler, in particular an inorganic oxide. These fillers can be used in particular to adjust the thermal expansion behavior and / or the corrosion resistance and / or the flow behavior, the filler preferably being in the form of particles and / or fibers. Examples of such fillers are MgO, Al 2 O 3 and / or stabilized ZrO 2 . These can be used in particular to adapt the thermal expansion behavior to metals as joining partners. The fillers are usually not integrated into the glass matrix, but are isolated in this, so to speak.
    The invention also comprises a joining connection between a first joining component and a second joining component by means of a previously described joining glass. A joining component is understood to mean any element that is connected to the joining glass. The joining glass is in particular a material connection with the respective joining component. A cohesive connection is characterized in that the connection partners, here the respective joining component with the joining glass, are held together by atomic or molecular forces. There are non-releasable connections that can only be separated by destroying the connecting means, here the joining glass. The joining glass is particularly advantageously able to provide a hermetically sealed joining connection between the joining components as joining partner.
    The joining connection of the joining components is produced by the joining glass and is accordingly present at the joining point of the respective joining component which is connected to the joining glass. The joint is accordingly the surface on the surface of the respective joint component that is in contact with the joint glass. The joining component can be connected to the joining glass over the entire surface, but also in any areas, and via this to the other joining component. As described, the joining glass according to the invention is intended for joining ceramics and / or metals. Accordingly, a joining connection according to the invention provides that the first joining component comprises a ceramic or a metal, at least at the joining point. The second joining component also comprises a ceramic or a metal, at least at the joining point. Combinations of metal and ceramic are of course also possible and encompassed by the invention. In combination, this also means that the second joining component can be a hybrid component that is composed of metal and ceramic in the area of the joining connection. In other words and, to put it in a nutshell, the joining glass can in particular be used to produce joining connections from metal to metal or from ceramic to metal or from ceramic to ceramic or from metal or ceramic to a hybrid component made of metal and ceramic.
    As described, the joining glass according to the invention is particularly suitable for the joining of aluminum oxide, so that it provides a joining connection according to the invention that the first joining component comprises aluminum oxide at least at the joint, in particular consisting of aluminum oxide. The second joining component comprises, at least at the joining point, a metal and, alternatively or in combination, aluminum oxide. The combination results in particular in a joining component in the form of a hybrid component which is composed of metal and aluminum oxide in the region of the joining connection.
    It is preferred if the aluminum oxide of the first joining component comprises α-aluminum oxide or β-aluminum oxide or β-aluminum oxide, in particular if it consists of these. The aluminum oxide of the second joining component is particularly preferred, if it consists of aluminum oxide at least at the joint or comprises this, likewise α-aluminum oxide or β-aluminum oxide or β-aluminum oxide. However, this does not mean that the embodiment of the aluminum oxide of the first joining component has to match the embodiment of the aluminum oxide of the second joining component, rather it can be advantageous if the embodiments of the aluminum oxide are different in the first and second joining component, e.g. if the first joining component comprises a-alumina and the second joining component ß-alumina or ß-alumina. This configuration is used in particular in SBB and is of interest to them.
    It is also possible and preferred if the ceramic instead of aluminum oxide from the class of NASICON ceramics (sodium super ion conductor, Na. Super ion conducting), typically of the type A x B y (PO 4 ) 3 with an alkali metal A (e.g. Na) and a multivalent metal ion B (e.g. Fe, Cr, Ti). All of the above-mentioned embodiments are also possible with these types of ceramic.
    Also possible are joining components in the housings of sensors and / or actuators which are exposed to aggressive media, in particular liquid sodium or sodium salts. Possible areas of application for this are e.g. in the synthesis of liquid sodium by electrolysis of molten salts and in the area of cooling of breeding reactors with liquid sodium.
    As described, the second joining component also preferably comprises a metal, at least at the joining point. Particularly preferably, this metal has a linear thermal expansion coefficient a 2O - 3 oo ° c on which (in the same temperature range) is greater or equal to the linear thermal expansion coefficient a 2O _ 3O o ° c of the ceramic, in particular of aluminum oxide is.
    CH 708 728 B1 The value of the linear thermal expansion coefficient a 2 o-3oo ° c of this metal is particularly preferably more than 8 · 10_ 6 K _1 . Examples of such preferred metals are stainless steels, low-carbon steels and / or nickel alloys.
    The joining connection according to the invention allows the production of electrochemical energy storage and / or energy generation units with increased service life and / or increased efficiency. These are therefore also included in the invention. Examples of electrochemical energy stores are accumulators in the charging mode, examples of electrochemical energy generation units are batteries or accumulators in the discharging mode. Reactors for chemical and / or biochemical reactions are also possible in which the energy state is represented by the respective oxidation and reduction state of the starting materials and products. An energy storage and / or energy generation unit according to the invention is particularly preferably a sodium-sulfur battery or sodium metal chloride battery with a joint connection according to the invention.
    The joining connection according to the invention also allows the production of lead-through elements, in particular electrical lead-through elements.
    An advantageous electrical bushing element comprises a metallic support element, which has a bushing opening, and a metallic functional element. The functional element is kept electrically insulated from the carrier element in the lead-through opening by the inventive joining glass described. The through opening is closed at the same time by the joining glass, in particular hermetically sealed.
    The joining glass according to the invention is very particularly preferably used for the production of a sodium-sulfur battery or a sodium metal chloride battery, in particular for hermetically sealing the housing thereof and / or for closing and / or connecting the membrane components in their electrolyte cells. The connection can also be made with suitable support elements, etc.
    The bushing element according to the invention is particularly preferably used in devices for the disposal of hazardous substances and / or in nuclear reactors, in particular in hatchery reactors, there in particular as an electrical feedthrough for the safety container and / or as an electrical feedthrough for the cooling circuit. This can include the primary and / or the secondary circuit, which are operated in particular in breeding reactors with liquid sodium as the cooling medium. The lead-through element can come into contact with the liquid sodium and must be able to withstand this permanently. With the lead-through element, pumps and / or sensors in the cooling circuit can be supplied with electrical current and / or signals can be derived from sensors. It is also possible to use the lead-through element in the containment of a reactor. In this case, it can come into contact with liquid sodium and / or sodium vapors, particularly in the event of a malfunction, and still reliably close the safety container. The invention also encompasses the use of a lead-through element described in devices for disposing of hazardous substances, for example when these are burned or chemically reacted, aggressive sodium compounds and / or liquid sodium and / or sodium vapor also being able to form.
    The invention is further explained on the basis of the figures. All figures are purely schematic, the dimensions of the real objects may differ from the dimensions and / or the proportions of the figures. It shows
    1a: the section through a first joining component, which is partially provided with joining glass,
    1b: the section through another first joining component, which is provided in areas with joining glass,
    2a: the section through a component group with a joint connection,
    2b: the section through another component group with a joint connection,
    3: the section through a ZEBRA battery,
    4: the section through another ZEBRA battery,
    5a: the section through a lead-through element
    5b: the top view of a lead-through element according to FIG. 5a,
    6: the section through a further bushing element,
    7: the section through the safety container of a reactor building,
    Fig. 8: the section through the reactor and the safety container of a reactor building.
    Fig. 1a schematically shows the section through a first joining component. The joining component (2) represents, so to speak, the substrate for the joining glass (1), which is located in regions on the surface of the joining component (2) and
    CH 708 728 B1, a cohesive connection with the joining component (2) has been entered into in these areas. The points at which the joining glass (1) is present can be the joining points and are further defined as the joining points at which joining connections are made with other joining components. The joining component (2) with joining glass (1) shown can be used, in particular, in combination with other joining components to produce joining connections. In the present example, the joining component (2) consists of ß-aluminum oxide or ß-aluminum oxide or NASICON. As described, it is also possible that the aluminum oxide (2) of the joining component is only present at the joining points at which the connection with the joining glass (1) is made, and the other areas of the joining component consist of other materials.
    Fig. 1b shows essentially the same joining component with joining glass as Fig. 1a, only that in this example the joining component (3) consists of a-alumina or at least includes this at the joining points at which the joining glass (1) is present is. All other statements made with regard to FIG. 1b can also be applied to FIG. 1b.
    Fig. 2a shows the section through a joint connection, which is formed by a component group connected by the joining glass (1) from the first joining component (2) and the second joining component (3). As can be seen from FIG. 2a, the object shown is in principle a combination of FIGS. 1a and 1b. The material of the first joining component (2) in this figure is again β-aluminum oxide or β-aluminum oxide and the material of the second joining component (3) is α-aluminum oxide. The joining glass (1) connects to the surfaces of the joining components (2, 3) at the joining points and can thus create a hermetic and permanent connection between the joining components (2, 3).
    Fig. 2b shows the section through a similar embodiment as Fig. 2a, only that the first joining component is composed of β-aluminum oxide or β-aluminum oxide (2) and α-aluminum oxide (3). In this exemplary embodiment, the second joining component (4) consists of a metal. It is readily apparent to the person skilled in the art that a large number of different overall components can be produced from the joint connections shown by appropriate combinations, which can be adapted to their use according to the requirements.
    In Fig. 3 the section through a schematic ZEBRA battery is shown. The battery is closed by the cup-shaped housing (4) and the cover (3). Housing (4) and cover (3) are connected to each other by the joining glass (1). The cover (3) represents, so to speak, the first and the housing (4), so to speak, the second joining component of the joining connection described above. The housing (4) of a ZEBRA battery usually consists of metal, e.g. made of a stainless steel, a nickel alloy or a low-carbon steel, and the cover (3) made of aluminum oxide, in particular a-aluminum oxide. The joining glass (1) according to the invention reliably and permanently creates a tight connection between the two joining components cover (3) and housing (4), so that the contents of the ZEBRA battery are securely sealed in the housing.
    Inside the housing is the hollow cylindrical semipermeable membrane (2), which is usually made of ß-alumina or ß-alumina. The space between the inner wall of the housing (4) and the outer wall of the membrane (2) is filled with liquid sodium (11), which forms the anode. Due to the contact with the conductive housing (4), this also acts as an anode. The interior of the hollow cylindrical membrane (2) is e.g. filled with sodium tetrachloroaluminate as electrolyte (10) and acts as a cathode. The semipermeable membrane (2) made of ß-alumina or ß-alumina is only permeable to Na ions. It is connected to the cover (3) by the joining glass (1). The membrane (2) represents, so to speak, the first joining component and the cover (3) the second joining component in the general principle of the joint connection described above. In this joint connection at this point of the ZEBRA battery, it is important that the joint glass (1) for the electrolyte (10) and the liquid sodium (11) is impermeable, since otherwise the electrolyte (10) and / or the liquid sodium (11) could be poisoned by the respective other substance, consequently the battery could be destroyed or at least its capacity could be reduced ,
    The cover (3) itself is an electrical insulator in this example, so that an electrode (52) is required in order to be able to connect the battery with anode and cathode to a circuit. In the present example according to FIG. 3, the metal rod (52) penetrates the cover (3) through the sleeve (51). At this point, it is also conceivable to guide the metal rod (52) or generally the electrode through the cover (2) in a glass-metal bushing with the joining glass according to the invention.
    Fig. 4 shows an alternative embodiment of the ZEBRA battery according to Fig. 3. Because the joining glass (1) at the connection of the housing (4) and cover (41) creates an electrically insulating joining connection between the two joining components, it would be it is also possible to manufacture the cover (41) from a metal or at least an electrically conductive material as shown in FIG. 4 and to design it geometrically so that it does not come into contact with the electrolyte (10) so that the electrode ( 52) can be dispensed with and the lid itself then acts as a cathode. The joining glass then connects in particular the three joining components housing (4), cover (3) and membrane (2) at one point, here in the form of a ring.
    5a schematically shows the section through a lead-through element (20). This contains the carrier element (30), here in the form of a metallic cylinder. This usually represents the external manager. In the applications described, it usually consists of steel. Carbon steels, austenitic and / or ferritic stainless steels can be particularly advantageous. Kovar can also be used for corresponding applications. However, it is also possible for the carrier element (30) to be produced from a ceramic. There is a through opening in the carrier element (30), which connects the top of the carrier element (30) to the rear thereof.
    CH 708 728 B1
    The functional element (31) is arranged in the through opening, here in the form of a rod-shaped electrical conductor, which usually represents the inner conductor. This can consist of various materials, usually Kovar and / or steel and / or copper and / or alloys, such as NiFe and / or CrNi alloys. The joining glass (1) fixes the functional element (31) in an electrically insulated manner from the carrier element (30) in the through opening and closes it. The joining glass (1) according to the invention has the advantage that a hermetically sealed closure can be achieved. Feed-through elements (20) are usually produced by fusing the joining glass (1) with the carrier element (30) and the functional element (31).
    Fig. 5b shows the top view of the lead-through element (20) according to Fig. 5a. In the case shown, the functional element (31) is arranged concentrically in the circular passage opening. This geometry is particularly suitable for so-called pressure glazing, in which the coefficient of thermal expansion of the carrier element (30) is greater than that of the joining glass (1). When cooling after melting, the carrier element (30) shrinks onto the joining glass (1), so to speak, and exerts a compressive stress on it, which increases the mechanical pull-out forces which are required for pressing the joining glass (1) out of the through opening.
    The bushing element (20) of FIGS. 5a and 5b represents a bushing element from the large bushing category.
    Fig. 6 shows the section through a further bushing element (20) with a plurality of bushing openings in a carrier element (30). This so-called planar element has dimensions that are wide rather than high. The through openings can be arranged in a matrix. The matrix itself is variable, which means that the location of the through openings can be selected depending on the desired application. This embodiment can e.g. used to provide electrical power to multiple electrical and / or electronic components, e.g. to drive them and / or to pass signals generated by these components through the carrier element (30). The carrier element (30) may or may not seal the housing of a device in question. The carrier element (30) can in particular be made of a metal and / or an alloy or a ceramic material.
    7 shows the containment (80) of an energy generating device, for example a reactor, in particular a nuclear reactor, or a device for removing dangerous materials. These must be securely encapsulated in the encapsulation, even in emergency and fault situations. A feedthrough element (20) according to the present disclosure is advantageously used to provide contact to the reactor and / or to devices within the containment. Such devices are e.g. Devices for monitoring the operating conditions of the reactor and / or for controlling the reactor or other devices.
    In Fig. 8 an energy generating device (81) such as a reactor is shown. The schematic representation of the reactor (81) contains its cooling circuit, in the case of a breeding reactor in particular its primary and / or secondary circuit, which is operated with liquid sodium as the coolant. Control and / or sensor and / or actuation devices such as electric motors, in particular in pumps, can be supplied with electrical current via the lead-through element (20). Likewise, the security container, as described in connection with FIG. 8, can be provided with a lead-through element (10).
    Joining glasses (1) according to the invention were produced in conventional glass melting processes. The details of the glass melting are known to the person skilled in the art and will not be repeated here.
    The following Table 1 summarizes compositions and physical properties of four exemplary joining glasses (1) No. 1 to No. 4 according to the invention.
    Composition: number 1 No. 2 No. 3 No. 4 SIO 2 49 44 40 42 B2O3 26 26 30 26 Na 2 O 8th 10 6 15 Al2O3 17 20 24 17 Characteristics: Tg [° C] 546 488 548 533 Density [g / cm 3 ] 2.35 2.26 2.43 2.40 U20-300 ° c [10 6 K 1 ] 5.80 6.61 5.62 8.34
    CH 708 728 B1
    Table 1: Examples of joining glasses according to the invention, percentages by weight based on oxide.
    Table 2 shows the composition and physical properties of joining glasses which lie outside the glass composition range according to the invention and are referred to below as comparative examples as VG 1 and VG 2.
    The glasses of the comparative examples have higher contents of SiO 2 and lower contents of B 2 O 3 and Al 2 O 3 than the joining glasses according to the invention.
    Composition: VG 1 VG 2 SiO 2 69.8 68.0 B2O3 15.6 13.0 N32O 7.2 12.0 Al2O3 5.4 5.0 ZnO 2.0 1.0 BaO - 1.0
    Characteristics:
    Tg [° C]
    505 565
    Density [g / cm 3 ]
    2.31 2.44
    U20-S00 c [10 6 K 1 ]
    5.2 6.7
    Table 2: Comparative examples of joining glasses, percentages by weight based on oxide.
    The resistance of the joining glasses according to the invention from Table 1 was determined in comparison to the glasses VG 1 and VG of the comparative examples in Table 2. For this purpose, a glass cube from the relevant glass with the edge length is placed in a bath of molten sodium at 300 ° C. for a defined period of 100 h and the appearance of the sample and the loss of mass are determined. All of the joining glasses according to the invention from Table 1 proved to be more stable than the comparative examples from Table 2 or had a greater thermal expansion, which makes them more suitable for producing joining connections with metals.
    The advantage of the joining glasses according to the invention over the prior art lies in their applicability for the production of joining bonds with ceramics and / or metals and in their improved chemical resistance.
    权利要求:
    Claims (16)
    [1]
    claims
    1. joining glass (1) for producing a joining connection with at least one ceramic or a metal which, apart from at most impurities, is free of ZrO 2 , containing, in% by weight on an oxide basis,
    SiO2 40-50 B2O3 > 25-30 Na 2 O 5-15 Al2O3 17-25 Σ MO 0- <2,
    where MO stands for, individually or in any combination, CaO and / or SrO and / or BaO.
    [2]
    2. joining glass (1) according to claim 1, containing individually or in any combination,
    ZnO 0-5
    TiO 2 0-5
    CH 708 728 B1
    SnO 2 0-5
    MgO 0-15.
    [3]
    3. joining glass (1) according to any one of the preceding claims, which has a linear thermal expansion coefficient «20-300 c in the temperature range from 20 to 300 ° C from 5.5 · 10 -6 K _1 up to 10.5 · 10 -6 K _1 has, preferably from 5.5 · 10 -6 K _1 up to 8.5 · 10 -6 K _1 , particularly preferably from 6.0 · 10 -6 K _1 up to 8.0 · 10 -6 K _1 .
    [4]
    4. Joining glass (1) according to any one of the preceding claims, which additionally contains up to 30 vol .-% of an oxidic filler, in particular for adjusting the thermal expansion behavior and / or the corrosion resistance and / or the flow behavior, the filler preferably in the form of Particles and / or fibers are present.
    [5]
    5. Joining connection between a first joining component (2) and a second joining component (3, 4, 41) by means of a joining glass (1) according to one of the preceding claims, wherein the joining glass (1) is the joining point of the first joining component (2) with the joining point of the second joining component (3, 4, 41) connects.
    [6]
    6. Joining connection according to claim 5, wherein the first joining component (2) comprises a ceramic at least at its joining point and the second joining component (3, 4, 41) comprises a metal and / or a ceramic at least at its joining point.
    [7]
    7. Joining connection according to one of claims 5 to 6, wherein the ceramic at the joint of the first joining component (2) and / or the second joining component (3, 4, 41) is selected from the group aluminum oxide and / or NASICON.
    [8]
    8. Joining connection according to one of claims 6 or 7, wherein the metal of the second joining component (41) has a linear thermal expansion coefficient a 2O -3oo ° c, which is greater than or equal to the linear thermal expansion coefficient a 2O -3oo ° c in the same temperature range Ceramic is.
    [9]
    9. Joining connection according to claim 5, wherein the first joining component (2) comprises a metal at least at its joining point and the second joining component (3) comprises a metal at least at its joining point.
    [10]
    10. Joining connection according to one of claims 6 to 9, wherein «20-300 C> 8 · 10 6 K 1 applies to the metal (41) of the second joining component.
    [11]
    11. Electrochemical energy storage and / or energy generation unit, preferably sodium-sulfur battery or sodium-metal chloride battery, contains at least one joint connection according to one of claims 5 to 10.
    [12]
    12. bushing element (20), preferably electrical bushing element, comprising at least one joint connection according to one of claims 5 to 10.
    [13]
    13. Electrical lead-through element (20) with a metallic carrier element (30) which has a lead-through opening, and a metallic functional element (31) which of the joining glass (1) according to one of claims 1 to 4 in the lead-through opening is electrically insulating from the carrier element (30) and the passage opening is kept closed.
    [14]
    14. Use of a joining glass (1) according to one of claims 1 to 4 for the production of a sodium-sulfur battery or a sodium-metal chloride battery for hermetically sealing the housing (4) and / or for closing the membrane components (2).
    [15]
    15. Use of a lead-through element (20) according to one of claims 12 to 13 in devices for the disposal of hazardous substances.
    [16]
    16. Use of a bushing element (20) according to one of claims 12 to 13 in nuclear reactors, in particular hatchery reactors, in particular as an electrical feedthrough for the safety container or as an electrical feedthrough for the cooling circuit.
    CH 708 728 B1
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    同族专利:
    公开号 | 公开日
    FR3013703B1|2019-06-14|
    DE102013224111A1|2015-06-11|
    JP6104226B2|2017-03-29|
    CN104671663B|2018-10-23|
    KR20150060529A|2015-06-03|
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    FR3013703A1|2015-05-29|
    CN109180003B|2021-12-10|
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    GB2522305A|2015-07-22|
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    CN104671663A|2015-06-03|
    GB201420295D0|2014-12-31|
    DE102013224111B4|2017-01-12|
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    法律状态:
    2016-10-31| PCAR| Change of the address of the representative|Free format text: NEW ADDRESS: GARTENSTRASSE 28 A, 5400 BADEN (CH) |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102013224111.9A|DE102013224111B4|2013-11-26|2013-11-26|Sodium-resistant joining glass and its use, joint connection, energy storage device and / or energy generating device|
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