EP2814784A1 - Zusammensetzung für die herstellung von glasloten für hochtemperaturanwendungen sowie deren verwendung - Google Patents
Zusammensetzung für die herstellung von glasloten für hochtemperaturanwendungen sowie deren verwendungInfo
- Publication number
- EP2814784A1 EP2814784A1 EP13706940.7A EP13706940A EP2814784A1 EP 2814784 A1 EP2814784 A1 EP 2814784A1 EP 13706940 A EP13706940 A EP 13706940A EP 2814784 A1 EP2814784 A1 EP 2814784A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- mol
- range
- glass
- composition according
- composition
- 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.)
- Ceased
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/062—Glass compositions containing silica with less than 40% silica by weight
- C03C3/064—Glass compositions containing silica with less than 40% silica by weight containing boron
- C03C3/068—Glass compositions containing silica with less than 40% silica by weight containing boron containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/095—Glass compositions containing silica with 40% to 90% silica, by weight containing rare earths
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/028—Sealing means characterised by their material
- H01M8/0282—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0271—Sealing or supporting means around electrodes, matrices or membranes
- H01M8/0286—Processes for forming seals
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL 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
- C03C2205/00—Compositions applicable for the manufacture of vitreous enamels or glazes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M2008/1293—Fuel cells with solid oxide electrolytes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- composition for the production of glass solders for high temperature applications and their use
- the invention relates to compositions for the production of glass solders for high temperature applications up to temperatures of about 1000 C and their use. They can preferably be used for joining and sealing to SOFC fuel cells.
- the glass solders For the glass solders to be used, this results in a multiplicity of requirements which they must satisfy: - When the bonding temperature is reached, the glass phase must have a sufficiently low viscosity ( ⁇ 10 6 Pas) to ensure good bonding to the metallic and ceramic joining partners.
- the proportion of glass phase must be sufficiently high (> 40 vol%) to allow sufficient flow of the glass.
- TAK thermal expansion coefficient
- the thermal expansion coefficient (TAK) is given in this document as the technical coefficient of thermal expansion.
- ⁇ (1 - 1 0 ) / 1 0 (T - To)
- the glass solder should have good chemical compatibility with the joining partners and high stability in dual atmospheres.
- the actual joining process usually begins with an amorphous glass solder, which has such a low viscosity when the joining temperature is reached that bonding of the molten glass to the joining partners can take place.
- an amorphous glass solder which has such a low viscosity when the joining temperature is reached that bonding of the molten glass to the joining partners can take place.
- the object of the crystalline phase is, on the one hand to the small thermal expansion coefficient (CTE) of the completely amorphous glass of about 4 x 10 "5 K" 1 to 7-10 "6 K” 1 to a value to lift the 's is only about 0.1 -10 "6 K" 1 to 2-10 "6” 1 below the TAK of the SOFC stacks materials to be joined.
- CTE small thermal expansion coefficient
- Suitable values for the TAK of crystalline glass solders for the SOFC are in the range of 9-10 "6 K " 1 to 11.5-10 "6 K -1 relative to a temperature range between room temperature and the glass transition temperature T g of the glass solder, where T g of 600 ° C to 700 C.
- T g glass transition temperature
- Consequences of excessive thermo-mechanical stresses in SOFC stacks are, for example, cracking and deformations of the components, which would adversely affect the functionality of the SOFC stacks.
- the crystalline solids content can increase the viscosity of the solder system, which gives the SOFC stacks an improved mechanical stability under operating conditions.
- glass solder compositions usually critical components such as alkali oxides (R 2 0), oxides of polyvalent ions (eg V 2 0 5 , CuO, Co 3 0 4 ) or heavy metal oxides (eg PbO, Bi 2 0 3 , CdO) may be included.
- R 2 0 alkali oxides
- oxides of polyvalent ions eg V 2 0 5 , CuO, Co 3 0 4
- heavy metal oxides eg PbO, Bi 2 0 3 , CdO
- BaO and CaO are so far the two most common components in glass ceramic solders for SOFC applications.
- the known in connection with these oxides glass solders have proportions of BaO and CaO in proportions to other relevant oxides (Si0 2 and Al 2 0 3 ) on crystallization processes to barium monosilicate (BaSi0 3 ),
- Barium silicates with variable stoichiometries (Ba 5 Si 3 0i 2 , Ba 3 Si 2 O g , BaSi 2 0 5 see this BaO-Si0 2 -hasendiagramm), Celsian phases (BaAl 2 Si 2 0 8 ) and others Ca-containing crystal phases (CaSi0 3 , anorthite) lead.
- some of these crystal phases have coefficients of thermal expansion which may be considered too low for use in glass solders and are desirably to be avoided.
- the scope of the known glass solders is essentially up
- the glass solder thus obtained is present after the addition in non-crystallized form. Crystalline phases are not formed in any form during a heat treatment which should be present to match certain properties in the structure of the glass.
- the coefficient of thermal expansion of the glass solder lies in the range between 45 ⁇ 0 "7 K “1 and 90 ⁇ 0 "7 K " 1, according to the aforementioned patent.
- the composition according to the invention for the production of glass solders for high-temperature applications contains SiO 2 with a content in the range from 48 mol% to 62 mol%, Al 2 O 3 with a fraction in the range from 0.5 mol% to 6 mol% , B 2 0 3 with a content in the range of 4 mol% to 12 mol% and BaO in a proportion in the range of 12 mol% to 30 mol% and CaO in a proportion of 2.5 mol% bis 15 mol% and / or an R 2 0 3 in a proportion in the range of 0.5 mol% to 15 mol%.
- the R 2 0 3 is selected from La 2 0 3 , Y 2 0 3 , Sc 2 0 3 and another oxide of a chemical element from the series of lanthanides (eg Nd 2 0 3 , Pr 2 0 3 , Sm 2 0 3 ). It may be favorable to choose the minimum proportion of R 2 0 3 to 2 mol%, preferably to 4.5 mol%.
- the glasses melted from these nominal compositions are preferably used in particulate form.
- the content of BaO contained should be in the range of 12 to 30 mol%. It is also permissible that in suitable Glaslotzusammen GmbHen CaO and La 2 0 3 , or a correspondingly substituted component, are included together. Here, the respective possible proportions of these oxides are to be seen independently of each other.
- a ratio of SiO 2 : BaO should be in the range of 1.9 to 3.6, preferably in the range of 2.4 to 3.4, and more preferably in the range of 2 , Be complied with 6 to 3.2.
- a preferred range of the ratio of the proportions of Si0 2 : BaO is between 2.2 and 4.5, and a particularly preferred ratio in the range of 2.5 to 3.8.
- a ratio of SiO 2 : BaO should be in the range of 2.3 to 4.3, preferably in the range of 2.6 to 4.0, and more preferably in the range of 3.0 to 3.8 be respected.
- At least one further oxide may additionally be present, which is selected, for example, from: rare earth oxides, Ta 2 O 5 , Nb 2 O 5 , SnO 2 , GeO 2 , As 2 O 3 and Sb 2 O 3 .
- the proportion of one or more of these oxides or oxides should be kept below 10 mol%. It is believed that one skilled in the art can select suitable oxides, other than those previously mentioned, and add them to the claimed glass compositions in such low amounts without substantially altering the essential properties of the glass solders. The claimed glass compositions and related relevant properties may be unaffected by such minor modifications.
- a proportion is preferred in the glass solder composition according to the invention to comply with Si0 2 in the range of 56 mol% to 60 mol%.
- a particularly preferred range is between 58 mol% and 60 mol%.
- a preferred range of BaO contained is from 14 mol% to 24 mol%. This range is particularly preferably between 12 mol% and 22 mol%.
- the content of B 2 O 3 contained should preferably be in the range of 4 mol% to 9 mol%, and more preferably 4 mol% to 7 mol%, when CaO is contained.
- the preferred range should be between 5 mol% and 10 mol% and more preferably between 4 mol% and 7 mol%.
- the content of Al 2 O 3 contained should preferably be in the range of 1 mol% to 4 mol%. Particularly preferred is a range between 2 mol% and 3.5 mol%, when CaO is contained. When R 2 0 3 contained , this particularly preferred range is between 1.5 mol% and 3 mol%.
- the content of B 2 O 3 contained should preferably be in the range of 4 mol% to 9 mol%. Particularly preferred is a range between 4 mol% and 7 mol%, when CaO is contained. When R 2 0 3 contained , the preferred range is between 5 mol% and 10 mol% and the particularly preferred range between 6 mol% and 9 mol%.
- a composition of the invention can be used so that after a heat treatment, a glass solder, with a semi-crystalline structure, the proportion of which is less than 50% by mass of crystalline phase, contained in the glass solder is.
- This structure can essentially consist of a barium silicate, barium calcium silicate, lanthanum silicate, lanthanum calcium silicate or a
- a partially crystalline glass solder thus obtained may have the following characteristics. There is a dilatometric softening point at a temperature of 650 ° C to 800 ° C and a glass transition temperature T G in the range of 600 ° C to 700 C. Furthermore, a glass solder according to the invention has a thermal expansion coefficient which lies in the range of 8 ⁇ 10 -6 K -1 to 12 ⁇ 10 -6 K -1 in a temperature range between 20 ° C. and the glass transition temperature T G. The heat treatment to be carried out for this is below described in the general description and in the embodiments.
- Glass solders obtained in this way can be processed at temperatures in the range of 800 ° C. to 1000 ° C., preferably between 850 ° C. and 950 ° C., and used for joining or sealing.
- a composition according to the invention may contain CaO or La 2 O 3 as important constituents, the molar compositions in which La 2 O 3 is present being only slightly different from the CaO-containing constituents.
- Lanthan boron silicates contain as exclusive crystal phases.
- either BaSi 2 O 5 or BaSi 2 O 5 in combination with Ba x Ca Y Si 2 O 5 represents the property-determining crystal phase (s). Further crystal phases do not occur or are the case to avoid from cristobalite.
- cristobalite Si0 2
- this crystal phase is basically to avoid, but can in proportions of less than 5% by mass (XRD analysis via Rietveld).
- thermodynamically stable crystal phases can be formed in the bonded glass solder structure (barium disilicate, barium calcium disilicate and minimal amounts of cristobalite, quartz, hexacelsian, barium monosilicate, calcium monosilicate). Due to the targeted adjustment of only a few crystal phases, with a proportion of less than 50% by mass, a semi-crystalline glass solder structure results in the joined state in which the properties of the residual glass phase can be continuously modified within certain limits.
- the glasses are easily adjustable in terms of relevant properties, such as their softening behavior and thermal expansion coefficients within certain limits with little effort.
- compositions with BaO-CaO-B There were 2 0 3 Al 2 0 3 -Si0 2 summarized in the tables below are examples of compositions with BaO-CaO-B. The individual compositions of samples were designated ECa and each subsequent digit.
- the crystal phase composition was determined after heat treatment by FESEM / EDX and XRD.
- the temperature was first raised to 950 ° C at a heating rate of 2 K / min. This maximum temperature was maintained for a period of 2 hours and then cooled to 850 ° C at a rate of 5 K / min. This temperature was held for 48 hours and then cooled to room temperature at a rate of 5 K / min.
- BaO CaO ratios lead to amounts of crystalline Ba 2 Si0 5 phase in the microstructure of the crystallized glass ceramics and to the formation of cristobalite (Si0 2 ) (see FIG. Likewise, BaO: CaO ratios of less than 2.4 in these compositions lead to the formation of CaSi0 3 phases (EDX analysis of a compound of ECa3).
- glass solder compositions are avoided, which lead to the formation of cristobalite, since crystal phases with such properties can lead to cracking or leaks in Glaslotgehege.
- the decreasing proportions of BaSi 2 0 5 phase for the composition ECa3 cause a significant decrease of the TAK compared to the compositions ECaO, ECal and ECa2.
- the data show that BaO: CaO ratios lead to only slightly varying TAK values up to a minimum of 2.4, which can be seen in Table 3 below.
- the BaO: CaO ratio was varied between 3.44 and 1.82, with the Si0 2 -, Al 2 0 3 - and B 2 0 3 shares remained unchanged.
- Table 4 shows that the respective TAK for given proportions for Si0 2 , Al 2 0 3 and B 2 0 3 for molar BaO: CaO ratios between 2.1 and 3, 44 changed only slightly and a chromium-containing materials, in particular for
- Interconnectors are used, showing favorable value.
- Table 5 TAK values of ECa glasses ECaO, ECal, ECa4 and ECa5 with varying Al 2 O 3 ratios for the temperature range between room temperature temperature and the respective glass transition temperature Tg of the crystallized glass
- FIG. 2 shows XRD measurements of ECa offsets with 7 mol% CaO and varying Al 2 O 3 fractions between 2 mol% and 5 mol% after a heat treatment for 48 h at 850 ° C.
- Si0 2 is the main network-forming component in compositions having molar proportions of more than 50 mol%. However, proportions of 54 mol% Si0 2 and more in combination with unfavorable proportions of the other components listed give corresponding proportions of glass solder compositions which have been used Run through by crimps typical heat treatments Cristobalit as unwanted crystal phase. The disadvantages of cristobalite in the glass solders have already been described.
- FIG. 3 shows TAK courses of the examined ECa compositions after a heat treatment: RT; 2 K / min -> 950 C / 2 h; 5 K / min -> 850 ° C / 48 h; 5 K / min -> RT.
- compositions ELa2, ELa4, ELa3 and ELa5 show in their temperature-dependent curves of the TAK ( Figure 4) a pronounced crystallization of cristobalite (elevation in the range of 230 ° C to 260 ° C). This behavior is also observed in the CaO-containing compositions ECa2 and ECa3 (see Figure 4). With La 2 0 3 in proportions of up to 4 mol%, no effective suppression of cristobalite formation is possible in this composition range. It can be assumed that a further increase in the Al 2 O 3 content in this regard can show a clearer effect.
- composition ELa6 In strongly attenuated form, and thus for use in SOFC still to a tolierbarem extent, the cristobalite formation occurs in composition ELa6, in which the La 2 0 3 content was raised to 9 mol% ( Figure 4).
- Comparable CaO-containing glasses can be obtained with the compositions ECa9 and ECal5.
- a comparison of the compositions of ELa6 and ELa7 shows the effect of a 2 mol% increased La 2 0 3 content, whereby the cristobalite formation can be suppressed to such an extent that they are detected neither as an increase in the measurement of the coefficient of thermal expansion nor XRD can be.
- BaSi 2 0 5 can also Barium-Calicium silicates, Lanthanum silicates be detectable. In the event that the glass solders contain calcium oxide and lanthanum oxide together, lanthanum-calcium silicates (eg Ca 3 La 6 (Si0) 6) can be detectable.
- a comparison of the glass solders obtained with the compositions ELa6 and ELa8 shows that increasing the Al 2 O 3 content from 2 mol% to 4 mol% leads to a reduced coefficient of thermal expansion of the crystallized microstructure, which after XRD analyzes on a low
- Table 9 Composition of the prepared and tested glass solders containing CaO and La203
- a uniform bonding temperature of 950 ° C was chosen.
- a screen printing paste was produced from the glass solder compositions and a peripheral frame was printed on substrates (30 mm ⁇ 30 mm ⁇ 2 mm 3 ) with a width of 3 mm and a height of 250 ⁇ m.
- the heat treatment for the joining process was carried out according to the following profile in air:
- helium leak rates were measured by means of a leak detector from Oerlikon. With the exception of samples of composition ECaO, dense model couplings could be made with the remaining ECa samples (helium leak rates less than 10 "5 1 mbar s " 1 ).
- Table 11 Sintering and softening behavior of the ECa glasses according to a heating microscopic analysis in air at 2 K / min and CFYai substrate; Helium leak rates of model assignments using formation of CFY substrates
- Table 12 Sintering and softening behavior of the glass solders obtained with ELa composition according to a heating microscopic analysis in air at 2 K / min and YSZ as substrate; Helium- Leak rates of model attachments using CFY
- Measured values are converted into a specific electrical resistance value via the dimensions of the glass soldering.
- Table 13 Specific electrical resistances of model couplings with different glass solders at 850 ° C after aging for 300 h at 850 ° C in a dual atmosphere and an applied electrical voltage of 0.7 V.
- FIG. 1 EDX analyzes of the partially crystalline microstructure for BaSi 2 0 5 barium disilicate, SiO 2 cristobalite, barium calcium silicate and a calcium-depleted glass matrix;
- FIG. 2 XRD measurements of ECa samples with 7 mol% CaO and modified Al 2 O 3 fractions between 2 mol% and 5 mol% after a heat treatment for 48 h at 850 ° C .;
- FIG. 3 shows courses of the temperature-dependent coefficients of thermal expansion for glass solders obtained from ECa samples with proportions of cristobalite determined by X-ray analysis after the following heat treatment: RT; 2 K / min 950 C / 2 h; 5 K / min -> 850 ° C / 48 h; 5 K / min - RT
- FIG. 4 shows courses of the thermal expansion coefficients of examined ELa glasses after the following heat treatment:
- the raw materials were homogenized in a plastic container on a pot roller for 60 minutes, this process being assisted by added grinding balls of Al 2 O 3 .
- the offset was inductively heated in air in a platinum 90-rhodium-10 glass crucible having a capacity of 200 ml with a high-frequency coil, and a pre-melt of the entire offset was prepared.
- the pre-melt crucible was kept at 1500 C in air in a muffle furnace (Carbolite HTF1800) for 2 h in air.
- the glass melt was then fritted in water and dried at 150 ° C in air for 12 h in a drying oven.
- the dried glass frit was first pre-comminuted in a carbide-lined disk vibrating mill (Retsch RS1) to a particle fraction ⁇ 500 ⁇ m (mesh size of a metal sieve).
- the actual grinding was carried out in a planetary ball mill (Fritsch Pulverisette 5) using agate containers and agate Grinding balls.
- the grinding conditions were chosen such that using the pre-shredded glass frit a particle size distribution with the following typical characteristics is obtained: D 10 about 2 ⁇ , D 50 about 4 ⁇ , D 90 about ⁇ (measurement in a Mastersizer 2000 according to Fraunhofer standard method and Dry dispersion of the powder).
- the glass powder thus obtained was made into a screen-printable paste using organic polymer-based binders and at least one solvent under conditions common in thick-film technology.
- the procedure for the preparation of a screen-printable paste of a glass powder or a ceramic powder can be considered as prior art.
- This paste was used, for example, to apply seams to CFY substrates (Plansee) for interconnectors of SOFC, as a substrate, with dimensions of 30 mm ⁇ 60 mm ⁇ 3 mm by means of screen printing.
- the glass paste was printed either as a single frame or in multiple printing (pressure-drying-pressure) as a peripheral frame on the steel substrate.
- the printed substrates were dried for about 20 minutes to 40 minutes at 120 ° C. to 140 ° C. in air in a drying oven.
- the thicknesses of the printed and dried joints of the printing paste were typically between 100 ⁇ and 500 ⁇ and the widths between 3 mm and 4 mm.
- a second steel substrate of the same type and with the same dimensions was placed on the printed substrate.
- a central bore with a diameter of 4 mm for the measurement of helium leak rates after joining was available.
- the model constructions thus constructed were weighted with a mass of approx. 20 g / cm 2 and added in air in a muffle furnace (Carbolite RWF1200) according to the following furnace profile: RT; 5 K / min ⁇ > 500 C / 2h; 2 K / min 950 C / 4h; -5 K / min - »850 C / 20 h; 5 K / min - RT.
- the offsets were homogenized on the lockable plastic containers on a roller mill for 60 minutes, this process being assisted by added grinding balls of Al 2 O 3 (diameter about 15 mm). subse- went d the entire offset was in a semi-continuous ; Electrically heated glass melting furnace (from HTM Reetz, Berlin), which was equipped with a 1 l -platinum 90 rhodium oil crucible, melted in air to give a glass. The total batch was again divided into three individual batches. This means that in each case 1/3 of the raw material offset was placed in the crucible within a period of 30 min. After completion of the task, the glass melt was held for 2 h at 1500 C and then poured into cold deionized water. The glass frit thus prepared was dried at 150 ° C in air for 12 h in a drying oven.
- the dried glass frit was first pre-shredded by means of a drum mill on a roller chair. By repeated screening a grain fraction ⁇ 500 ⁇ (mesh size of a metal mesh) was realized. The milling of the thus pre-crushed fraction was carried out in a counter-jet mill (Alpine fluidized bed opposed jet mill
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE102012003338A DE102012003338A1 (de) | 2012-02-17 | 2012-02-17 | Zusammensetzung für die Herstellung von Glaslotenfür Hochtemperaturanwendungen sowie derenVerwendung |
PCT/EP2013/052679 WO2013120803A1 (de) | 2012-02-17 | 2013-02-11 | Zusammensetzung für die herstellung von glasloten für hochtemperaturanwendungen sowie deren verwendung |
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EP2814784A1 true EP2814784A1 (de) | 2014-12-24 |
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EP13706940.7A Ceased EP2814784A1 (de) | 2012-02-17 | 2013-02-11 | Zusammensetzung für die herstellung von glasloten für hochtemperaturanwendungen sowie deren verwendung |
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US (1) | US9714190B2 (de) |
EP (1) | EP2814784A1 (de) |
JP (1) | JP6140195B2 (de) |
DE (1) | DE102012003338A1 (de) |
WO (1) | WO2013120803A1 (de) |
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DE102012003338A1 (de) | 2012-02-17 | 2013-08-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Zusammensetzung für die Herstellung von Glaslotenfür Hochtemperaturanwendungen sowie derenVerwendung |
CN107298528B (zh) * | 2017-06-30 | 2019-08-30 | 东旭科技集团有限公司 | 铝硼硅酸盐玻璃及其制备方法和应用 |
DE102018209040A1 (de) | 2018-06-07 | 2019-12-12 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Abdichtung für eine stoffschlüssige Verbindung mit Abdichtwirkung an ther-misch hoch belasteten Bauteilen sowie ein Verfahren zu ihrer Herstellung |
CA3117892A1 (en) | 2018-11-26 | 2020-06-04 | Owens Corning Intellectual Capital, Llc | High performance fiberglass composition with improved elastic modulus |
MX2021005663A (es) | 2018-11-26 | 2021-07-07 | Owens Corning Intellectual Capital Llc | Composicion de fibra de vidrio de alto rendimiento con modulo especifico mejorado. |
US20220315479A1 (en) * | 2021-04-05 | 2022-10-06 | Bloom Energy Corporation | Glass ceramic seal material for fuel cell stacks |
CN113880430B (zh) * | 2021-10-29 | 2023-11-28 | 长春工业大学 | 用于连接透明镁铝尖晶石陶瓷的玻璃焊料及连接透明镁铝尖晶石陶瓷的方法 |
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US20060019813A1 (en) * | 2004-07-23 | 2006-01-26 | Nippon Sheet Glass Company, Limited | Sealing glass composition, sealing glass frit, and sealing glass sheet |
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US5176772A (en) * | 1989-10-05 | 1993-01-05 | Asahi Glass Company Ltd. | Process for fabricating a multilayer ceramic circuit board |
JPH10139477A (ja) | 1996-11-13 | 1998-05-26 | Nippon Electric Glass Co Ltd | 高膨張ガラス組成物 |
US6124224A (en) * | 1998-09-02 | 2000-09-26 | Ferro Corporation | High temperature sealing glass |
KR100693938B1 (ko) * | 2005-09-20 | 2007-03-12 | 요업기술원 | 고체산화물 연료전지용 고온 밀봉재 |
JP2009184903A (ja) | 2008-01-09 | 2009-08-20 | Sumitomo Chemical Co Ltd | チタン酸アルミニウム系セラミックスの製造方法 |
US8691470B2 (en) * | 2008-11-12 | 2014-04-08 | Bloom Energy Corporation | Seal compositions, methods, and structures for planar solid oxide fuel cells |
DE102009038812A1 (de) * | 2009-08-31 | 2011-03-10 | Uhde Gmbh | Hochtemperatur-beständige kristallisierende Glaslote |
JP5928777B2 (ja) * | 2011-01-18 | 2016-06-01 | 日本電気硝子株式会社 | 高膨張結晶性ガラス組成物 |
DE102012003338A1 (de) | 2012-02-17 | 2013-08-22 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Zusammensetzung für die Herstellung von Glaslotenfür Hochtemperaturanwendungen sowie derenVerwendung |
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2012
- 2012-02-17 DE DE102012003338A patent/DE102012003338A1/de active Pending
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2013
- 2013-02-11 JP JP2014557001A patent/JP6140195B2/ja active Active
- 2013-02-11 EP EP13706940.7A patent/EP2814784A1/de not_active Ceased
- 2013-02-11 WO PCT/EP2013/052679 patent/WO2013120803A1/de active Application Filing
- 2013-02-11 US US14/378,819 patent/US9714190B2/en active Active
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---|---|---|---|---|
US20060019813A1 (en) * | 2004-07-23 | 2006-01-26 | Nippon Sheet Glass Company, Limited | Sealing glass composition, sealing glass frit, and sealing glass sheet |
Also Published As
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JP2015513512A (ja) | 2015-05-14 |
WO2013120803A1 (de) | 2013-08-22 |
US9714190B2 (en) | 2017-07-25 |
US20150038312A1 (en) | 2015-02-05 |
DE102012003338A1 (de) | 2013-08-22 |
JP6140195B2 (ja) | 2017-05-31 |
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