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    • 专利摘要:
    The present invention relates to a sealing glass which has improved water resistance, free of PbO, with the exception of at most a few impurities, and which has a coefficient of thermal expansion a (25-300) ranging from 14.10-6K-1 to 17.10-6K-1 and preferably has a glass transition temperature Tg ranging from 390 ° C to 430 ° C, containing, in molar percentage on an oxide basis, from 5 to 7 of B2O3, 10 to 14 Al2O3, 36 to 43 P2O5, 15 to 22 Na2O, 12.5 to 20 K2O, 2 to 6 Bi2O3 and > 0 to 6 of oxide R, wherein the oxide R is an oxide selected from MnO 2, SiO 2, SnO 2, Ta 2 O 5, Nb 2 O 5, Fe 2 O 3, GeO 2, CaO and mixtures thereof.
    公开号:FR3071243A1
    申请号:FR1858294
    申请日:2018-09-14
    公开日:2019-03-22
    发明作者:Ina Mitra；Miriam Kunze；Linda Johanna Bartelt；Sabrina Wimmer；Frank Kroll；Hauke Esemann；Bernd Hoppe；Jorg Witte
    申请人:Schott AG；
    IPC主号:
    专利说明:

    High expansion sealing glass having improved water resistance, and uses of this glass
    The subject of the present invention is firstly a sealing glass having a high expansion, in particular a phosphate glass with high expansion, which is suitable in particular for assembling components consisting of metals, in particular light metals, and the invention also having for object seals comprising this sealing glass, and the uses thereof. Compared with the state of the art, the sealing glass according to the invention has better water resistance.
    A person skilled in the art knows that a glass or a sealing glass within the meaning of the present disclosure is an amorphous compound of the individual components of the glass. For the purposes of the present invention, crystal zones may be present. Sealing glass can also be designated by the term "inorganic multicomponent glass". The sealing glass is free of PbO, with the exception of a few impurities, in particular unavoidable impurities. Impurities can be introduced by natural contamination of raw material components and / or through residues in the facilities used for the production of sealing glass. The maximum amount of these impurities generally does not exceed 1000 ppm and is advantageously not more than 600 ppm. PbO should not be present in the sealing glass of the invention, or at least its presence is limited, because it poses ecological problems, and taking into account the absence of PbO, the glass sealing according to the invention contributes to the ecological character of the articles produced with this glass.
    It is particularly advantageous that the sealing glass is also free of BaO, with the exception of a few impurities at most. As an indication, the upper limit for contamination with BaO can be 1000 ppm, advantageously 500 ppm, and particularly advantageously 100 ppm. Under special operating conditions, there are areas of contact of BaO with metals as assembly partners, which can weaken the joint.
    The sealing glass according to the invention has a coefficient of linear thermal expansion a (25-300) ranging from M.IO ^ K ' 1 to 17.10' 6 K ' 1 , at temperatures ranging from 25 ° C to 300 ° C . Therefore, it is suitable for making joints, especially with light metals, which have a relatively high coefficient of thermal expansion. The sealing glass preferably has a glass transition temperature Tg ranging from 390 ° C to 430 ° C. Tg can be easily measured by those skilled in the art, using known methods.
    The melting temperature, which is important for making glass-to-metal joints, is much more difficult to determine. It is always higher than the Tg, but it is relatively low for the sealing glasses of the invention and thus allows use for the assembly of light metals which generally have a low melting point. Since Tg is much easier to measure, Tg is used as an indication of the melting temperature. To make a joint, the melting temperature of the sealing glass must be lower than the melting point of the metal assembly partner, in particular lower than the melting point of the light metals used.
    The sealing glass according to the invention has improved resistance to water, compared with the state of the art. This is particularly advantageous when the seals made with this glass are exposed to environmental influences and / or to substances containing water, for example reaction vectors and / or electrolytes. This of course also applies to water vapor.
    The sealing glass according to the invention contains, in molar percentage on an oxide basis, from 4 to 8% of B2O3 or, advantageously, from 5 to 7% of B2O3, from 10 to 14% of AI2O3, 36 to 43% P2O5, 15 to 22% Na 2 O, 12.5 to 20% K 2 O, 2 to% B12O3 and a total of> 0 to 6% of at least one oxide additional, called "oxide R". This means that the oxide R is necessarily present in a proportion greater than 0% in the sealing glass according to the invention.
    Unless otherwise indicated, all the contents mentioned here are indicated in molar percentage on an oxide basis.
    The oxide R is chosen from MnO2, S1O2, SnCh, Ta2O5, Nb2O5, Fe2O3, GeCh, and their mixtures.
    The sealing glass according to the invention has a coefficient of thermal expansion a (25-300) lying in the range from M.IO ^ K ' 1 to π.ΙΟ ^ Κ- 1 , in particular from Ιό.ΙΟ ^ Κ ' 1 to 17. ÎO ^ K 1 . Therefore, it is suitable for making joints with metals with high expansion, in particular with light metals and / or stainless steels with high expansion.
    The inventors have found that the water resistance of the sealing glass comprising the indicated components is surprisingly considerably improved by the presence of B12O3 and of the oxide R indicated, in accordance with the invention. It is believed that B12O3 and the oxide R act synergistically and form, at least in certain areas of the glass matrix, connected areas which stabilize the microstructure of the glass, so that the ions are less easily leached from the matrix glass in case of water attack. This was not to be expected from the state of the art.
    Phosphate glasses are known for example from document WO 2012/110247 A1. Phosphate glasses according to WO 2012/110247 A1 are brazing glasses which are used to join metals having a high thermal expansion and low melting points, for example by soldering. B12O3 is not present in the PbO-free variants. Likewise, the oxide R is not mentioned. Consequently, the document WO 2012/110247 A1 does not provide any indication on sealing glasses corresponding to the invention, in particular to the improvement in the resistance to water obtained by it.
    WO 2012/1 10243 A1 discloses phosphate glass solders which may contain B12O3. It has been found that these materials can be attacked by water, under specific operating conditions and / or fields of application. In particular, the materials disclosed by WO 2012/110243 A1 do not indicate an oxide R.
    Other glass solders based on phosphate glass are known from numerous documents. Thus, the document US Pat. of P2O5 and 5 to 15 mol% of PbO and / or BaO. The glass brazing disclosed in US 5,262,364 has thermal expansion a which is in the range of 16.10 ' 6 K _1 to ΣΙ.ΙΟ ^ Κ' 1 . A disadvantage of brazing according to US 5,262,364 resided, inter alia, in the fact that the brazing glass necessarily contained PbO or BaO as well as a relatively high proportion of Na2O. The brazing glass according to US 5,262,364 does not contain B12O3 and has a relatively low resistance to water.
    Document US 5,965,469 A discloses a glass solder or a fusing glass intended for use in an airtight package for high frequency applications. The brazing of glass with high expansion free of lead and PbO known from US 5,965,469 A comprises, in the examples, from 7.5 to 12 mol% of Al2O3 and from 40 to 50 mol% of P2O5. B12O3 is not mentioned. As a result, these materials tend to have relatively high contents of AI2O3 and P2O5 and do not suggest an interaction between B12O3 and the oxide R to improve water resistance.
    A disadvantage of all the phosphate glasses known from the state of the art lies in their low resistance or in a resistance which needs to be improved with respect to humidity, that is to say their resistance to water. However, moisture resistance is required and is critical in many applications. When high expansion phosphate glasses are used in bushings for storage devices and also batteries and capacitors, humidity resistance in particular plays an important role. This applies in particular to the humidity of the ambient air or wetting with water.
    In the case of a sealing glass according to the invention, the improved resistance to humidity is obtained, as assumed and described above, by the interaction of B12O3 and the oxide R, in particular with the contents indicated . As explained, the oxide R comprises at least one of the oxides CaO, MnCh, S1O2, Ta2Û5, SnCh, Nb2Û5, Fe2Û3, GeCh and any combination thereof which, as described, are always present in combination with B12O3 to achieve the objectives of the invention. Here, MnCh, Ta2Û5 and Nb2Û5 seem to have the greatest effect on better water resistance. S1O2 not only improves water resistance but also the possibility of rational production of sealing glass and its resistance to acids. However, S1O2 also increases the melting temperature. The properties of the sealing glass which play a role for the product to be produced with this glass can thus be influenced by an appropriate selection of the constituents of the oxide R and / or combinations thereof.
    According to a preferred embodiment, the sealing glass comprises, as oxide R, in mol% on an oxide basis, from 3.0 to 6.0 of MnÜ2. The inventors have found and confirmed by experiments that good water resistance can thus be obtained. Preferably, the MnO2 can be present in a proportion ranging from 3.2 to 4.9% mol, advantageously also from 3.4 to 4.9% mol. Experiments have shown that the MnO2 content notably improves the adhesion of sealing glass to light metals, in particular to aluminum or aluminum alloys. Hermetically sealed joints with light metals, in particular aluminum and / or aluminum alloys, can thus be produced advantageously and in a particularly rational manner. There are also indications that this also applies to titanium and / or titanium alloys.
    According to another preferred embodiment, the sealing glass contains SiCh, as an alternative or in addition to the components mentioned above, in an amount ranging from 0.01 to 1.8 mol% on a base of oxide, and advantageously from 0.01 to 1.6 mol%. With these contents, it is possible to produce sealing glasses with good water resistance. Resistance to electrolytic solutions, as used for example in capacitors and / or batteries and / or rechargeable batteries, is also good.
    Advantageously, the sealing glass contains, as R oxide, as an alternative or in addition to the oxides R mentioned above, from 0.01 to 2.8 mol% of GeCh and / or 0.01 to 2.4 mol% of SnCh and / or 0.01 to 2.1 mol% of Fe2O3 and / or 0.01 to 2.2% mol of Ta2O5 and / or 0.01 to 2.0% mol of Nb20s and / or 0.01 with 0.4 mol% of CaO.
    Preferably, it is also advantageous that 0 to 0.3% of CaO and / or 3.5 to 4.7% of MnCh and / or 0.01 to 1.1% of S1O2 are present as the oxide R.
    According to another particularly preferred embodiment, the sealing glass contains, in molar percentage on an oxide basis, 36 to <42% of P2O5, particularly advantageously 37.6 to 39.9%. In addition, in a particularly advantageous manner, the sealing glass contains, in molar percentage on an oxide basis, 5.5 to 6.8% of B2O3, 11.4 to 12.8% of Al2O3, 15.4 to 20.9% Na 2 O, 12.8 to 19.8% K 2 O, 2.5 to 4.5% Bi 2 O 3 .
    All the preferred and / or particularly advantageous ranges mentioned in the present description can be combined, individually or in any combination, with the aforementioned ranges of the other respective components.
    The molar fraction of the alkali metal oxides L12O and / or Na2O and / or K2O is preferably limited to a maximum of 36% mol and, particularly advantageously, to maximum 35% mol, in particular the sum of all the oxides of alkali metals L12O and / or Na2Û and / or K2O and / or CS2O. This applies to all of the preferred and preferred ranges listed. This helps to improve water resistance. However, the inventors have found that the alkali metal oxides are also necessary to obtain the high thermal expansion of the sealing glass. This leads to a conflict between the objectives which is treated, in accordance with the invention, by a preferred minimum content of 32 mol% of alkali metal oxides. The lower limit of the content of alkali metal oxides is 27.5 mol%. Advantageously, the content of alkali metal oxides is at least 30% mol, in particular at least 31% mol and, particularly advantageously, at least 33% mol.
    According to a particularly advantageous embodiment, the sealing glass is free of CS2O, with the exception of at most a few impurities. A content of 500 ppm, in particular 200 ppm, can also be indicated as an upper limit for this contamination.
    As described above, the sealing glass of the invention has a coefficient of thermal expansion a (25-300) comprised in the range from U.IO ^ K ' 1 to ÎÎ.IO ^ K' 1 , in particular of ÎS.IO ^ K ' 1 to U.IO ^ K' 1 . The thermal expansion of the glass is thus of the same order of magnitude as that of common metals, such as aluminum (a ~ 23.10 6 I <') or copper (a ~ 16.5.10 6 I < _l ). There are high-expansion stainless steels whose thermal expansion is also in the range from ÎO.IO ^ K ' 1 to U.IO ^ K' 1 . The steels with high expansion among these stainless steels can also be bonded to the sealing glass of the invention, in particular when the sealing glass of the invention is selected so that its thermal expansion is greater than that of the respective stainless steel.
    The transition temperature Tg of the glass, as defined for example in "Schott Guide to Glass, Second Edition, 1996, Chapman & Hall, pages 18 to 21", is preferably in the range from 390 ° C at 430 ° C. As explained above, this allows a joint to be made with the metals described, and on the other hand it also guarantees heat resistance during the operation of a device produced using the sealing glass. For example, the sealing glass can be used in battery boxes and / or rechargeable battery boxes. In the event of a large current draw or a short circuit, the temperatures rise sharply and the sealing glass is able to withstand them when precise design parameters for the housings are respected. In other words, the sealing glass of the invention allows the manufacturer of cases and / or batteries to produce batteries and / or rechargeable batteries and / or capacitors and / or supercapacitors which have increased safety, even in the event of a short circuit.
    It is particularly advantageous for the sealing glasses according to the invention to present not only a transition temperature Tg of the glass in the range from 390 ° C to 430 ° C but also a melting temperature below 600 ° C. For the purposes of the present invention, the melting temperature or the brazing temperature of the glass or glass ceramic is the temperature of the glass or glass ceramic at which the glass material softens and is thus applied firmly against the metal to be bonded by glass melting, so as to establish a seal between the glass or the ceramic glass and the metal. The melting temperature can for example be determined by means of the hemisphere forming temperature described in R. Gôrke, K.-J. Leers: Keram. 1.48 (1996) 300-305, or in accordance with DIN 51730, ISO 540 or CEN / TS 15405 and 15370-1, the disclosure of which content is incorporated by reference in its entirety into the present patent application. The measurement of the hemisphere formation temperature is explained in detail in document DE 10 2009 011 182 A1, the disclosure of the content of which is incorporated by reference in its entirety into the present patent application. In accordance with DE 10 2009 011 182 A1, the hemisphere formation temperature can be determined by a microscopic method using a heating stage microscope. It characterizes the temperature at which an initially cylindrical test piece melted to form a hemispherical mass. It is possible to assign to the hemisphere forming temperature a viscosity of approximately log 11 · = 4.6 dPas, which can be deduced from reading the specialized literature.
    If a glass without crystallization, for example in the form of a glass powder, is melted and then cooled so as to solidify, it can generally be melted again at the same melting temperature. In the context of a seal comprising a glass without crystallization, this means that the operating temperature to which the seal may be exposed in the long term must not be higher than the melting temperature applied for the production of the component nor, advantageously, at the transition temperature Tg of the glass, which is lower than the melting temperature, in order to guarantee the mechanical stability of the component.
    According to a preferred embodiment, the sealing glass comprises crystalline zones which comprise crystalline phases containing phosphate. The crystalline phases can be formed in particular during the process of melting the glass with the assembly partner. The material comprising the crystalline phases has a higher melting point than that of the initial material. This achieves a maximum operating temperature which is higher than the melting temperature.
    Preferably, the crystalline phases comprise crystals of the B12O3 - P2O5 system and / or of the K2O - AI2O3 P2O5 system, in particular of the K2O - AI2O3 - P2O5 system.
    The present invention also relates to a glass powder comprising a sealing glass according to the invention.
    The glass compositions, as used for the purposes of the present invention, are generally produced from a glass powder which is melted and, under the action of heat, establishes the connection joint, or short joint, with the components to be assembled. The melting temperature is generally on the order of magnitude of the hemisphere forming temperature of glass. Glasses with relatively low melting temperatures are also called brazing glasses. In this case, the term "brazing temperatures" is used in place of "melting temperatures". The melting temperature or brazing temperature can deviate by + 20 K from the hemisphere formation temperature.
    The glass mentioned above can be brazed or melted in normal atmospheres, in particular with Al (including aluminum alloys), and / or Ti (including titanium alloys) and / or Cu. The glasses of the invention are particularly suitable for contact with aggressive media containing fluorine and can be used, for example, as electrolytes in lithium-ion batteries.
    The sealing glasses or the glass compositions in accordance with the invention exhibit high chemical resistance to electrolytes containing water and also to non-aqueous battery electrolytes, in particular to battery electrolytes containing carbonates, preferably mixtures of carbonates with an electrolyte salt, in particular comprising LiPF6.
    The invention includes not only the sealing glass but also the composite of the sealing glass of the invention, with a metal. Such a composite is generally designated by the term “glass-metal composite”. Another object of the invention is therefore a glass-metal composite, in particular a light glass-metal composite and / or a glass-light metal alloy composite, comprising a sealing glass according to the invention.
    Thanks to its properties, the sealing glass is particularly well suited to the production of a glass-metal composite comprising light metals, which is also included in the invention. As is known, light metals are metals, including the alloys of said metals, having a density of less than 5 g / m 3 . Light metals which are particularly suitable for producing the glass-metal composite according to the invention are magnesium and magnesium alloys, titanium and titanium alloys, as well as aluminum and aluminum alloys.
    Light metals have in common that they only withstand thermal stress to a certain extent. Aluminum and aluminum alloys cannot be heated to more than about
    600 ° C, because above the components made of aluminum soften and become unusable for the application.
    It is also advantageous and encompassed within the scope of the invention that glass-metal composites comprising steel and / or stainless steel and / or copper and / or copper alloys and / or AlSiC can be produced using the sealing glass of the invention. In particular, it is possible to assemble a component made of one of the metals mentioned, with a component or part of a component of one of the other metals mentioned, using the sealing glass. We then obtain a glass-metal composite which, on one interface, has a bond with one of the metals mentioned and, on the other interface, a bond with the same metal or a different metal. The glass-metal composite described particularly benefits from the improved properties of the sealing glass described above.
    In addition to the glass of the glass composition and the glass composite, the invention also provides a crossing, in particular an electrical crossing, and / or an electrical and / or electronic and / or electrochemical device. Preferably, this is a battery, in particular a lithium-ion battery, a rechargeable battery, in particular a rechargeable lithium-ion battery, a capacitor, a supercapacitor, a sensor housing, an actuator housing, a microcontroller housing and / or a medical implant which may in particular be introduced into the human or animal body and / or may be fixed thereto and / or to a diagnostic and / or therapeutic instrument.
    Although it is often described here by way of example for battery bushings, the invention is not limited to these. The glass compositions can be used in any type of bushing, in particular also in those where the main element and / or the housing and, optionally, also the conductor is made of light metal, in particular aluminum or titanium, including including the alloys thereof. Possible crossings are for example crossings for components, in particular electronic components, which are used in light construction, for example in aeronautical construction and in space navigation, and must in particular have sufficient heat resistance. These electronic components can for example be sensors and / or actuators.
    The subject of the invention is also the use of a sealing glass according to the invention, in a bushing, in particular an electrical bushing, comprising at least one main element composed of metal, in particular of a light metal and / or a light metal alloy, having at least one opening through which a functional element has been passed and coated with sealing glass in the opening, the opening being closed, preferably hermetically, by the glass of sealing, the glass coating preferably being of the compressed type.
    Advantageously, the functional element is, at least in the region of the glass coating, a conductor substantially in the form of a spindle, the essentially spindle-shaped conductor preferably comprising, at least in the region of the coating, copper and / or aluminum.
    The invention also relates to the use of a composite of a glass-metal composite as defined above, in an electrical and / or electronic and / or electrochemical device, having a housing provided with the glass-metal composite and / or a crossing.
    Advantageously, the electrical and / or electronic and / or electrochemical device is chosen from batteries, rechargeable batteries, capacitors, supercapacitors, sensor boxes, actuator boxes, microcontroller boxes, medical implants, articles suitable for being placed on the human or animal body, diagnostic and / or therapeutic instruments.
    The bushings, in particular the battery bushings, in particular for a lithium-ion battery, preferably for a rechargeable lithium-ion battery, comprise a main element which has at least one opening through which a conductor, in particular a conductor substantially in the form of pin, is passed through a glass material having the composition according to the invention, the main element preferably consisting of a material with a low melting point, in particular a light metal, preferably aluminum, AlSiC , magnesium or titanium. Alloys, in particular light metal alloys such as aluminum alloys, magnesium alloys or titanium alloys, for example TÎ6246 or TÎ6242, are also conceivable. Titanium is a material that is compatible with the human body, so it is used for medical applications, for example in the field of prosthetics and / or therapy and / or diagnostics. It is also often used in particular applications, because of its particular strength and resistance and its low weight, for example in the field of racing and also for aeronautical applications.
    Other materials for the main element and / or the casing, in particular a battery casing, are metals, in particular steel, non-oxidizing steel, stainless steel or tool steel which is intended for subsequent heat treatment. The stainless steels which can be used are, for example, -2. In order to obtain particularly good weldability, both for laser welding and for resistance welding, it is clearly preferable to use stainless steels, in particular Cr-Ni steels having the material numbers in accordance with standardization. European (EN) 1.4301, 1.4302, 1.4303, 1.4304, 1.4305, 1.4306, 1.4307, as material for the main element and / or the part forming the housing, in particular the battery element housing. As normal steel, it is possible to use St35, St37 or St38.
    According to a preferred embodiment, the sealing glass in a glass-metal composite, in particular also in a passage, can be covered, at least in portions, by a covering glass or a covering polymer. So
    particularly advantageous, the cover glass has a
    higher chemical resistance than sealing glass, including higher resistance to water.
    Preferably, the cover glass is a titanate glass. A glass of titanate, for the purposes of the present invention, contains in particular, in% by weight on an oxide basis, 4% or
    more than T1O2, in particular 13 to 28% by weight of T1O2.
    Advantageously, the titanate glass is a glass of alkali metal silicate titanate containing 13 to 18% by weight of TiCU and having an alkali content according to a range going from 22 to 52% by weight and an S1O2 content according to a range going from 24 to 44% by weight.
    The cover glass, in the form of a titanate glass, particularly advantageously contains the constituents
    following, or get oxidized: composed of these, in% by weight, on a basis
    T1O2 4 to 28 SiO 2 24 to 44 Li 2 O 0 to 3, in particular 1 to 3 K 2 O 10 to 27 Na 2 O 12 to 22. Glass of recovery cited above, in the form of a
    glass of titanate, also contains particularly
    advantageousoxide: following constituents, in% by weight, on a base
    B2O3 0 to <3 Al2O3 0 to 2, especially 0 to <2 BaO 0 to <11 CaO 0 to 1 CuO 0 to <7 Fe2O3 0 to <5
    MgO
    P 2 O 5 PbO
    Sb 2 O 3
    SnO 2
    SrO
    V 2 O 5
    ZrO 2
    Bi 2 O 3 to <0.5 to 3, especially 1 to 3 to <0.5 to <7 to <4 to <2.5, especially 0 to <2, especially 0 to 0.05 to 13, especially 1 to 13, especially> 5 to 13 to 1 to 19, especially 0 to 18, especially 0 to <10.
    The coating of the conductor with glass in the opening, in order to make a crossing, can be carried out as follows:
    The glass material having the composition according to the invention is first introduced into the opening of the main element, together with the pin-shaped conductor. Then, the glass is heated, at the same time as the conductor, in particular the pin-shaped conductor, in particular up to the melting temperature of the glass, so that the glass material softens and encloses the conductor, in particular the conductor. pin-shaped, in the opening and presses against the main element. Since the melting point of both the material of the main element and the conductor, in particular of the pin-shaped conductor, is higher than the melting temperature of the glass material, the main element as well as the shaped conductor are present in the solid state. The melting temperature of the glass material is advantageously 20 to 150 K lower than the melting point of the material of the main element and the pin-shaped conductor. If, for example, aluminum is used as a light metal, with a melting point Tmeiting = 660.32 ° C, the glass melting temperature is in the range from 350 ° C to 640 ° C, preferably in the range from 350 ° C to 600 ° C, particularly advantageously in the range from 350 ° C to <580 ° C, and especially in the range from 450 ° C to <560 ° C. Instead of a light metal, such as aluminum, an aluminum alloy, magnesium, a magnesium alloy, titanium or a titanium alloy, it is also possible to use a SiC matrix infiltrated with Al as material for the main element. Such a material is also called "AlSiC". AlSiC has a core of SiC in which Al has diffused. The properties, in particular the coefficient of expansion, can be adjusted by means of the proportion of Al. AlSiC exhibits in particular a lower thermal expansion than pure aluminum.
    If light metals are additionally used as materials for the conductors, for example the pin-shaped conductor or the electrode connection component, the light metals are also characterized by a specific electrical conductivity in a range from 5.10 6 S / m to 50.10 6 S / m.
    Other materials would be steel, non-oxidizing steel or stainless steel.
    The material of the conductor, in particular of the pin-shaped conductor, may be identical to the material of the main element, that is to say for example aluminum or AlSiC. This has the advantage that the coefficients of expansion of the main element and the metal pin are identical. The coefficient of expansion a of the glass or glass ceramic material must then be adapted to a single material. On the other hand, the external conductor may include stainless steel or steel.
    It is also possible to provide that the conductor, in particular the pin-shaped conductor, comprises Cu, CuSiC or copper alloys, Mg or magnesium alloys, gold or gold alloys, silver or silver alloys, NiFe, a NiFe envelope with an internal copper face, and also a cobalt-iron alloy.
    For aluminum or aluminum alloy, in particular for the conductor, preferably:
    EN AW-1050 A
    EN AW-13 50
    IN AW-2014
    EN AW-3003
    EN AW-4032
    EN AW-5019
    EN AW-5056
    EN AW-5083
    EN AW-5556A
    EN AW-6060
    EN AW-6061.
    For copper or copper alloys, in particular for the conductor, preferably:
    Cu-PHC 2.0070
    Cu-OF 2.0070
    Cu-ETP 2.0065
    Cu-HCP 2.0070
    Cu-DHP 2.0090
    The bushings, in particular the battery bushings, comprising the glass composition in accordance with the invention, are characterized in that a coating of glass in a main element with a low melting point is possible and that sufficient strength, for example example with water and / or a battery electrolyte, is guaranteed.
    In particular, better chemical stability with respect to aqueous fluids and in particular also non-aqueous battery electrolytes, which are generally aggressive, is guaranteed for the phosphate glasses according to the invention.
    The resistance of the glasses of the invention to battery electrolytes can be verified by grinding the glass composition to obtain a glass powder having a particle size of d50 = 10 μm and by placing it in the electrolyte for a period predetermined, for example a week. "D50" means that 50% of all particles - or grains - of the glass powder are smaller than or equal to a diameter of 10 µm. A mixture of carbonates, namely ethylene carbonate and dimethyl carbonate, in a ratio of 1: 1, with for example one mole of LiPF6 as the electrolyte salt, is used as the non-aqueous electrolyte. After exposing the glass powder to the electrolyte, it can be filtered out and the electrolyte can be analyzed for the glass components extracted from the glass.
    Another advantage of the glass composition according to the invention which can be used in a battery bushing with one or more pins made of aluminum lies in the fact that the melting of the glass with the light metal which surrounds it or with the metal of the conductor, in particular in the form of a metal pin, can also be produced in a gaseous atmosphere which is not an atmosphere of protective gas. Likewise, it is not necessary to create a vacuum for Al fusions, this fusion can be carried out in air.
    For both types of fusion, N2 or Ar can be used as a protective gas. As a pretreatment for melting, the metal is cleaned and / or pickled, targeted oxidized, if necessary, or provided with a coating.
    Another test of resistance of the electrolyte is carried out for example by producing a piece of glass with dimensions 8 × 8 × 2 mm and by subjecting it to a visual evaluation, and also by carrying out a quantitative analysis of the test solution of the electrolyte, concerning the components extracted from the test tube, that is to say the contents of the alkali metals Li, Na, K, Cs and also P and Bi, after 10 days, 20 days, 30 days and not more than 40 days.
    If the dissolution of the test tube has progressed too far, the test in the electrolyte is stopped prematurely, and the day of the stop is recorded.
    In addition to their resistance to electrolytes, the glasses according to the invention have also been checked with regard to their resistance to water or resistance to humidity.
    The moisture resistance was determined as described below. Two 8x8x2 mm glass pieces were placed in an air-conditioned cabinet at 85 ° C and 85% relative humidity for 50 days. Then, the resistance was assessed visually according to the so-called “four eyes” principle, in each case after 2 to 3 days.
    Surprisingly, the sealing glasses according to the invention have a high resistance to water and at the same time a high chemical stability towards non-aqueous electrolytes and also electrolytes containing water, as well as a high coefficient of thermal expansion.
    This is particularly surprising because it is assumed that the higher the coefficient of thermal expansion, the more unstable the glass becomes. It is therefore surprising that, despite the high coefficient of expansion and the low melting temperature, the glasses according to the invention have better stability.
    As mentioned above, the glasses have a surprising and significantly better water resistance. This improvement can be attributed in particular to the presence of oxide R described above. This effect is surprising because it is presumed that glass materials with high thermal expansion must also have more loose bonds inside the glass network, and the oxide R mentioned above apparently stabilizes the glass network, in particular in conjunction with B12O3, without preventing thermal expansion. Such an effect was not predictable. Likewise, the sealing glasses according to the invention made it possible to produce a hermetically sealed connection, in particular with the metals mentioned.
    On the other hand, the invention provides for the glass composition indicated in accordance with the invention to provide it with more fillers, for example with a view to adapting the expansion, that is to say the adaptation of the coefficient of thermal expansion. This makes it possible in particular to reduce the coefficient of thermal expansion.
    In order to allow the glass composition to be heated by infrared heating, the glasses mentioned above can be provided with dopants which have a maximum emission situated in the range of infrared radiation, in particular IR radiation from an IR source. The materials which illustrate this effect are pigments of Fe, Cr, Mn, Co and V. Glass which has been treated in this way can be locally heated in a targeted manner by infrared radiation.
    On the other hand, the crossing, in particular a crossing of a battery or of a capacitor or of a supercapacitor, comprising the glasses according to the invention is characterized by a high resistance to heat, in particular by a resistance to temperature variations, compared to the crossing of the state of the art, in particular those comprising a polymer as a sealing material. An airtight junction is obtained even when the temperature changes or when the temperature varies. The hermetic junction guarantees that no liquid, in particular a battery liquid, can escape and / or that humidity does not penetrate into the case. For the purposes of the present invention, a hermetic junction means that the helium leakage rate is <1.10 ' 8 mbar ls' 1 , preferably <1.10 ' 9 mbar ls' 1 , for a pressure difference of 1 bar.
    On the other hand, the sealing glass, the gasket and / or the bushing, in particular the bushing of the capacitor and / or of the supercapacitor and / or of the battery, has satisfactory chemical resistance, in particular with respect to water and at least vis-à-vis the nonaqueous electrolytes studied.
    The bushings comprising the glass composition according to the invention or the sealing glasses can be used in electrical devices, in particular a storage device, in particular a battery, and preferably a battery cell. The battery cell housing is preferably made of the same material as the main element of the bushing, including a light metal. In the case of battery cells, the main cell is preferably part of the battery box. The battery is preferably a lithium-ion battery.
    The battery and / or the capacitor and / or the supercapacitor may in particular have an electrolyte containing water or a non-aqueous electrolyte. The nonaqueous electrolyte can in particular be based on carbonate, in particular based on a mixture of carbonates. The carbonate mixture can include ethylene carbonate mixed with dimethyl carbonate and an electrolyte salt, for example LIPF6. An example of such an electrolyte is the known battery electrolyte LP30. Another category of battery electrolytes includes water, along with adipic acid and ammonia. The resistance of the sealing glass of the invention to water and to this electrolyte was tested.
    Table 1 first shows practical examples of compositions of the sealing glass according to the invention, in mol% on an oxide basis, WE designating a practical example of a sealing glass according to the invention.
    In Table 2, sealing glasses which do not conform to the invention have been studied as comparative examples, CE designating a comparative example.
    The water resistance of all the practical examples was determined as described above. Based on the results of the tests, a classification of water resistance was established to distinguish between "good", "satisfactory" and "unsatisfactory". The resistance evaluation was carried out visually according to the four-eye principle:
    Good: geometry and color of the specimen unchanged
    Satisfactory: specimen of defined geometry, slight change in color and transparency
    Unsatisfactory: modified geometry and color of the sample
    The resistance to LP 30 and to the electrolyte described, containing water, was also determined for most of the sealing glasses according to the invention.
    The glasses were studied with respect to resistance to electrolytes, using a piece of glass 8 x 8 x 2 mm. The study was carried out on the basis of the components extracted from the test piece by leaching, in particular alkali metals Li, Na, K and / or P and / or Bi, after 10, 20, 30 and not more than 40 days.
    The resistance evaluation was carried out visually according to the four-eye principle:
    Bulk material was categorized as follows: Good: unchanged specimen geometry and color
    Satisfactory: specimen of defined geometry, slight change in color and transparency
    Not satisfactory: geometry and color of the sample changed
    Likewise, the electrolyte solution was visually categorized:
    Good: Electrolyte: NO color change
    Satisfactory: Electrolyte: slight color change
    Unsatisfactory: Electrolyte: dark coloring
    All the practical examples of the sealing glasses of the invention have good water resistance. This applies to all the oxides R mentioned. It is interesting to note that, although good resistance to water is obtained in the case of WE11 and WE12, the resistance to electrolytes containing water is much less good. This shows that the attack of the sealing glass by electrolytes containing water occurs not only through water but also through the electrolyte salts and other substances present in the electrolyte. However, the sealing glasses corresponding to WE11 and WE12 also exhibit good resistance to the non-aqueous electrolyte LP30. However, CE5 and CE17 show that the resistance of sealing glasses to electrolytes containing water can be significantly better than resistance to water.
    Tables 1 and 2 also show the values for Tg. Tg is simple to determine and provides an indication of the melting or processing temperature. Although Tg is significantly lower than these, the lower Tg, the lower the melting or processing temperature too. Since in all practical examples, Tg is clearly below the melting point, in particular of light metals, these are also suitable for producing joints with light metals and / or metals having a similar low melting point. All the sealing glasses according to the invention in Table 1 have a high expansion, that is to say that they have a coefficient of thermal expansion CTE which makes them suitable for producing joints with the metals mentioned, in particular light metals.
    All the sealing glasses according to the invention in Table 1 have a high expansion, that is to say that they have a CTE coefficient which makes them glasses suitable for making joints with the metals mentioned, in particular the light metals;
    On the other hand, all the sealing glasses according to the invention in Table 1 adhere so well to the metals mentioned, in particular to light metals, that a hermetic seal is obtained between the sealing glass and the metal.
    Thus, the sealing glasses of the invention simultaneously meet many requirements, namely a water resistance which is at least good, a high CTE coefficient and a low treatment temperature or Tg, which makes it possible to carry out joined with the metals mentioned, in particular with the light metals, as well as, advantageously, to obtain good resistance to the non-aqueous electrolyte LP30 and, in most embodiments, good resistance to electrolytes containing the water.
    The comparison of the practical examples according to the invention in Table 1 with the comparison examples in Table 2 shows that despite similar basic glass systems, the presence of the oxide R mentioned above results in a very significant improvement in the water resistance. It is interesting to note that all of the comparative examples in Table 2 have satisfactory water resistance at best. Some comparative examples even have absolutely unsatisfactory water resistance.
    By comparing, for example, WE2 with CE2, it can be seen that the P2O5 content is significantly different: in the case of CE2, it is greater than the content according to the invention, and the glass has a significantly lower resistance to water and a unsatisfactory resistance to LP30.
    Table 2 shows the comparative examples CEI to CE19 which represent sealing glasses which are not the subject of the invention. The water resistance of the sealing glasses of all the comparative examples from IEC to CE19 does not exceed the "satisfactory" evaluation. For some, it is even unsatisfactory. In comparison, the sealing glasses according to the invention, comprising the oxide R as a constituent of the composition, have a water resistance which is at least good, which is a significant improvement compared to the state of the art. CE18 and CE19 are even devitrified during the production of the joint and are therefore not usable for the production thereof.
    On the other hand, if the proportion of P2O5 is reduced, better resistance to water is expected, but the coefficient of thermal expansion is then reduced to an extent such that a bond with light metals does not is no longer possible.
    Most sealing glasses according to the invention also have good resistance to electrolytes containing water. This also applies to chemical resistance, compared to the nonaqueous electrolytes described above.
    The composition of the sealing glass of the invention is balanced accordingly, so that a number of requirements are met at the same time. These relate in particular to water resistance, the coefficient of thermal expansion and, preferably, chemical compatibility with light metals, which is a prerequisite for making a joint. The sealing glass must in particular be capable of wetting the light metal. There is an interaction between all of the aforementioned components of a sealing glass according to the invention, which has the effect of satisfying the prerequisites mentioned above. The inventors have created the possibility of indicating a range of compositions for sealing glasses having improved resistance to water and the coefficient of thermal expansion of which enables joints to be made with light metals.
    An in-depth study of the practical examples shows that a complex interaction of the components, such as P2O5 and the alkali metals and also B12O3 and the oxide R, must take place within the ranges of compositions indicated, which leads to the improvement of the resistance to water compared to the comparative examples and therefore to the sealing glasses of the state of the art.
    Due to the complex nature of this interaction, the result is surprising and not predictable.
    The invention will be described below with the aid of drawings and practical examples, without being limited thereto.
    In the drawings, Figure 1 shows a crossing according to the invention; and Figure 2 shows another crossing according to the invention, with a covering material.
    Figure 1 shows a crossing 1 according to the invention. This bushing 1 comprises as a conductor, in particular as a pin-shaped conductor, a metal pin 3 which is preferably made of a material, for example aluminum or copper, and also, as an element main 5, a metal part which, according to the invention, consists of a metal with a low melting point, that is to say a light metal, in particular aluminum. The metal pin 3 passes through an opening 7 which passes through the metal part 5. Although a single metal pin passing through the opening is shown, it is also possible to pass several metal pins through the opening, without leaving the field of application of the invention.
    The outer contour of the opening 7 is preferably round or else oval. The opening 7 crosses the entire thickness D of the main element or of the metal part 5. The metal pin 3 is melted in a glass material 10 and is inserted, in the glass 10, in the opening 7 passing through the main element 5. The glass material 10 is the sealing glass according to the invention. The opening 7 is made in the main element 5, for example by a separation process, preferably by stamping. To obtain a hermetic seal at the place where the metal pin 3 passes through the opening 7, the metal pin 3 is melted in a glass stopper composed of a glass material 10 according to the invention. A significant advantage of this manufacturing process lies in the fact that the ejection of the glass stopper, together with the metal pin, is avoided from the opening 7, even in the presence of increased loads acting on the glass stopper , for example in case of compression load. The melting temperature of the glass according to the invention, with the main element, is 20 K to 100 K lower than the melting temperature of the material of the main element 5 and / or of the pin-shaped conductor.
    The passage illustrated in FIG. 2 corresponds to the passage in FIG. 1, except that the covering material 11, which, as explained above, can be a covering polymer or, particularly advantageously, a covering glass, has been applied to the glass material or the glass stopper 10. In a particularly advantageous manner, the covering glass 11 is the titanate glass described above.
    In particular, the covering material 11 can be applied to the outside of the bushing. The exterior is opposite the interior. The inside is usually the inside of a case. The glass material 10 is therefore generally in contact with the electrolytes, in particular a battery and / or a rechargeable battery and / or a capacitor and / or a supercapacitor. Therefore, the glass 10 of the glass stopper must be resistant to this electrolyte. As indicated above, the sealing glass of the invention resists water and water-containing electrolytes and / or non-aqueous electrolytes which have been studied. The covering material 11 on the outside does not come into contact with the electrolytes but, on the other hand, it is exposed to influences from the environment. Consequently, the covering material 11 can be optimized in terms of different properties, for example for even better water resistance, impact resistance, abrasion resistance and the like. The titanate glass described is for example not as resistant to electrolytes containing water, and in particular to non-aqueous electrolytes, as the sealing glass of the invention, but on the other hand it can be more resistant to water. . Consequently, the crossing corresponding to FIG. 2 constitutes a preferred embodiment of a crossing.
    The composition of the sealing glass according to the invention, as described here, has the advantage that the glass materials have very high coefficients of thermal expansion which are included in the range of 14. ΙΟ ' 6 K ' 1 , preferably in the range from 15. ΙΟ' 6 K ' 1 to 17. ΙΟ' 6 K ' 1 , for temperatures in the range from 20 ° C to 300 ° C and therefore in the range of thermal expansion of light metals such as aluminum, but also of similar metals for the conductors 11 substantially in the form of pins which pass through the glass material, for example copper. Thus, aluminum has a thermal expansion a = 23.10 ' 6 K' and copper has an expansion of 16.5. ÎO ^ K ' 1 , at room temperature. To prevent the light metal of the main element and possibly also of the metal pin from melting or deforming during the coating with the glass, the melting temperature of the glass is lower than the melting temperature of the material of the element principal and / or driver.
    The melting temperature of the glass composition to be used is then in the range from 250 ° C to 650 ° C. The coating of the conductor 3 substantially in the form of a pin with glass, in the main element 5, before the insertion of the bushing in the opening 7, is carried out by heating the glass with the conductor, in particular the conductor in spindle shape, up to the melting temperature of the glass, so that the glass material softens and encloses the conductor in the opening, in particular the spindle-shaped conductor, and is applied against the main element 5. If, as indicated above, aluminum is for example used as a light metal, with a melting point T m eiting = 660.32 ° C, for the main element 9, the melting temperature of the glass is preferably in the range of 350 ° C to 640 ° C, as noted above.
    The material of the pin-shaped conductor 3 is preferably identical to that of the main element or belongs to at least the same category of materials. In particular for electrochemical applications, the material of the conductor is generally selected according to the electrolytes used and according to the function in the cell. The pin-shaped conductor may comprise, as a material, aluminum, an aluminum alloy, AlSiC, copper, a copper alloy, CuSiC alloys or NiFe alloys, a material with a copper core, i.e. a NiFe envelope having a copper or CF25 interior, i.e. a cobalt-iron alloy, silver, a silver alloy, gold or an alloy of 'gold.
    The crossing described here is particularly advantageously a coating of compressed glass. Here, the sealing glass is placed with the conductor, at least one, in a housing element and / or main element and is then heated, so that all the elements are interconnected by fusion. During cooling, the sealing glass solidifies and the housing and / or the main element contracts more strongly than the glass. Due to the different coefficients of thermal expansion of the materials used, the sealing glass is subjected to compression in the opening of the bushing and forms a seal. The coefficient of thermal expansion of the joint partner, which here is generally the metal, in particular the light metal, is greater than that of the sealing glass.
    The glass coating comprising the glass indicated in Table 1 forms a hermetic seal, as described above. This applies in particular to bushings produced using the indicated glass materials. All the glasses mentioned have been tested in bushings, with aluminum as the material of the main element, and have made it possible to form a hermetic seal.
    A light metal such as aluminum (Al), AlSiC, an aluminum alloy, magnesium, a magnesium alloy, titanium or a titanium alloy, is preferably used as the material for the main element. Other possible materials for the main element are metals such as steel, non-oxidizing steel, stainless steel or tool steel.
    The glass compositions of the invention give sealing glasses, in particular for use in joints with light metals, having a low treatment temperature, a melting temperature which is lower than the melting point of aluminum, a has a high coefficient of expansion and excellent resistance to battery electrolytes, as well as considerably improved water resistance. Although the glass compositions have been described for use in bushings, in particular battery bushings, they are not limited to this use, and other fields of application are, for example, the sealing of cases, of sensors and / or actuators or also capacitors and / or supercapacitors. In principle, bushings are suitable for all uses in light constructions, in particular as bushings in electrical components which must be light and withstand heat. Such components exist for example in aeronautical construction and space navigation. Use in the field of medical technology, in particular in diagnostic instruments and / or implants, is also possible.
    Compared with the known high-expansion sealing glasses, the high-expansion sealing glasses according to the invention have the advantage of being much more resistant to water. This is believed to be the result of the interaction between B12O3 and the described oxide R, which apparently stabilize, at least in certain regions, the lattice of the glass matrix, so that the sensitive constituents thereof, in particular the phosphorous constituents are not leached or at least leached less easily. At the same time, the sealing glasses of the invention can form a particularly tight seal with light metals. As a result, the sealing glasses according to the invention are particularly useful in products subject to high stresses and / or mass produced, for example in medical products and / or batteries intended for electromobility.
    Table 1: Practical examples
    WE1 WE2 WE3 WE4 WE5 WE6 WE7 WE8 WE9 WE10 WE11 B2O3 6.2 6.2 6.1 5.85 6.1 6.5 5.9 6.15 6.15 6.25 6 A12O3 12.15 12.25 11.85 12.2 12.35 12.5 11.2 12.1 12 12.05 12.1 P2O5 40.55 38 39.5 38.2 38.3 38.7 41.7 41.7 41.7 41.6 41.75 B12O3 3.45 3.75 2.85 3.7 3.8 3.8 3.4 4.4 4.4 4.5 4.4 L12O Na 2 O 15.9 16.8 15.9 16.45 16 20.4 16.1 16.05 16.2 15.9 16.1 K2O 17.65 18.7 18.85 19 19 13.3 17.5 17.65 17.5 17.7 17.7 BaO CaO 0.1 0.15 0.15 0.3 0.15 0.1M11O2 3.75 3.9 4.5 4 4.05 4.4S1O2 0.25 0.25 0.3 0.3 0.25 0.3 4.2 0.05 0.05 0.15 0.15 GS SnO 2 2 Fe 2 O> 3 1.8 Ta2O5 1.9 Nb 2 O 5 1.85PbO Total 100 100 100 100 100 100 100 100 100 100 100 Total oxide R 4.1 4.3 4.95 4.6 4.45 4.8 4.2 1.95 2.05 2 1.95 Tg [° C] 401 407 411 409 404 425 411 421 416 422 413 Sft [° C]567CTE [25; 300] 16.2 16.23 15.48 16.22 16.16 15 16.4 15.5 16.1 16 15.8 CTE [25; Tg] 18.7 Resistance at the water good good good good good good good good good good good Electrolyte containing water good good good good good good satisfactory LP 30 good good good good good good good
    Table 1 (continued)
    WE12 WE13 WE14 WE15 WE16 WE17 WE18 WE19 WE20 WE21 WE22 B2O3 6.3 7 7 5.2 7 6.9 6.9 6.9 6.9 6.9 5.85 A12O3 12.2 13 13 11.1 13 13 13 13 13 13 12.5 P2O5 41.4 36.1 39.3 42 39.3 39.3 39.3 39.3 39.5 39.5 38.75 B12O3 3.6 5.8 5.8 4.6 5.8 5.8 5.8 5.8 5.8 5.8 3.85 Li 2 O Na2O 15.9 20.4 20.4 21.3 20.4 20.4 20.4 20.4 20.4 20.4 17.25 K 2 0 18 14.38 14.38 12.5 14.38 14.4 14.3 14.3 14.3 14.3 16.3 BaO CaO0.12 0.12 0.1 0.120.1 M11O23.23.2 4 S1O2 0.051.4 GeO 2 2.55 0.2S11O2 0.3 Fe2O3 0.3 Ta 2 O 5 0.1 Nb 2 O 5 0.1PbO Total 100 100 100 100 100 100 100 100 100 100 100 Total R oxide 2.6 3.32 0.12 3.3 0.12 0.2 0.3 0.3 0.1 0.1 5.5 Tg [° C] 420 Sft [° C] CTE [25; 300] 16 16.6 16.6 15.8 16.3 16.3 16.2 16.2 16.2 16.2 15.7 CTE [25; Tg] Water resistance good good good good good good good good good good good Electrolyte containing water unsatisfactory LP 30 good
    CTi C * D
    EC10 4.7 8.7 43.3 O 17.317.3 8.7100 o 354 14.9EC9 7.6 4.2 47.5 o28.3 12.4 100 o 325 OEC8 4.8 8.6 43.3 o17.3 17.3 8.7100 o 375 16.5EC7 6'9 in 39.5 5.820.4 14.4 100 o16.4EC6 3.6 10.75 48.1 3.9Ό 17.5 0.05 100 0.05 407 16.7CE5 K) O 36.67.7 K) 19.55.2 100 O 334 19.2EC4 5.446.4 -T28.4 16.30.05 0.05 100 o 28623.8 EC3 7.6 4.2 46.5 -28.3 12.4 100 o 339 19.7CE2 5.8 12.3 43.55 4.415.8 18.05 O 100 o 425 15.9IEC Ό40 OK) 00O 100 o 401 16.3 inO m inO OΛ inOm OJ ocùZ o£ BaO CaO OCD ZnO O<Z)U PbO Total Total oxide R Tg [° C] CTE [25; 300] CTE [25; Tg]
    ^ r
    not satisfied tory 1 <Z) O CÙ<Z) year <Z)ΰ O CÙ XVS 1 <Z) O CÙ<Z) year <Z)ΰ O CÙ XVS O1 <Z) VS cùcù <Z)<Z) cù X1 <Z) Ocù bornO C <Z) cù vsVS<Z) OOcù XX O XVS 1 <Z) O O <U es vs<Z) vsVS <Z)g isaCÙ isac Ocù<Z) cùX O X X VS 1 <Z) O<Z) Ocù VScù VSvs <Z) cù<Z) cùs<Z) <Z) ΰ CÙΰ CÙX O XO X VS VS 1 <Z) O<Z) Ocù VScù VSvs <Z) cù<Z) cùs ΰ <Z)CÙΰ aisO X O XO X VS VS O O 1 <Z) O <Z) VS<Z) VSvs cù cù<Z)cù isa <Z)g cù<Z) <Z) CÙ<Z) cùcùX X O C XO<Z) O <U <Z) VSes VSVScù<Z) cùvs cù <Z)g <Z)O <Z) cù CÙXXO XVS O OO ΌO O c>> VS>>cù<Z) at tro cù C Otro OO o o in <Z) OQ ΰ o where O Q Ph o4M (J lh M hJ
    x> cû
    H
    EC 19 8.7 6.4 32.8 3.3 7.4 17.9 23.5 100 O22.9CE 18 13.632.7 -T26.2 18.5 100 o21.0EC17 9.4 6.35 35.35 3.932.3 100 Ό 349 19.9EC16 8.9 9'9 35.56'9 23.1 l> 100 O 350 CE 15 4.7 9.5 37.9 16.4 CN 12.4 100 12.4 360 17.4EC14 00 9.4 38.4 2.319.8 17.9 O 10.3 100 10.4 341 18.9EC 13 5.2 12.7 39.5 2.916.5 CN O-T100 O 367 CNEC12 4.837.142.1 -T100 o 359 14.8EC11 4.843.334.6 15.3100 o 369 13.7 inO m inO OΛ inOm OJ OcùZ O£ BaO CaO OCD ZnO o<Z)U PbO Total Total oxide R Tg [° C] CTE [25; 300] CTE [25; Tg]
    not satisfied tory 1 <Z) O CÙ<Z) year <Z)ΰ O CÙVS 1 <Z) O oO VS<Z) vs <Z) VS <Z) isaCÙ isa fi fi<Z)cù<Z) fi <Z) fi O C X XX 1 <Z) o l <Z) O cù VS fi VS <Z) cù <Z) fi<Z) <Z) ΰ o CÙ X we fi X VS VS1 <Z) Ocù rt O C <Z) cù fi<Z) Ocù X o XVS 1 <Z) ocù rt o c <Z) cù fi<Z) ocù X o XVS 1 <Z) ocù rt o c <Z) cù fi<Z) ocù X o XVS 1 <Z) o CÙ<Z) year <Z)ΰ O CÙ XVS 1 <Z) O CÙ<Z) year <Z)ΰ O CÙ XVS 'CÙ O oo Όo o C>> VS>>cùo cùo fi _ <Z) O <Z) -o CÙ O lec So fi o lec inPh o4 lh M (J lh M hJ
    权利要求:
    Claims (15)
    [1" id="c-fr-0001]
    1. Sealing glass, having improved resistance to water, free of PbO, with the exception of a few impurities at most, and having a coefficient of thermal expansion a (25-300) ranging from M.IO ^ K ' 1 to 10 ^ K ' 1 and preferably having a glass transition temperature Tg ranging from 390 ° C to 430 ° C, containing, in molar percentage on an oxide basis,
    b 2 o 34 to 8 A1 2 Ü3 10 to 14 P 2 o 536 to 43 Na 2 O 15 to 22 K 2 O 12.5 to 20 Bi 2 O3 2 to 6 oxide R > 0 to 6, where the oxide R is an oxide chosen from MnO 2 , SiO 2 , SnO 2 , Ta 2 Os
    Nb 2 O 5 , Fe 2 O3, GeO 2 , CaO and their mixtures.
    [2" id="c-fr-0002]
    2. Sealing glass according to claim 1, characterized in that it comprises, as oxide R, in molar percentage on an oxide basis,
    MnO 2 3.0 to 6.0, preferably 3.2 to 4.9.
    [3" id="c-fr-0003]
    3. Sealing glass according to claim 1 or 2, characterized in that it comprises, as oxide R, in molar percentage on an oxide base,
    SiO 20.01 to 1.8 and / or GeO 20.01 to 2.8 and / or SnO 20.01 to 2.4 and / or Fe 2 O3 0.01 to 2.1 and / or T a 2 Os 0.01 to 2.2 and / or Nb 2 O 50.01 to 2.0 and / or
    CaO 0.01 to 0.4.
    [4" id="c-fr-0004]
    4. Sealing glass according to any one of the preceding claims, characterized in that the sealing glass contains, individually or in any combination, in molar percentage on an oxide basis,
    P2O5 36 to <42, preferably 37.6 to 39.9, and / or
    B2O3 5.5 to 6.8 and / or
    AI2O3 11.4 to 12.8 and / or
    Na2Û 15.4 to 20.9 and / or
    K2O 12.8 to 19.8 and / or
    B12O3 2.5 to 4.5.
    [5" id="c-fr-0005]
    5. Sealing glass according to any one of the preceding claims, characterized in that the total content of alkali metal oxides L12O and / or Na2Û and / or K2O is not more than 36 mol%, preferably not more than 35 mol%, in particular the sum of all the alkali metal oxides L12O and / or Na2O and / or K2O and / or CS2O.
    [6" id="c-fr-0006]
    6. Sealing glass according to 1 ‘any one of the preceding claims, characterized in that the sealing glass has crystalline zones comprising crystalline phases containing phosphate.
    [7" id="c-fr-0007]
    7. Sealing glass according to claim 6, characterized in that the crystalline phases comprise crystals of the B12O3 - P2O5 system and / or of the K2O - AI2O3 - P2O5 system, preferably crystals of the K2O - AI2O3 - P2O5 system.
    [8" id="c-fr-0008]
    8. Glass powder comprising a sealing glass as defined in any one of claims 1 to 7.
    [9" id="c-fr-0009]
    9. Glass-metal composite, in particular a light glass-metal composite and / or a glass-light metal alloy composite, comprising a sealing glass as defined in any one of claims 1 to 7.
    [10" id="c-fr-0010]
    10. Glass-metal composite according to claim 9, characterized in that the metal is chosen from aluminum, aluminum alloys, titanium, titanium alloys, magnesium, magnesium alloys, AlSiC, steel, stainless steel, copper and copper alloys.
    [11" id="c-fr-0011]
    11. Glass-metal composite according to claim 9 or 10, characterized in that the sealing glass is covered, at least in portions, with a covering glass or a covering polymer, the covering glass preferably having higher chemical resistance than the sealing glass, in particular a higher higher water resistance, the cover glass preferably being a titanate glass.
    [12" id="c-fr-0012]
    12. Use of a sealing glass according to any one of claims 1 to 7, in a bushing, in particular an electrical bushing, comprising at least one main element composed of metal, in particular of a light metal and / or of a light metal alloy, having at least one opening through which a functional element has been passed and coated with sealing glass in the opening, the opening being closed, preferably hermetically, by the sealing glass , the glass coating preferably being of the compressed type.
    [13" id="c-fr-0013]
    13. Use according to claim 12, characterized in that the functional element is, at least in the region of the glass coating, a conductor substantially in the form of a pin, the conductor essentially in the form of a pin preferably comprising, at less in the region of the coating, copper and / or aluminum.
    [14" id="c-fr-0014]
    14. Use of a glass-metal composite as defined in any one of claims 9 to 11, in an electrical and / or electronic and / or electrochemical device, having a housing provided with the glass-metal composite and / or d 'a crossing.
    [15" id="c-fr-0015]
    15. Use according to claim 14, characterized in that the electrical and / or electronic and / or electrochemical device is chosen from batteries, rechargeable batteries, capacitors, supercapacitors, sensor boxes, actuator boxes, microcontroller cases, medical implants, articles able to be placed on the human or animal body, diagnostic and / or therapeutic instruments.
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    同族专利:
    公开号 | 公开日
    KR20190031163A|2019-03-25|
    DE102017216422B3|2019-01-03|
    JP6505303B2|2019-04-24|
    US20190084871A1|2019-03-21|
    JP2019052081A|2019-04-04|
    KR20190110976A|2019-10-01|
    US10654745B2|2020-05-19|
    KR102025850B1|2019-09-26|
    KR102343527B1|2021-12-28|
    CN109502998A|2019-03-22|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5262364A|1991-09-23|1993-11-16|The United States Of America As Represented By The United States Department Of Energy|High thermal expansion, sealing glass|
    US5965469A|1998-03-20|1999-10-12|Sandia Corporation|High thermal expansion sealing glass for use in radio frequency applications|
    EP1464089B1|2002-01-09|2012-05-02|Alfred E. Mann Foundation for Scientific Research|Hermetic seals for lithium-ion batteries|
    RU2366040C2|2004-12-28|2009-08-27|Текникал Юниверсити Оф Денмарк|Method of obtaining compounds metal-glass, metal-metal and metal- ceramics|
    CN101447266B|2007-11-27|2012-09-05|兴亚株式会社|Zinc oxide multilayer chip piezoresistor and manufacturing method thereof|
    DE102009011182B4|2009-03-04|2017-03-23|Schott Ag|Crystallizing glass solder, composites and its use|
    HUE053333T2|2011-02-18|2021-06-28|Schott Ag|Feed-through|
    US10224521B2|2011-02-18|2019-03-05|Schott Ag|Feed-through|
    DE112012002421A5|2011-06-10|2014-03-20|Schott Ag|Duch leadership|
    JP2013157161A|2012-01-30|2013-08-15|Hitachi Chemical Co Ltd|Electronic component, manufacturing method of the same and seal material paste used therefor|
    JP5868818B2|2012-09-27|2016-02-24|株式会社ノリタケカンパニーリミテド|Phosphate glass bonding material|
    DE102013006463B4|2013-04-15|2017-01-19|Schott Ag|execution|
    DE102014016600A1|2014-11-11|2016-05-12|Schott Ag|execution|US20200149635A1|2018-11-12|2020-05-14|Stephen Vincent Rust|Hermetic glass-to-metal seal reinforced with a ceramic disc to prevent crack propagation|
    US10847288B2|2019-01-25|2020-11-24|Anthony Bellora|High fidelity feedthrough system|
    CN111003945A|2019-12-30|2020-04-14|西安赛尔电子材料科技有限公司|Preparation method of sealing glass material and sealing process thereof|
    CN111847882A|2020-08-10|2020-10-30|河北曜阳新材料技术有限公司|Low-temperature sealing glass and preparation method thereof|
    法律状态:
    2019-09-26| PLFP| Fee payment|Year of fee payment: 2 |
    2020-09-14| PLFP| Fee payment|Year of fee payment: 3 |
    2021-09-21| PLFP| Fee payment|Year of fee payment: 4 |
    2021-12-24| PLSC| Publication of the preliminary search report|Effective date: 20211224 |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102017216422.0A|DE102017216422B3|2017-09-15|2017-09-15|High-expansion bonded glass with improved water resistance and its applications|
    DE1020172164220|2017-09-15|
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