EP2473454A2 - High-temperature resistant crystallizing solder glasses - Google Patents

High-temperature resistant crystallizing solder glasses

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Publication number
EP2473454A2
EP2473454A2 EP20100760584 EP10760584A EP2473454A2 EP 2473454 A2 EP2473454 A2 EP 2473454A2 EP 20100760584 EP20100760584 EP 20100760584 EP 10760584 A EP10760584 A EP 10760584A EP 2473454 A2 EP2473454 A2 EP 2473454A2
Authority
EP
European Patent Office
Prior art keywords
mol
temperature resistant
temperature
ceramic
glass
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20100760584
Other languages
German (de)
French (fr)
Inventor
Steffen Schirrmeister
Bernd Langanke
Thomas Schiestel
Björn HOTING
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Borsig Process Heat Exchanger GmbH
ThyssenKrupp Industrial Solutions AG
Original Assignee
Borsig Process Heat Exchanger GmbH
ThyssenKrupp Uhde GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to DE200910038812 priority Critical patent/DE102009038812A1/en
Application filed by Borsig Process Heat Exchanger GmbH, ThyssenKrupp Uhde GmbH filed Critical Borsig Process Heat Exchanger GmbH
Priority to PCT/EP2010/005194 priority patent/WO2011023372A2/en
Publication of EP2473454A2 publication Critical patent/EP2473454A2/en
Withdrawn legal-status Critical Current

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    • C04B37/00Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/02Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles
    • C04B37/023Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used
    • C04B37/025Joining burned ceramic articles with other burned ceramic articles or other articles by heating with metallic articles characterised by the interlayer used consisting of glass or ceramic material
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    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02Frit compositions, i.e. in a powdered or comminuted form
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    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04Frit compositions, i.e. in a powdered or comminuted form containing zinc
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    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/06Frit compositions, i.e. in a powdered or comminuted form containing halogen
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    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES, OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
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    • C04B2235/65Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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    • C04B2235/656Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
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    • C04B2237/30Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32Ceramic
    • C04B2237/34Oxidic
    • C04B2237/345Refractory metal oxides
    • C04B2237/348Zirconia, hafnia, zirconates or hafnates
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    • C04B2237/30Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/40Metallic
    • C04B2237/405Iron metal group, e.g. Co or Ni
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    • C04B2237/50Processing aspects relating to ceramic laminates or to the joining of ceramic articles with other articles by heating
    • C04B2237/76Forming laminates or joined articles comprising at least one member in the form other than a sheet or disc, e.g. two tubes or a tube and a sheet or disc

Abstract

The invention relates to high-temperature resistant crystallizing solder glasses which contain 20-45 mol% of BaO, 40-60 mol% of SiO2, 0-30 mol% of ZnO, 0-10 mol% of AI2O3, 0-5 mol% of BaF2, 0-2 mol% of MgO, 0-2 mol% of CaO, 0-2 mol% of TiO2, 0-10 mol% of B2O3, as well as 0,5-4 mol% of M2O3 (M = Y, La or rare earth elements) and/or 0.5-4 mol% of ZrO2, and to the use thereof.

Description

 High temperature resistant crystallizing glass solders

The invention relates to a high-temperature-resistant crystallizing glass solder of a specific composition according to claim 1, which can be used as Fügeglaslot.

For this purpose, a glass is used, which during the high

Temperatures performed joining process crystallized. In this case, crystalline phases precipitate with high coefficients of thermal expansion.

Glass solders and crystallizing glass solders are today often for

Production of composites used. Here, for example, two metals or alloys of different composition or two ceramics of different composition or structure or a metal are added to a ceramic. It is also possible that one or both of the materials to be joined consist of a metal / ceramic composite.

Ceramic oxygen-transporting membranes are used in particular in high-temperature processes. For example, they are an inexpensive alternative to cryogenic air separation in oxygen production and are used in the synthesis of synthesis gas by partial oxidation of

 Hydrocarbons such as methane used, which proceeds according to the following reaction equation:

(1) 2 CH 4 + O 2 → 2 CO + 4H 2

Other applications are in the production of oxygen-enriched air, as described for example in DE 102005 006 571 A1, the oxidative dehydrogenation of hydrocarbons or hydrocarbon derivatives, the oxidative coupling of methane to C 2+ , and the water and

Nitrous oxide decomposition.

Ceramic membranes are often used as tubes, which are often integrated into modules. A special form of the tubes are ceramic hollow fibers with a diameter of less than 5 mm. Such modules should on the one hand be chemically and thermally loadable, on the other hand they must guarantee a gas-tight seal. The integration of pipe or pipe

Hollow fiber membranes in modules can be formed by forming an embedding, too Potting called, from a potting compound, also potting mass or

Called connecting material done.

As suitable for this purpose material come ceramic materials in question, which is similar to the material from which the ceramic membrane itself, or is the same and thus have optimum compatibility. The problem, however, is that such layers can not be sintered gas-tight without irreversibly altering the ceramic hollow fiber membrane itself. A method for producing such a module with the aid of ceramic material as Pottungsmasse is described for example in EP 0941759 A1. WO 2006089616 describes a potting, which consists of at least three layers comprising at least two different potting compounds. In this case, the two outer layers of ceramic material may be formed and the intermediate layer may be formed of glass. A disadvantage of this type of potting is that glass, because of its oxides, such as zirconium oxide or iron oxide, is a very reactive component and destroys the oxidative constituents of the ceramic material.

The construction of chemically and thermally resilient modules with

ceramic tube, hollow fiber or capillary membranes therefore requires the adaptation of Pottmaterialen. Usually have glasses that soften at a lower temperature, higher thermal expansion coefficients than glasses that soften at higher temperature. Thus, if a composite material with a glass solder as joining compound at a higher temperature (eg 800 0 C) is to be used, then no glasses are available, the z. B. a softening temperature> 800 0 C and at the same time have a thermal expansion coefficient>10> 10 "6 K " 1 . A mechanically and thermally stable joint connection can not be created here by a glass solder, but by a crystallizing glass solder.

To produce a crystallizing glass solder, a glass of suitable composition is first melted, cooled to room temperature without crystallizing and then comminuted. The aim is typically particle sizes between 1 and 200 microns. Then the glass powder is applied to one or both workpieces to be joined. For this application, a number of excipients, such as aqueous or non-aqueous solvents, oils or polymer solutions are used. But it is also possible to apply ceramic films on one or both workpieces to be joined

In a further step, the workpieces to be joined with the glass solder are then heated to a suitable temperature. Here, the glass particles sinter together and connect with both to be joined workpieces. The

But bringing the workpieces together can only be done at high temperatures. The sintering is to be done by viscous flowing into each other of the glass. If the glass particles are largely sintered together and connected to the workpieces to be joined, crystallization should occur. Of the

Crystallization process can also be brought about by changing the temperature. Depending on the chemical composition of the glass solder, a temperature above or below the actual bonding temperature can be used. After completion of the joining process, the workpieces are firmly connected. Materials of glass ceramic in the most diverse

Compositions are state of the art. Thus, glass ceramics from the BaO-CaO-Al 2 O 3 -SiO 2 system are used for joining high-temperature fuel cell stacks. In addition to high temperature resistance, the following requirements are imposed on this material. On the one hand, the joining material should be very stable, it should have an electrically insulating property and, on the other hand, it must not react with gases such as H 2 , O 2 , H 2 O and CH 4 . In addition, it should have good adhesion to the metallic surface of the fuel cell stacks (Schwickert T. et al., Mat.-wiss., And Werkstofftech., 33, 363-366, 2002). To a glass-ceramic, especially for the use of embedding, too

Potting called, of ceramic membranes in metallic moldings is suitable, again special requirements. In addition to one

Temperature resistance of up to 900 ° C and a gas-tight closure, the glass ceramics used must be chemically inert to oxide ceramics having a perovskite structure, a Brownmilleritstruktur or Aurivilliusstruktur, and / or additionally chemically inert to metallic

Be high-temperature materials. This counteracts the problem of destruction of the materials outlined above.

In addition, the glass-ceramics must have a thermal

Have expansion coefficient equal to that of oxide ceramics or is similar and / or have a thermal expansion coefficient that is similar to or similar to that of high-temperature metallic materials.

[0016] metals usually have linear thermal expansion coefficient between 10> 10 '6 and 16> 10 -6 K' 1. Adjust the expansion coefficient not to of the solder material, occur during temperature changes voltages, which eventually lead to destruction of the composite. Tolerable are in general, differences in the linear thermal expansion coefficient of less than 1-2> 10 "6 K '1 . If the workpieces to be joined have different coefficients of thermal expansion, then the expansion coefficient of the crystallized glass solder should be as close to the center as possible.

Sintering and crystallization of the glass solder are not always separated in time and temperature or separable processes. Usually, they run rather simultaneously. Here, the sintering rate increases with the temperature, and the same applies to the crystallization rate of the glass. It should therefore be found at each concrete joining problem a time and temperature window in which the sintering process is much faster than the crystallization. Therefore, a crystallizing bonding glass solder must have the right (high) expansion coefficient to be sintered under the respective applicable conditions without crystallization occurring beforehand and continue to be sufficiently thermally stable at use temperature, i. H. do not soften.

Oxidative crystal phases of high thermal expansion that can be precipitated from oxide glasses are primarily

Alkaline earth metal. The phases BaSi 2 O 5 and Ba 3 Si 5 O 13 in G. Oelschlegel, Glastechnische Berichte 44 (1971), 194-201, Ba 2 Si 3 O 8 in G. Oelschlegel, Glastechnische Berichte 47 (1974 ), 24-41, also quantitatively described in terms of their linear thermal expansion coefficient. Furthermore, in the literature glass ceramics with other alkaline earth oxides (SrO, CaO), for example in Lahl, J. Mater. Be. 35 (2000) 3089, 3096, which also thermal

Have expansion coefficients>10> 10 "6. These glass ceramics consist not only of the desired crystal phase and high coefficients of expansion but also of other phases.

Glass phases and have mostly much lower thermal

Expansion coefficient. The reason for this is that a glass, for example of composition 50 BaO> 50 SiO 2, crystallizes far too quickly to densely sinter as a powder. The crystallization process would start much too soon and prevent sintering. By relatively small additions of additives such as boron oxide or alumina, the crystallization process can be slowed down. However, this also involves a reduction in the coefficient of thermal expansion. Furthermore, it is known that these components in other

Glass compositions rather promote crystallization. For example, it is very often described in the literature that ZrO 2 acts as a nucleating agent Maier, cfi Ber. DKG 65 (1988) 208, Zdaniewski, J. Am. Ceram. Soc. 58 (1975) 16, Zdaniewsi, J. Mater. Sei, 8 (1973) 192. In the MgOZAI 2 O 3 ZSiO 2 system , the addition of ZrO 2 leads to a

Nucleation in the volume can be brought about in the first place Amista et al. J. Non-Cryst. Solids 192/193 (1995) 529. Without presence of ZrO 2 (or TiO 2 ) surface crystallization is observed here. The volume nucleation rate is increased by many orders of magnitude by adding a few% ZrO 2 .

The development of a crystallizing glass solder, which has all the above properties and with which the problems of common glass ceramics known from the prior art can be avoided, the present invention has made the task.

This is achieved by the use of a high temperature resistant crystallizing glass solder containing 20-45 mol% BaO, 40-60 mol% SiO 2 , 0-30 mol% ZnO, 0-10 mol% Al 2 O 3, 0-5 Mol% BaF 2 , 0-2 mol% MgO, 0-2 mol% CaO, 0-2 mol% TiO 2 , 0-10 mol% B 2 O 3 , and 0.5-4 mol% M 2 O 3 ( M = Y, La or rare earth metals) and Z or contains 0.5-4 mol% ZrO 2 . Instead of the BaF 2 , it is also possible to use other fluxes known to the person skilled in the art.

According to the invention, the additives known from the prior art with other additives, especially La 2 O 3 andZoder ZrO 2 can be combined.

Surprisingly, even small additions of ZrO 2 , La 2 O 3 or rare earths are extremely effective here. However, the additives La 2 O 3 or ZrO 2 suppress the crystallization even without the simultaneous presence of B 2 O 3 or Al 2 O 3 , thus making it possible to use a crystallizing glass solder. The high-temperature-resistant crystallizing glass solders advantageously contain 35-45 mol% BaO, 40-50 mol% SiO 2 , 5-8 mol% Al 2 O 3 , 0-2 mol% MgO, 0-2 mol% CaO, 0- 2 mol% Ti0 2 , 5-10 mol% B 2 O 3 , and 0.5-4 mol% M 2 O 3 (M = Y, La or rare earth metals) and Z or 0.5-4 mol% ZrO 2 . In a further advantageous composition of

high-temperature-resistant crystallizing glass solders contain these 20-30 mol% BaO, 50-60 mol% SiO 2 , 10-25 mol% ZnO, 0-3 mol% Al 2 O 3 , 0.5-3 mol% B 2 O 3 , and 0.5-4 mol% M 2 O 3 (M = Y, La or rare earth metals) and / or 0.5-4 mol% ZrO 2 . Further, a high temperature resistant crystallizing glass solder of composition 30-40 mol% BaO, 40-50 mol% SiO 2 , 0-10 mol% ZnO, 5-8 mol% Al 2 O 3 , 2-10 mol% B 2 O 3 , and 0.5-4 mol% M 2 O 3 (M = Y, La or

Rare earth metals) and / or 0.5-4 mol% ZrO 2 .

Preferably, the high temperature resistant crystallizing glass solder from 34-44 mol% BaO, 40-50 mol% SiO 2 , 5-8 mol% Al 2 O 3 , 0-5 mol% BaF 2 , 0-2 mol% MgO , 0-2 mol% CaO, 0-2 mol% TiO 2 , 5-10 mol% B 2 O 3 , and 0.5-4 mol% M 2 O 3 (M = Y, La or rare earth metals) and / or 0 , 5-4 mol% ZrO 2 together.

Optionally, the high temperature resistant crystallizing glass solder 35- 40 mol% BaO, 40-48 mol% SiO 2 , 0-2 mol% MgO, 0-2 mol% CaO, 0-2 mol% TiO 2 , 4-6 mol % B 2 O 3 and 4-6 mol% Al 2 O 3 , 1-3 mol% M 2 O 3 (M = Y, La or rare earth metals) and / or 1-3 mol% ZrO 2 .

Particularly preferred is the high temperature resistant

crystallizing glass solder of 22-28 mol% BaO, 45-55 mol% SiO 2 , 15-19 mol% ZnO, 0-2 mol% Al 2 O 3 , 0-2 mol% MgO, 0-2 mol% CaO, 0 -2 mol% TiO 2 , 0-2 mol% B 2 O 3 , and 0.5-2 mol% M 2 O 3 (M = Y, La or rare earth metals) and / or 0.5-2 mol% ZrO 2 together.

The crystallizing glass solders of molten and crushed glass particle size of 1 and 200 microns are advantageously prepared, these are preferably made of molten and crushed glass particle size of 10 and 150 .mu.m, and these are particularly preferred from molten and crushed glass particle size made of 30 and 125 microns. The finer the particle size, the faster crystallization takes place.

Advantageously, the high temperature resistant crystallizing glass solder is used as a gas-tight joining glass solder for the connection of metallic high-temperature materials and ceramics or of ceramic / metal composite materials.

 Preferably, in this process, a metal and a ceramic are joined together. This is particularly preferably a metallic one

High-temperature nickel-based material and an oxide ceramic. The oxide ceramic advantageously has a perovskite-like structure or a Brownmillerite structure or a Aurivilliusstruktur and the ceramic preferably has a cubic or tetragonal stabilized zirconia structure.

Hereinafter, the present invention is based on various

Embodiments will be described in more detail. Embodiment 1

A hollow ceramic fiber suitable for separating air in the pressure gradient (mixed electron / oxygen ion conductor) is intended to be joined to a nickel / iron based high temperature alloy. Both materials to be joined have linear thermal expansion coefficients of 14-15> 10 -6 K -1 in the temperature range from 25 to 850 ° C.

Through the metal a 2 mm thick hole is drilled. Using a drill with a diameter of 8 mm in the same position, the metal is drilled approx. 4 mm deep to form a conical depression with the 2 mm hole at the top. A ceramic hollow fiber with a diameter of 1, 8 mm is now inserted into this hole. 0.3 g of a glass powder of composition 15 ZnO 25BaO 1 B 2 O 3 - 1 ZrO 2 - 1 La 2 O 3 57SiO 2 is added to the conical recess.

 For this purpose, a particle size fraction of 50-80 μm obtained by sieving is used.

Subsequently, the assembly of metal, hollow fiber and glass is placed in an oven and heated to a temperature of 900 0 C. The heating rate is 5 K / min. The final temperature is held for 1 h and the furnace is then cooled. There is obtained a gas-tight joint connection. The composite can be used at temperatures of up to 900 0 C. Embodiment 2

 A ceramic hollow fiber and a high temperature alloy having properties as described in Embodiment 1 are to be joined together.

In the metal a cylindrical hole of 4 mm depth and 10 mm diameter is introduced. In the bottom of this hole now a total of 7 holes are introduced with a diameter of 1, 5 mm. Through these holes will be

Hollow fiber membrane of 1, 3 mm diameter introduced.

To prepare the joint compound is a glass of the composition

36.25 BaO7.5 Al 2 O 3 -5B 2 O 3 -2ZrO 2 -2La 2 O 3 -3BaF 2 -44.25SiO 2 with a grain fraction of 30-125 μm. From this, a pourable slurry is prepared with a 2% solution of polyvinyl alcohol in water and filled into the cylindrical bore. After drying, the assembly is brought to a temperature of 950 ° C. This is up to 600 0 C, the heating rate 1 K / min and at a higher temperature 5 K / min.

Embodiment 3

A ceramic hollow fiber and a high-temperature alloy having properties as described in Embodiment 1 are to be joined together.

 A hollow fiber bundle is introduced into a polymer mold (0 = 25 mm).

 A ceramic non-aqueous slurry based on ethanol, polyvinyl butyral

Hydroxypropylcellulose is prepared from a glass of composition 41.75 BaO 7.5 Al 2 O 3 SB 2 O 3 I ZrO 2 - 1 La 2 O 3 42, 25SiO 2 . This is a grain fraction 30 -

50 μm, which was made by seven used.

 The slurry is poured into the polymer mold. It is then dried and the

Molded body removed from the mold and sintered at 920 0 C in the oven. Of the

 Shaped body has a diameter of 22 mm after sintering.

The sintered shaped body is then placed on a metal plate with a hole (0 =

16 mm), so that the hollow fiber, the inner edge of the metal plate and the glassy crystalline shaped bodies (0 = 22 mm) overlap by approx. 3 mm.

In a second temperature treatment step, this arrangement is now heated to 980 0 C and left for 1 h at this temperature. Embodiment 4

A flat membrane made of ceramic (thickness 1 mm), which was produced by film technology, is to be joined to a high-temperature alloy. Both materials have linear thermal expansion coefficients 14-15> 10 "6 K -1 in the temperature range from 25 to 850 ° C.

For this purpose, from a glass of the composition 19th

ZnO 25BaO-1 B 2 O 3 -2ZrO 2 -2La 2 O 3 '51SiO 2 a pourable slip on

Ethanol / propanol base with the addition of hydroxypropyl cellulose, polyvinyl alcohol, octyl phthalate, surfactants and polyethylene glycol produced. This is used to produce a ceramic foil by the Docter Blade process. From this are cut out with a CO 2 laser contours. These films are then placed on the metal plate and then the ceramic flat membrane

applied.

This arrangement is sintered at 950 0 C, kept at this temperature for 1 h. The heating rate was 1 K / min up to a temperature of 650 0 C and then 5 K / min.

Embodiment 5 A flat membrane made of tetragonal stabilized zirconia ceramic (thickness 200 μm, linear thermal expansion coefficient: 10> 10 "6 K " 1 ) is produced by film technology. This is to be joined to a high-temperature alloy (linear thermal expansion coefficient 11, 5> 10 '6 K ' 1 ).

This is done from a glass of

Composition-35BaO-3B 2 θ3-2Zrθ2 2La2θ37Al2θ3-51SiO 2 an ethanol / propanol based paste with the addition of hydroxypropyl cellulose, polyvinyl alcohol, and octyl phthalate. This paste contains 50% by volume glass. This paste is used to make a joint between the zirconia ceramic and the high temperature alloy. This arrangement is sintered at 950 0 C, held for 1 h at this temperature and then brought to a temperature of 880 ° C and held at this temperature for another 5 h. The heating rate was 2 K / min.

Claims

claims
1. Containing high temperature resistant crystallizing glass solders
 20-45 mol% BaO,
40-60 mol% SiO 2 ,
 0-30 mol% ZnO,
0-10 mol% Al 2 O 3 ,
0-5 mol% BaF 2 ,
 0-2 mol% MgO,
0-2 mol% CaO 1
0-2 mol% TiO 2 ,
0-10 mol% B 2 O 3 SO
0.5-4 mol% M 2 O 3 (M = Y, La or rare earth metals) and / or
0.5-4 mol% ZrO 2 .
High-temperature resistant crystallizing glass solders according to claim 1, characterized in that
 35-45 mol% BaO,
40-50 mol% SiO 2 ,
5-8 mol% Al 2 O 3 ,
 0-2 mol% MgO,
 0-2 mol% CaO,
0-2 mol% TiO 2 ,
5-10 mol% B 2 O 3 as well
0.5-4 mol% M 2 O 3 (M = Y, La or rare earth metals) and / or
0.5-4 mol% ZrO 2
 are included.
High temperature resistant crystallizing glass solders according to claim 1, characterized in that:
 20-30 mol% BaO,
50-60 mol% SiO 2 ,
 10-25 mol% ZnO,
0-3 mol% Al 2 O 3 ,
0.5-3 mol% B 2 O 3 as well
0.5-4 mol% M 2 O 3 (M = Y, La or rare earth metals) and / or 0.5-4 mol% ZrO 2
are included.
High temperature resistant crystallizing glass solders according to claim 1, characterized in that:
 30-40 mol% BaO,
40-50 mol% SiO 2 ,
 0-10 mol% ZnO,
5-8 mol% Al 2 O 3 ,
2-10 mol% B 2 O 3 as well
0.5-4 mol% M 2 O 3 (M = Y, La or rare earth metals) and / or
0.5-4 mol% ZrO 2
are included.
High temperature resistant crystallizing glass solders according to claim 1, characterized in that:
 34-44 mol% BaO,
40-50 mol% SiO 2 ,
5-8 mol% Al 2 O 3 ,
1-5 mol% BaF 2 ,
 0-2 mol% MgO,
 0-2 mol% CaO,
0-2 mol% TiO 2 ,
5-10 mol% B 2 0 3 as well
0.5-4 mol% M 2 O 3 (M = Y, La or rare earth metals) and / or
0.5-4 mol% ZrO 2
are included.
High temperature resistant crystallizing glass solders according to claim 1, characterized in that:
35-40 mol% BaO 1
40-48 mol% SiO 2 ,
4-6 mol% Al 2 O 3 ,
 0-2 mol% MgO,
 0-2 mol% CaO,
0-2 mol% TiO 2 ,
4-6 mol% B 2 O 3 as well 1-3 mol% M 2 O 3 (M = Y 1 La or rare earth metals) and / or
1-3 mol% ZrO 2
 are included.
7. High temperature resistant crystallizing glass solders according to claim 1, characterized in that:
 22-28 mol% BaO,
45-55 mol% SiO 2 ,
 15-19 mol% ZnO,
0-2 mol% Al 2 O 3 ,
 0-2 mol% MgO,
 0-2 mol% CaO,
0-2 mol% TiO 2 ,
0-2 mol% B 2 O 3 as well
0.5-2 mol% M 2 O 3 (M = Y, La or rare earth metals) and / or
0.5-2 mol% ZrO 2
 are included.
8. High temperature resistant crystallizing glass solders according to one of
 above claims characterized in that the crystallizing glass solders are made of melted and crushed glass of particle size of 1 and 200 microns, preferably from molten and
 crushed glass particle size of 10 and 150 microns are made and more preferably made of molten and crushed glass particle size of 30 and 125 microns.
9. High temperature resistant crystallizing glass solders according to one of
 above claims characterized in that the glass ceramic as a gas-tight joining glass solder for the connection of metallic
 High temperature materials and ceramics or ceramic / metal composite materials is used.
10. High-temperature resistant crystallizing glass solders according to claim 9, characterized in that a metal and a ceramic are joined together.
11. High-temperature resistant crystallizing glass solders according to claim 10, characterized in that a metallic high-temperature material based on nickel and an oxide ceramic are joined together.
12. High-temperature resistant crystallizing glass solders according to claim 11
 characterized in that the oxide ceramic has a perovskite-like structure or a brownmillerite structure or an Aurivillius structure.
13. High temperature resistant crystallizing glass solders according to claim 11
 characterized in that the ceramic has a cubic or tetragonal stabilized zirconia structure.
EP20100760584 2009-08-31 2010-08-25 High-temperature resistant crystallizing solder glasses Withdrawn EP2473454A2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE200910038812 DE102009038812A1 (en) 2009-08-31 2009-08-31 High temperature resistant crystallizing glass solders
PCT/EP2010/005194 WO2011023372A2 (en) 2009-08-31 2010-08-25 High-temperature resistant crystallizing solder glasses

Publications (1)

Publication Number Publication Date
EP2473454A2 true EP2473454A2 (en) 2012-07-11

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EP (1) EP2473454A2 (en)
JP (1) JP2013503095A (en)
DE (1) DE102009038812A1 (en)
WO (1) WO2011023372A2 (en)

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DE102012003338A1 (en) * 2012-02-17 2013-08-22 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Composition for the production of glass solders for high temperature applications and their use
JP6032014B2 (en) * 2012-04-24 2016-11-24 日本電気硝子株式会社 Crystalline glass composition
DE102013209970B3 (en) 2013-05-28 2014-07-24 Schott Ag Glassy or at least partially crystalline joining material and its use and jointing
KR101457614B1 (en) * 2013-05-31 2014-11-10 한국세라믹기술원 Glass composition for solid oxide fuel cell sealant, sealant and the manufacturing method using the same
CN105776868B (en) * 2016-03-29 2019-01-25 西安赛尔电子材料科技有限公司 A kind of high temperature resistant height insulation seal glass and preparation method thereof

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Also Published As

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DE102009038812A1 (en) 2011-03-10
US20120183785A1 (en) 2012-07-19
JP2013503095A (en) 2013-01-31
WO2011023372A2 (en) 2011-03-03
WO2011023372A4 (en) 2011-06-23
WO2011023372A3 (en) 2011-04-28

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