KR20070059159A - High strength insulating joints for solid oxide fuel cells and other high temperature applications and method of making - Google Patents

Abstract

A seal formed between two parts that will remain gas tight in high temperature operating environments which experience frequent thermal cycling, which is particularly useful as an insulating joint in solid oxide fuel cells. A first metal part is attached to a reinforcing material. A glass forming material in the positioned in between the first metal part and the second part, and a seal is formed between the first metal part and the second part by heating the glass to a temperature suitable to melt the glass forming materials. The glass encapsulates and bonds at least a portion of the reinforcing material, thereby adding tremendous strength to the overall seal. A ceramic material may be added to the glass forming materials, to assist in forming an insulating barrier between the first metal part and the second part and to regulating the viscosity of the glass during the heating step.

Description

HIGH STRENGTH INSULATING JOINTS FOR SOLID OXIDE FUEL CELLS AND OTHER HIGH TEMPERATURE APPLICATIONS AND METHOD OF MAKING}

The invention has been carried out with government support under Arrangement DE-FC26-02NT41246 granted by the United States Department of Energy. The government has certain rights in the invention.

The present invention relates to systems and methods for forming high strength, gas-tight, insulating joints between components used in high temperature applications, and joints made therefrom. Although not intended to be limiting, the invention is particularly useful when used in the fabrication and operation of solid oxide fuel cells.

A solid oxide fuel cell (SOFC) is a solid state device that converts chemical energy of incoming fuel directly into electricity through an electrochemical reaction. Due to its high efficiency and low heat dissipation, SOFCs are increasingly interested in many industries such as the device and automotive industries. Among other SOFCs, the planar shape is expected to provide a more mechanically robust, high power density, and more cost-effective design for high volume manufacturing. In SOFC stacks, interconnects are used to physically separate fuel on the cathode side and air or oxidant on the anode side. It also acts as a bi-polar plate, in which a number of ceramic cells or PENs (Positive Cathode-Electrolyte-Negative anodes) are electrically connected in series within the stack. In order for the SOFC stack to work correctly, the interconnects must be hermetically sealed to adjacent components, ie the PEN or a metal frame supporting the PEN. The seal between adjacent interconnects must be electrically insulated to prevent shorting. Such electrically insulated seals are often performed using glass-ceramic, and other sealing techniques are also contemplated. In order to maintain structural stability and minimize degradation of SOFC performance, the sealing material must be chemically compatible with the interconnects.

In most planar SOFC stacks operating at moderate temperatures (700-800 ° C.), the interconnects are generally made of ferritic stainless steel and sealed with sealing glass to its adjacent elements.

One of the inherent problems found during glass sealing is the formation of an oxidant scale at the interface between the glass and the metal structural element. Initially this scale layer adhered well to the underlying metal substrate, but after prolonged exposure to the high temperature operating conditions of the SOFC stack, the scale thickened and weakened, eventually resulting in glass-metal sealing joints, especially during thermal cycling, It may cause a malfunction. One way to alleviate this problem is to roughen the surface of the metal substrate so that the glass seal is mechanically held in place. However, simple sand blasting or grain boundary etching does not provide a surface that is “rough” enough to form a seal that will not fail under normal operating conditions of the SOFC stack.

Another problem is that it is difficult to control the viscosity of the glass at the sealing temperature and the glass can become very fluid. If the glass is too fluid, it may squeeze out during the sealing process, especially if the parts are loaded or squeezed in the sealing step to ensure that the parts match exactly.

Thus, there is a need for an improved method for joining metal and ceramic components used in high temperature applications such as those found in SOFCs.

It is therefore an object of the present invention to provide a method of forming a seal capable of maintaining airtightness in a high temperature operating environment which experiences frequent thermal cycling between the metal part and the second part. Another object of the present invention is to provide a seal having an insulating property which prevents electrical conductivity between the first metal part and the second part by this method. These and other objects of the present invention are first achieved by providing a first metal part and a second part. The second component may be ceramic or metal. In embodiments where the second part is a metal, the second part may be treated in the manner described below for the first metal part.

Metal reinforcing materials, such as, but not limited to, porous meshes or series of metal protrusions (including but not limited to metal spheres, particles, wires, screens, and fibers) are attached to the first metal part. Any prior art method for attaching the reinforcing material to the metal part to form a durable and strong connection between the screen or other reinforcing material and the first metal part is suitable, and brazing, welding Methods such as, sintering, and the like, are not limited thereto. A glass forming material is then positioned between the first metal part and the second part, and the glass is heated to a temperature suitable for softening the glass forming material to form a seal between the first metal part and the second part. . In this way, a glass or glass-ceramic layer is formed which is bonded at one side with the first metal part and at the opposite side with the second part.

Prior to cooling, the formed molten glass will penetrate through the reinforcing material and thereby encapsulate at least a portion of the attached metal screen or metal projection. In this way, when tensile, shear or torsional forces are applied to the joint, a significant portion of the load is transferred from the glassy matrix to the metal-metal bond between the reinforcing material and the underlying metal substrate. This metal-metal bond will withstand substantially higher loads than planar glass-oxide scale-metal interfaces present in traditional glass-metal joints. Second, the reinforcing material acts as a metal reinforcing phase in the glass or glass-ceramic matrix, and accordingly the base glass material by various crack deflection and crack blunting mechanisms. Improves fracture toughness. Both effects significantly increase the strength of the composite seal than with traditional glass-metal seals.

The motivation for the development of the present invention was to provide a solid insulating joint in a solid oxide fuel cell, but one of ordinary skill in the art would appreciate that the joint of the present invention, and the method for forming the joint of the present invention, It will be appreciated that it is equally applicable to any environment that requires airtightness, insulation sealing between the first metal part and the second part, in particular a high temperature operating environment for the parts. Thus, the present invention should not be construed as being limited to applications including solid oxide fuel cells, but instead should be construed to cover any and all applications in which robust insulating joints are required.

In addition, the motivation for the development of the present invention was more particularly to provide a sturdy insulated joint between two metal parts in a solid oxide fuel cell, but those skilled in the art will appreciate that the joint, And the method for forming a joint of the present invention is equally applicable to an environment where only one of the parts is a metal part. For example, although not intended to be limiting, in many designs for solid oxide fuel cells, there is also an interface between the metal part and the ceramic part, which may require airtightness, insulation sealing. Thus, the present invention should not be construed as being limited to an application involving a seal between two metal parts in a solid oxide fuel cell or otherwise, but instead any two parts wherein at least one of the parts is a metal. It should be construed to cover any and all applications where a strong insulated joint is required between.

Preferably, although not intended to be limiting, the metal parts and metal reinforcing materials used in the present invention are selected as hot stainless steel and hot superalloy. Representative high temperature stainless steels will include Durafoil (alpha-4), Fecralloy, stainless steel coated with alumina, and Crofer-22APU. Representative superalloys will include Heynes 214, Nicrofer 6025, and Ducralloy. The metal parts and the reinforcing components need not be identical alloys, but they must be compatible with each other under planned conditions for sealing and future service.

Preferably, although not intended to be limiting, the thickness of the joint formed by the present invention is within the range of about 0.1 mm to 2 mm.

When forming the joints of the invention, ceramic material will be in parallel between the first metal part and the second part. The ceramic material will serve two or more functions. For example, the ceramic material integral with the glass formed from the glass forming material will assist in forming an insulating barrier between the first metal part and the second part. In addition, the ceramic material will help to adjust the viscosity of the glass during the heating step. Preferably, but not intended to be limiting, the ceramic material is such that the molten glass is sufficiently viscous such that the reinforcing material and the second part adhered to the metal part between the metal part and the second part. Modifying the molten glass in such a way as to maintain separation between, or between the reinforcing material attached to the first metal part and the reinforcing material attached to the second metal part, thereby resulting in an electrical passage between the two parts. To prevent its formation.

At the same time, the molten glass maintains sufficient fluidity to encapsulate and penetrate the glass into the tempered material attached to the parts, thereby encapsulating the tempered material and the underlying metal substrate. It is preferable to attach directly to the reinforcing material and the lower metal substrate. In this way, the glass is bonded directly to the parts, forming a gas tight seal between the parts, and at the same time penetrating into the reinforcing material to form a very durable bond. Preferably, but not intended to be limiting, the ceramic material is selected from zirconia, stabilized zirconia, alumina, nickel oxide, and combinations thereof.

In order to minimize or control the amount of protruding during sealing, the present invention relates to a glass-forming material prior to using a small monosize ceramic (typically yttria stabilized zirconia) sphere at about 2-5% by volume for the sealing. It is considered to put it in, which is not intended to be limiting. The ceramic spheres remain geometrically stable at the sealing temperature and retain their rigid solid form, while the glass softens and flows. The spheres act simultaneously as load columns and geometric spacers to prevent excessive glass from escaping between the two sealing surfaces during the heating and compressing steps employed to form the seal. The spheres also reduce possible metal-to-metal contact in the cell frame, thereby preventing the stack from electrically shorting.

Also preferably, but not intended to be limiting, the ceramic is provided in small fibers approximately 1 mm in length and 20 μm in diameter, which is homogeneously distributed in the glass forming material prior to heating and sealing formation. It is. One example of a suitable ceramic of this type is a Type ZYBF material available from Zircar Zirconia, Inc. of Florida, New York. Also preferably, but not intended to be limiting, glass forming materials that do not contain ceramics or particulates are locally used and penetrated into each of the reinforcing surfaces on the two metal parts, for example as a paste. . A second glass forming material comprising ceramic fibers, spheres, or porous matting is placed between the two parts and sealed by heating. Thus, both glass penetration into the reinforcing material and the formation of an electrically insulating seal can be easily assured.

The glass itself comprises about 10 mol% B ₂ O ₃ , about 35 mol% SiO ₂ , about 5 mol% Al ₂ O ₃ , about 35 mol% BaO, about 15 mol% CaO and barium aluminosilicate family Other forms of glass and combinations thereof, including but not limited to. The glass is preferably mixed with an organic binder material, such as that available from Ferro Corporation, Cleveland, Ohio. Proper selection of binders and accompanying solvents allows glass-forming pastes to be produced or thin sheets or tapes of glass-forming materials to be prepared. . In particular, the paste allows the glass forming material to be applied to the metal part and the second part in the correct position and in the correct amount, such that a gas tight seal is formed. The metal part and the second part are then placed together and heated at a sufficient time and at a sufficient temperature to completely oxidize and vaporize, thus removing the organic binder and melting the glass forming material to penetrate the bonded reinforcing material Forming the glass encapsulating the bonded reinforcing material, but not at least partially, forms the hermetic, insulating joint of the present invention. For the preferred material described herein, heating at 825 ° C. for 1 hour is sufficient to form the joint.

The following detailed description of the embodiments of the present invention will be more readily understood when interpreted in conjunction with the drawings.

FIG. 1 is a comparison of SOFC window frame members against rupture test specimens (not shown on relative scale).

FIG. 2 is a diagram of a cassette to cassette seal. FIG.

3 is a schematic diagram of a breaking test apparatus.

A series of experiments were performed to illustrate the apparatus and method of the present invention and to test the joints or seals formed by the present invention. While these experiments are useful for describing certain features and aspects of the present invention, they should not be construed as describing all of the various aspects of the present invention. As will be appreciated by those skilled in the art, including, but not limited to, the selection of materials and the methods and operating parameters used to combine the materials, from the experiments described herein Through significant changes many of the advantages of the present invention can be readily achieved. Accordingly, the present invention should be construed broadly to include all such improvements and equivalents covered by the appended claims.

This invention contemplates the use of reinforcing materials, for example metal powders, metal wires, mesh screens or a series of metallic protuberances, the metal protrusions being sintered, It is machined from any other form of metal that can be etched or secured to a substrate or substrate and then surrounded by sealing glass. One concept of the present invention is that when a tensile or shear or torsional force is applied to the joint, the load is a metal-to-metal junction between the reinforcing material and the substrate. -metal joins). This metal-to-metal junction will withstand much higher loads than glass-oxide scale-metal interfaces.

In order to test the durability of the seal formed by the present invention, a series of parts were joined. In one embodiment, a first part, similar to a regular washer, comprising a metal ring having an inner diameter of 15 mm and an outer diameter of 44 mm, engages with a second part comprising a flat disk having a diameter of 25 mm. It became. After the various metals have been selected, a glass forming material is placed between the parts, the glass forming material is heated at a temperature sufficient to melt the glass forming material for a sufficient time, thereby forming them into glass and the glass on the surface of the metal part. By allowing them to bond, various metals were bonded together. In some experiments, only the glass forming materials were used to form a bond, and in other experiments, a screen, generally of the same shape as the corresponding metal parts, was first welded to the part described herein, and in another experiment Also, the additional ceramics described herein have also been added to the glass forming material.

In a second embodiment, a metal screen generally shaped the same as the metal ring was first welded to a second part comprising the component described herein and the ceramic bilayer disk, the ceramic double layer disk being the disk. It is constructed nominally with an 8 μm thick YSZ layer attached to a 350 μm thick cathode material sealed with glass, as described above on the YSZ plane of. In comparison, SOFC window frames consist of a metal support plate, a glass forming material, and a cathode / electrolyte. The SOFC cassette consists of the window frame described above, which is coupled (by laser welding) to a metal separator plate. The sealed metal ring for the ceramic double layer disc test specimen approximates the seal of the window frame member, while the sealed metal ring for the metal disc specimen approximates the seal between the cassettes, which will form a complete SOFC stack. When used.

The first and second parts were then tested to see if there was a conductive path from the first part to the second part. Finally, pressure was applied through the hole in the first part until the seal broke and the second part "popped off", ie broken. This breaking strength test does not provide an absolute measure of the various seal strengths, but compares the same parameters as the various materials used in the part, i.e. the presence of the reinforcing material and the presence or absence of the ceramic added to the glass forming material. The relative strength of the seal can be measured well. Table 1 summarizes examples of various test pieces, the metal member, the sealing type, and the ceramic member used in the test of the present invention.

Table 2 summarizes the breaking strength values as a function of test conditions. All strength values are reported in pounds per square inch (psi). The sealed specimens were made using a 20 mil cropper-22APU and Ni-YSZ / YSZ bilayer prepared as described herein. Sealing was performed at 825 ° C. for 1 hour and then annealed at 750 ° C. for 4 hours before cooling to room temperature. Thermal cycle testing was performed by heating at room temperature to 750 ° C. for 10 minutes, holding at 750 ° C. for 10 minutes, and then cooling to room temperature for 40 minutes. Age testing (soaking) was performed in static air at 750 ° C.

The glass identified as “G-18” includes about 10 mol% B ₂ O ₃ , about 35 mol% SiO ₂ , about 5 mol% Al ₂ O ₃ , about 35 mol% BaO, about 15 mol% CaO, and preferred Organic binder vaporized during the heating step described in the embodiments.

As an example, Figure 1 shows how the tests of the present invention are performed. The test essentially employs the principal fuel cell component, i.e., the thumbnail of the window frame and cassette as the test specimen. According to FIG. 1, the metal washer 1 acts as a metal mold of the SOFC. A 25 mm diameter ceramic bi-layer coupon 2, ie a metal disk, is sealed directly to the metal washer 1 by a glass seal 3. In comparison, the framework 4 of the same structure as used for the pSOFC stack exhibits an outer diameter of 44 mm with a center of 15 mm in diameter, which is advantageous for an anode-supported double layer coupon 5. Sealed with a seal (3). Like the actual ceramic pSOFC cell, the double layer coupons 2 and 5 carried by the cathode consist of NiO-5YSZ as the cathode and 5YSZ as the electrolyte. The double layer coupons were produced by tape casting and co-sintering techniques developed at the Pacific Northwest National Laboratory. To prepare the anode layer, NiO (JT Baker) at a 38:25:37 volume percent ratio for a day and a half, with a dispersion system of polyvinyl butyral binder and 2-butanone / ethyl alcohol solvent , 5YSZ (Zirconia Sales, Inc.), and carbon black (Colombia) powder were ball milled. The slurry was cast over a silicon coated mylar to form a tape of ˜0.4 mm thick after the solvent evaporated. The electrolyte tape ball milled 5YSZ with a polyvinyl butyral binder and a 2-butanone / ethyl alcohol dispersion system for 2 days to form a tape having an as-dry thickness of about 50 μm. The slurry was prepared by casting the slurry onto a silicone coated mylar by the doctor blade technique. The negative and electrolyte tapes were then laser cut into piles of 100 × 100 mm size. A plurality of negative electrode tape piles were stacked together with one layer of the above electrolyte tape to apply heat and pressure to form one green double layer tape. A disk 30 mm in diameter is cut from the laminated tape using a circular hot knife. The green part was then sintered in air at 1350 ° C. for 1 hour, yielding a finished bilayer member having a nominal diameter of 25 mm, a nominal thickness of 600 μm and an average electrolyte thickness of ˜8 μm. .

The metal materials employed in the manufacture of rings and discs are obtained as sheets with a thickness of 300 μm in as-annealed conditions, unless otherwise specified. The flat washer and disc shaped specimens were cut from the sheet by electrical discharge machining and the sealing surface was polished to a nominal 10 μm diamond grit finish and sprayed with deionized water. The grit is removed, sonicated for 10 minutes in acetone and washed with methanol before use. The reinforcing material, for example a metal screen nominally the same size and structure as the ring and disc pieces, is cut and spot welded into corresponding flat metal parts to form a reinforcing surface for the glass matrix in the seal. Form.

The glass sealing composition, referred to as G-18, for example, is based on glass initially melted from a mixture of the following oxides of barium potassium aluminosilicate designed in the industry: 10 mol% B ₂ O ₃ , 35 mol% SiO ₂ , 5 mol% Al ₂ O ₃ , 35 mol% BaO, and 15 mol% CaO. The G-18 powder was ground to an average particle size ˜20 μm and mixed with a polyvinyl butyral binder system to be dispensed onto the substrate surface at a constant rate of 0.075 g / linear cm using an automatic syringe dispenser. To form a paste. In this way, the glass paste is dispensed to the YSZ side of the double layer disc or the reinforcing material side of the metal disc. Each disc is then placed centered on the washer specimen, weighed 50 g, and heated in air according to the following sealing schedule: heated to 850 ° C. at 10 ° C./min at room temperature and 1 at 850 ° C. It is maintained for hours, cooled to 5 ℃ / min to 850 ℃, and held for 4 hours at 750 ℃, then cooled to 5 ℃ / min to room temperature.

As shown in FIG. 2, the SOFC cassette is a repeating unit of the SOFC stack. It consists of a ceramic PEN 10 (double layer with an anode layer applied) sealed with a metal mold 12 to form the window frame described above, which is bonded (by laser welding) to the metal separator 14. In the GFM concept, the reinforcing material 16 (eg mesh) is first bonded to the sealing surface of each cassette, and the surface around each manifold opening 18 and of the cassette 20 External surface. In order to ensure electrical insulation between the cassettes, glass forming materials 22, including ceramic spacer materials (fibers, spheres, particulates, etc.) are generally used to completely seal adjacent cassettes to each other. . The entire stack of cassettes is generally combined in one sealing operation.

A schematic of the experiment used for the fracture test is shown in FIG. 3. The test sample is placed in a fixture consisting of a bottom flange 30 and a top flange 32, and a connector 34 fixes and centers the two flanges 30, 32. On, the O-ring 36 is pressed against the bottom surface of the washer. Compressed air pumped along air line 40 is used to apply pressure to the backside of the washer specimen up to 150 psi, the maximum rated pressure. A digital regulator (38) causes the pressure to slowly increase to a given set value behind the coupled double layer disk (33). The volume of this compressed gas can be isolated between the specimen and the valve, allowing for leak checking in the seal due to pressure reduction. In this way, the device can be used to measure the airtightness of a given seal's configuration without causing breakage of the seal. Conversely, by increasing the pressure to the point at which the specimen breaks, the maximum pressure that the specimen can withstand can be measured using the pressure gauge 42. At least six specimens were tested for each binding condition.

Specimen configuration according to FIG. 1. All metal substrates are 20 mils thick. Psalter Ring member Sealing type Disc member 430-G18T-Bi 430 stainless steel G-18 glass, applied as a thin cast tape (prepared with an organic binder) cut into ring shapes Double Layer Supported by NiO-YSZ Cathode 430-G18T-APU 430 stainless steel G-18 tape (same as above) Croper-22 APU 430-G18DF-Bi 430 stainless steel G-18 glass prepared as paste (containing 8% YSZ fiber) Double Layer Supported by NiO-YSZ Cathode OxAPU-G18T-Bi Oxidized Croper-22 APU at 800 ° C. for 2 hours before sealing G-18 tape (same as above) Double Layer Supported by NiO-YSZ Cathode APU-G18DGFM-Bi Cropper-22 APU board with spot-welded cropper-22 APU mesh (100 × 100 plain weave, wire diameter 0.006 ") G-18 glass prepared as paste (containing 8% YSZ fiber) Double Layer Supported by NiO-YSZ Cathode APU-G18DGFM- APU Cropper-22 APU Board with Spot Welded Croper-22 APU Mesh (100 × 100 Plain Weave, Wire Diameter 0.006 ") G-18 glass prepared as paste (containing 8% YSZ fiber) Cropper-22 APU Board with Spot Welded Croper-22 APU Mesh (100 × 100 Plain Weave, Wire Diameter 0.006 ")

Sealing type Exam conditions Average intensity Strength Strength 430-G18T-Bi Sealed immediately 23 18 27 430-G18T-Bi 3 thermal cycles 21 14 28 430-G18T-APU Sealed immediately 33 28 38 430-G18T-APU 3 thermal cycles 25 21 27 430-G18DF-Bi Sealed immediately 21 15 31 430-G18DF-Bi 5 thermal cycles 17 9 27 OxAPU-G18T-Bi Sealed immediately 29 23 43 OxAPU-G18T-Bi 5 thermal cycles 18 13 23 APU-G18DGFM-Bi Sealed immediately 121 87 132 ^** APU-G18DGFM-Bi 5 thermal cycles 129 114 134 ^** APU-G18DGFM-Bi 10 thermal cycles 128 114 134 ^** APU-G18DGFM-Bi 100 hours of heat aging 124 110 134 ^** APU-G18DGFM-APU Sealed immediately 133 132 ^** 136 ^** APU-G18DGFM-APU 5 thermal cycles 133 131 ^** 135 ^** APU-G18DGFM-APU 10 thermal cycles 134 131 ^** 136 ^** APU-G18DGFM-APU 100 hours of heat aging 133 132 ^** 136 ^**

In the systems and methods of the present invention, it is evident that various changes, additions or deletions can be made without departing from the basic teaching thereof. In addition, the various elements and steps described herein are illustrative of the embodiments currently contemplated as preferred embodiments and should be construed to include equivalents thereof.

Claims (40)

a. Providing a first metal part and a second part; b. Attaching a reinforcing material to the metal part; c. Providing a glass forming material arranged between the first metal part and the second part; And d. The glass forming material penetrates into the reinforcing material, encapsulating at least a portion of the reinforcing material and bonding to at least a portion of the reinforcing material, further sealing an airtight between the first metal part and the second part. heating the second component, the tempered material, and the glass forming material to form a gas tight seal Seal manufacturing method comprising a. The method of claim 1, wherein the metal parts are selected from the group consisting of high temperature stainless steel and high temperature superalloy. The stainless steel of claim 2 wherein the high temperature stainless steel is Durafoil (alpha-4), Fecralloy, stainless steel coated with alumina, and Crofer-22APU. Method selected from the group consisting of. The method of claim 2, wherein the high temperature superalloy is selected from the group consisting of Haynes 214, Nicrofer 6025, and Ducralloy. The method of claim 1, wherein the seal has a thickness in the range of about 0.1 mm to 2 mm. 2. The method of claim 1, further comprising adding a ceramic material to the glass forming material disposed in parallel between the first metal part and the second part, thereby between the first metal part and the second part. Forming an insulating barrier in the substrate. The method of claim 6, wherein the ceramic material is selected from the group consisting of zirconia, stabilized zirconia, alumina and magnesium oxide. The glass forming material of claim 1, wherein the glass forming material comprises about 10 mol% B ₂ O ₃ , about 35 mol% SiO ₂ , about 5 mol% Al ₂ O ₃ , about 35 mol% BaO, about 15 mol% CaO, and the heating. And an organic binder which is vaporized during the step. The method of claim 1 wherein the second part is a metal part. The method of claim 1 wherein the second part is a ceramic part. As a joint between the first metal part and the second part, a. A first metal part with reinforcing material attached, b. A second component, and c. A glass seal, bonded to the first metal part on one side and to the second part on the other side, wherein the glass encapsulates at least a portion of the reinforcing material and at least a portion of the reinforcing material. A glass seal that bonds and forms an airtight seal between the first metal part and the second part, Joint comprising a. The joint according to claim 11, wherein the metal part is selected from the group consisting of high temperature stainless steel and high temperature superalloy. The joint of claim 12, wherein the high temperature stainless steel is selected from the group consisting of Durafoil (alpha-4), pecralloy, stainless steel coated with alumina, and Croper-22APU. 13. The joint of claim 12, wherein the high temperature superalloy is selected from the group consisting of highness 214, nickroper 6025, and ducralloy. The joint of claim 11, wherein the seal has a thickness in the range of about 0.1 mm to 2 mm. 12. The method of claim 11, further comprising a ceramic material disposed in parallel between the first metal part and the second metal part, whereby the second part is integral with glass formed from the glass forming material; A joint formed between said first metal component. The joint of claim 16 wherein the ceramic material is selected from the group consisting of zirconia, stabilized zirconia, alumina and magnesium oxide. The glass of claim 11, wherein the glass comprises about 10 mol% B ₂ O ₃ , about 35 mol% SiO ₂ , about 5 mol% Al ₂ O ₃ , about 35 mol% BaO, and about 15 mol% CaO. Joint to be made. 12. The joint of claim 11 wherein said second part is a metal part. 12. The joint of claim 11 wherein said second component is a ceramic component. As an insulated joint in a solid oxide fuel cell, a. A solid oxide fuel cell having at least a first metal part and a second part, b. The first metal part to which the reinforcing material is attached, and c. Glass seal, wherein the glass seal is coupled to the first metal part on one side and to the second part on the other side, wherein the glass encapsulates at least a portion of the reinforcement material and binds to at least a portion of the reinforcement material. , Joint comprising a. The joint according to claim 21, wherein the metal part is selected from the group consisting of high temperature stainless steel and high temperature superalloy. The joint according to claim 22, wherein the high temperature stainless steel is selected from the group consisting of Durafoil (alpha-4), pecralloy, stainless steel coated with alumina and Croper-22APU. 23. The joint of claim 22, wherein the high temperature superalloy is selected from the group consisting of highness 214, nickroper 6025, and ducralloy. The joint of claim 21 wherein the seal has a thickness in the range of about 0.1 mm to 2 mm. 22. The method of claim 21, further comprising a ceramic material disposed in parallel between the first metal part and the second part, whereby the second part and the one being integral with glass formed from the glass forming material. And forming an insulating barrier between the first metal parts. The joint of claim 26 wherein the ceramic material is selected from the group consisting of zirconia, stabilized zirconia, alumina and magnesium oxide. The glass of claim 21, wherein the glass comprises about 10 mol% B ₂ O ₃ , about 35 mol% SiO ₂ , about 5 mol% Al ₂ O ₃ , about 35 mol% BaO, and about 15 mol% CaO. Joint to be made. The joint of claim 21 wherein the second part is a metal part. The joint of claim 21 wherein the second part is a ceramic part. a. Providing a first metal part and a second part; b. Attaching a reinforcing material to the metal part; c. Providing YSZ spheres dispersed in a glass forming material arranged between the first metal part and the second part; And d. The glass forming material penetrates into the reinforcing material to encapsulate at least a portion of the reinforcing material and couple to at least a portion of the reinforcing material, further forming an airtight seal between the first metal part and the second part. Heating the first metal part, the second part, the reinforcing material, and the glass forming material. Metal-to-ceramic seals manufacturing method comprising a. 32. The method of claim 31, wherein the metal part is selected from the group consisting of high temperature stainless steel and high temperature superalloy. The method of claim 32, wherein the high temperature stainless steel is selected from the group consisting of durafoil (alpha-4), pecralloy, stainless steel coated with alumina, and Croper-22APU. 33. The method of claim 32, wherein the high temperature superalloy is selected from the group consisting of highness 214, nicroper 6025, and ducralloy. The method of claim 31, wherein the seal has a thickness in the range of about 0.1 mm to 2 mm. 32. The method of claim 31, further comprising adding a ceramic material to the glass forming material disposed in parallel between the first metal part and the second part, thereby integrally with the glass formed from the glass forming material. Forming an insulating barrier between the second component and the first metal component. 37. The method of claim 36, wherein the ceramic material is selected from the group consisting of zirconia, stabilized zirconia, alumina and magnesium oxide. The method of claim 31, wherein the glass forming material comprises about 10 mol% B ₂ O ₃ , about 35 mol% SiO ₂ , about 5 mol% Al ₂ O ₃ , about 35 mol% BaO, about 15 mol% CaO, and the heating. A method comprising the organic binder vaporized during the step. 32. The method of claim 31, wherein the second part is a metal part. 32. The method of claim 31, wherein the second part is a ceramic part.

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