Advanced mica based seal and methods for making and using

Abstract

A mica based compressive seal has been developed exhibiting superior thermal cycle stability when compared to other compressive seals known in the art. The seal is composed of compliant glass or metal interlayers and a sealing (gasket) member layer composed of mica that is infiltrated with a glass forming material, which effectively reduces leaks within the seal. The compressive seal shows approximately a 100-fold reduction in leak rates compared with previously developed hybrid seals after from 10 to about 40 thermal cycles under a compressive stress of from 50 psi to 100 psi at temperatures in the range from 600° C. to about 850° C.

Description

FIELD OF THE INVENTION

[0003] The present invention relates to an advanced multilayer compressive seal, generally. More particularly, the present invention relates to an advanced mica-based sealing (gasket) member for use in multilayer compressive seals applicable to high-temperature devices and methods of making and using. High-temperature devices include electrochemical devices such as solid oxide fuel cells, syngas generators, and membrane reactors whereby different gaseous streams internal to the device at elevated temperatures must be kept separate from each other. The sealing member and compressive seal of the present invention exhibit superior thermal cycling stability and low effective leak rates compared to other seals known in the art.

BACKGROUND OF THE INVENTION

[0004] High-temperature devices that can convert chemical energy of a fuel such as hydrogen directly into electrical energy at high efficiency and low or no air pollution are of great commercial interest. Such devices include high-temperature electrochemical devices, solid oxide fuel cells (SOFC), and other similar structures such as interconnects. Electrochemical devices having multiple components, such as, for example, solid oxide fuel cell (SOFC) stacks, syngas membrane reactors, oxygen generators and the like require seals to separate the various gaseous components [e.g., H2 (fuels) and O2 (oxidants)] and to prevent the streams from mixing with each other. Mixing of the gas streams has a variety of negative consequences, depending upon the type of device and the composition of the gaseous streams. One major problem resulting from mixing of such gases is the possibility of thermal combustion of the gases and the resulting failure of the device. Thus, to ensure high efficiency and to maintain the stack structural integrity, seals are needed to separate the various gaseous components (fuels and oxidants). Such seals must be non-conducting, have chemical, mechanical, and/or thermal compatibility with other structural components of the devices. The seals must also exhibit very low operational leak rates in severe (oxidizing, reducing, and humid) environments as well as long-term thermal cycling stability at elevated temperatures.

[0005] Continued thermal cycling at high operating temperatures up to about 850° C. results in increased leak rates in mica-based compressive seals, a consequence of damage resulting from fragmentation, cleavage, micro-stress fractures, and similar processes to the microstructure of the mica substrate matrix. Such damage introduces leak paths or void spaces (interstices) that are continuous in three dimensions. High leak rates and thermal cycling instability of current seals under routine high temperature operation represent two of the most challenging hurdles remaining for significant advancement to be made in the long-term success of high-temperature devices, including electrochemical devices such as SOFCs, and/or toward developing and/or deploying long-term viable components in other similar high temperature devices.

[0006] Accordingly, there remains a need to provide advanced seals and sealing structures having low effective leak rates and superior thermal cycling stability such that at the operating temperatures of these high temperature devices (up to about 850° C.), gaseous leaks (e.g., H2 gas into the air stream or vice versa) do not cause undesirable local heating leading to structural or functional failure of the device.

SUMMARY OF THE INVENTION

[0007] The present invention relates generally to components, structures, and methods for preparing seals applicable for sealing in high-temperature devices. More particularly, the present invention is an advanced mica-based sealing (gasket) member that finds application in multilayer compressive seals useful in high-temperature devices such as electrochemical cells, solid oxide fuel cells, gas reactors, syngas reactors, and the like. The sealing member of the present invention exhibits superior thermal cycling stability and effectively low leak rates at high operating temperatures up to about 850° C., and methods for making and using the same.

[0008] In a previous invention (U.S. application, Ser. No. 10/134,072 filed Apr. 27, 2002) we have demonstrated that by adding additional compliant interlayers (glass or metal) to mica-based seals, leak rates at about 800° C. can be reduced several thousand times compared to mica-based seals presently known in the art. A barium aluminum silicate glass (G-18) is one of a number of representative materials found to exhibit excellent Coefficient of Thermal Expansion (CTE) matching properties for use in SOFC and electrochemical devices, as detailed in U.S. patents to Meinhardt et al. (U.S. Pat. No. 6,430,966 and U.S. Pat. No. 6,532,769) hereby incorporated by reference.

[0009] The multilayer compressive seal of the instant invention comprises a sealing (gasket) member having a mica based member infiltrated with at least one member selected from of a group of a suitable glass forming, melt forming, or composite material(s), and, at a minimum, two (2) compliant glass or metal interlayers disposed so as to be aligned with the opposing surfaces of the sealing member. The sealing member may also be disposed so as to be in contact with other materially and functionally important substrates, layers, surfaces, junctions, interconnects, or components of the compressive seal or of the target application or device. For example, bounding surfaces of a typical high-temperature device include such components as cathodes, anodes of an electrochemical stack or device, YSZ components, interconnects, ceramics, SOFC junctions and components, and the like. In one embodiment of the present invention, the compliant glass or metal interlayers are disposed along the opposing surfaces of an infiltrated sealing (gasket) member in further contact with a bounding surface electrolyte or interconnect, thereby acting as an interface between the sealing member and other non-compliant surfaces.

[0010] In a preferred embodiment, the sealing (gasket) member of the present invention is composed of a mica in a paper form, e.g., as discrete flakes pressed into a thin paper. Phlogopite and Muscovite micas are available commercially (McMaster-Carr, Atlanta, Ga. and Cogebi Inc., Dover, N.H.) in paper form or as flakes. Other mineral types for mica include Biotite, Fuchsite, Lepidolite, and Zinnwaldite, which may also find application.

[0011] For compressive seals, a degree of mismatch exists between the various components of the compressive seal or device. To minimize the mismatch, the sealing member of the present invention preferably comprises mica having a Coefficient of Thermal Expansion (CTE) in the range from 7-17 ppm/° C. Phlogopite, for example, has an average (room temperature to −800° C.) CTE of about 10 ppm/° C.; Muscovite has a comparable CTE of about 7 ppm/° C. Comparable metallic components (for example, interconnects for use in SOFCs) have preferred CTE values in the range from about 12 ppm/° C. to 17 ppm/° C. In addition, the selected micas are preferably of a paper form (i.e., as discrete flakes pressed into a thin paper) thereby providing an open matrix structure and for ease of handling. For example, Phlogopite mica papers are easily infiltrated by delivering the infiltrating material (e.g., dissolved or solvated glass or melt forming material) in a carrier liquid to the top of the mica paper. In addition, they remain at a relatively constant thickness during handling. The as received naturally cleaved Muscovite mica, being in a monolithic form, has no porosity but does cleave into multiple sublayers (˜2-10 microns thick) after firing to a temperature >600° C. as it loses chemical water (˜4%) and tends to expand significantly in apparent thickness as the sublayers become separated from each other. Since the naturally cleaved Muscovite mica as received has no cracks or openings in the top sublayer, the infiltrating process requires soaking the whole mica sheet in the applicable infiltrating liquid or material. The sealing (gasket) member is preferably of a thickness in the range from about 25 microns to about 1 millimeter. However, thickness of the mica is less important than that the mica be properly infiltrated and prepared for use as described hereinafter.

[0012] Prior to infiltration, the mica sealing member substrate may be heated in an oven at a temperature between 500° C. to 700° C. for from 1 to 4 hours to remove any organic binders (typically present at about 34% by weight in standard commercially available mica papers). Infiltration of the sealing (gasket) member generally comprises introducing a glass or melt forming material into the matrix of the mica substrate such that continuous flow paths representing potential and real leak paths within the matrix are effectively blocked and/or sealed. The infiltrating material comprises at least one member of a suitable group of glass or melt forming materials, oxides, composites, mica:glass composites, or like material(s). Upon heating, the infiltrating material becomes fixed in the plurality of spaces (voids, flow paths, leak paths, necking areas, interstitial spaces, gaseous leak paths, etc.) of the sealing member, creating discontinuities in the three dimensional flow paths of the substrate matrix, thereby effecting sealing. The infiltrated sealing member likewise effects sealing when incorporated in a multilayer compressive seal or selected high temperature device.

[0013] In one embodiment of the method of the present invention, infiltrating a sealing member for use as a sealing (gasket) member comprises the steps: 1) infiltrating (permeating) the sealing member matrix (mica substrate, paper, etc.) with an infiltrating material, for example, a saturated liquid solution comprising a dissolved or solvated glass (or melt) forming material, 2) fixing (adhering) the glass forming material within the voids (and more specifically at junctions, necking areas, and/or interstitial spaces) of the matrix, for example, by drying the sealing member in an oven at a temperature of about 50° C. for ˜1 hour, and 3) incorporating the infiltrated sealing member in a compressive seal, (e.g., in a hybrid multilayer seal under a selected compressive stress), or assembling the sealing member as a component in a high-temperature device for a desired application. For example, an infiltrated sealing member incorporated in a compressive seal, electrochemical device, SOFC, or comparable device under compressive stresses in the range from 25 psi to 300 psi, more preferably in the range from 50 psi to 100 psi.

[0014] In yet another embodiment of the method of the present invention, infiltrating the sealing member alternately comprises the steps: 1) providing an infiltrating material comprising mica (e.g., flakes or particles) and a glass (or melt) forming material in a mica:glass composite, 2) forming and/or fashioning a sealing (gasket) member in a desired shape and thickness using standard glass forming, preparation, manufacturing, and/or processing techniques known to those of ordinary skill in the art, e.g., slip-casting, tape casting, tape calendaring, die pressing, or the like), 3) fixing the infiltrated material within the sealing (gasket) member matrix at room temperature for ˜4 hours or a temperature of 50 IC for ˜1 hour, and 4) incorporating the infiltrated sealing member in a compressive seal, or assembling in a high-temperature device.

[0015] It will be recognized and appreciated by persons of ordinary skill in the art that infiltrating the mica-based matrix may be accomplished in a variety of different ways. Thus, no limitation in scope is herein intended by the disclosure of the preferred embodiments.

BRIEF DESCRIPTION OF THE DRAWINGS

[0016] A more complete appreciation of the invention will be readily obtained by reference to the following description of the accompanying drawings in which like numerals in different figures represent the same structures or elements.

[0017] FIG. 1A. illustrates the microstructure in a commercially available mica paper showing a continuous three-dimensional leak path following “burnout” of the organic binder.

[0018] FIG. 1B. shows a schematic drawing of a representative mica paper infiltrated with a glass or melt forming material. The figure shows the infiltrated mica paper at elevated temperature under applied stress with the continuous leak path being blocked.

[0019] FIG. 1C. illustrates the differences in leak paths for the as-received mica and the infiltrated mica paper (in a hybrid design with a compliant interlayer disposed adjacent on opposite sides of the mica paper). The leak path in the as received mica paper is continuous in three (3) dimensions.

[0020] FIG. 2 illustrates the effect of thermal cycling on normalized leak rates for a non-infiltrated Phlogopite mica paper.

[0021] FIG. 3 illustrates shows the leak rates of two H3BO3 (aq) infiltrated Phlogopite mica papers (Samples A and B) versus the number of thermal cycles.

[0022] FIG. 4 illustrates the thermal cycling effect on normalized leak rates at 800° C. of the Bi(NO3)3(aq)-infiltrated Phlogopite mica.

[0023] FIG. 5 shows leak rates results for a mica:glass (90 v %:10 v %) composite seal compressed at 100 psi.

[0024] FIG. 6 shows the results of the mica:glass (80 v %:20 v %) composite seal compressed at 50 psi.

DETAILED DESCRIPTION OF THE INVENTION

[0025] FIGS. 1A-1-C illustrate the components of an advanced mica-based sealing (gasket) member 30 and compressive seal 100 according to an embodiment of the present invention. The sealing member 30 is generally composed of a mica paper 20 comprising overlapping mica flakes 22 compressed in a thin paper form and a plurality of spaces (voids, flowpaths, interstices, necking areas, leak paths, etc.) 24 (FIG. 1A). The microstructure and thermal behavior of mica papers have been described in some detail elsewhere (see “Ultra-low Leak Rate of Hybrid Compressive Mica Seals for SOFCs”, Yeong-Shyung Chou, Jeffry W. Stevenson, and Lawrence A. Chick, Pacific Northwest National Laboratories, Materials Resource Department, P.O. Box 999 Richland, Wash. 99352) hereby incorporated by reference. The sealing member 30 is infiltrated as shown in FIG. 1B whereby the voids and interstitial spaces of the mica paper 20 substrate or matrix are filled, sealed, or otherwise made discontinuous with an infiltrating material 32. As shown in FIG. 1C, the infiltrated sealing member 30 may then be incorporated as a central sealing component of a compressive seal 100 or other high temperature device. The seal 100 further comprises a 1st and 2nd interlayer 40 of a compliant material, as for example, glass or metal (metal or metal foil), and a 1st and 2nd bounding component 50, for example a 1st and 2nd SOFC component (component I and component II in FIG. IC). The interlayers 40 may be of an identical or different material in the seal 100 depending on the selection of bounding surface materials or components 50.

[0026] Two Phlogopite [(KMg3(AlSi3O10)(OH)2)] mica papers were tested, Sample A [Phlogopite paper, McMaster-Carr, Atlanta, Ga.] having a nominal thickness of about 100 microns (˜4 mils), and Sample B [Cogemica AP-80, Cogebi Inc., Dover, N.H.] having a thickness of about 75 microns (˜3 mils). Sample A contained an organic binder (between 2-5% by weight); Sample B contained no organic binder. Examples 1 through 4 present different embodiments of an infiltrated sealing (gasket) member 30 that may be assembled in a compressive seal 100 or incorporated into a high-temperature device.

EXAMPLE 1

[0027] In one embodiment, the infiltrated sealing (gasket) member 30 was prepared using a liquid infiltration solution comprising at least one glass or melt forming material. The solid glass former was dissolved in an aqueous liquid to a point of saturation, and subsequently delivered into a plurality of spaces 24 (e.g., voids, interstices, flow paths, leak pathways, etc.) within the matrix of the mica substrate 20 using standard liquid delivery techniques (e.g., pipet). Subsequent drying of the substrate 20 fixes the glass or melt former within the matrix, preparing the infiltrated sealing (gasket) member 30 for use. The sealing member 30 was subsequently leak tested in a simulated multilayer compressive seal (hybrid) 100 under a selected compressive stress in the range from 50 to 100 psi under repeated thermal cycling conditions and at expected operating temperatures up to 850° C., and more preferably in the range from 650° C. to 850° C.

[0028] Experimental

[0029] Sample A was heat treated at ˜700° C. for 4 hours to remove organic binders present in the substrate matrix prior to the liquid infiltration step. Sample B was used as received. FIG. 1A illustrates the typical mica paper following removal of any organic binder (e.g., after “burnout”). The figure shows a plurality of spaces (voids, continuities, flow paths, interstitial spaces) 24 of the mica substrate 20 member, prior to infiltration, comprising three-dimensional flow paths largely responsible for generating gaseous leaks in a high-temperature device. FIG. 2 presents normalized leak rates as a function of thermal cycles for a typical non-infiltrated Phlogopite mica (nominal thickness of about 0.1 mm), illustrating the effect of thermal cycling. As shown in the figure, thermal cycling under a compressive load of 100 psi leads to unacceptable leak rates for the non-infiltrated mica paper, about 0.025 sccm/cm, on average.

[0030] Glass or melt forming materials suitable for infiltrating and preventing leaks in the mica substrate are preferably a) non-corrosive, b) soluble in an aqueous medium, miscible in an organic solvent (e.g., Methyl Ethyl Ketone), or mobile in a carrier liquid, and c) have melting point (MP) temperatures above 450° C., more preferably in the range from about 450° C. to about 850° C. so as to be operable in a high-temperature device. Solubility of a glass or melt forming material is a selection criterion based in part on convenience and ease of use. For example, boric acid (H3BO3) has proven to be an excellent candidate based in part on its aqueous solubility, as well as its melting point properties. Bismuth nitrate [Bi(NO3)3.5H2O is equally workable despite its more limited aqueous solubility due to its operable melting point. Both candidates are suitable infiltrating materials for effecting sealing in a sealing (gasket) member 30 destined for incorporation in a high temperature device. In contrast, pure SiO2, another oxide, is not an ideal material for infiltrating the sealing (gasket) member 30 given its many crystalline phases and exceptionally high melting point (˜1400° C.). As another example, pure P2O5 is an equally daunting material, given the corrosivity and reactivity in the reducing and wet environments of an SOFC. The person of ordinary skill in the art will recognize that many materials may be suitable as infiltrating materials. For example, selection criteria may be appropriately based on 1) material oxidation states, 2) glass or melt forming properties, 3) associated chemical properties, e.g., solubility, melting points, etc., 4) solvation properties in various liquid carriers and/or solvents, and 5) other properties associated with the material mixtures or compositions. Thus, no limitation is hereby intended by the disclosure of the preferred embodiments.

[0031] In a first embodiment of the method of the present invention, boric acid (H3BO3) was selected for use as a glass forming material for infiltration, given its high aqueous solubility and ease of handling. A saturated infiltration solution was prepared by dissolving an excess of H3BO3 in de-ionized water. The temperature for infiltrating the matrix of the mica paper 20 substrate of the sealing member 30 was selected to be in the range from 70° C. to 90° C. where boric acid has higher solubility. The boric acid solution was delivered via standard pipette into the matrix (by wetting, dripping, wicking, etc.) of the mica paper 20, thereby infiltrating (saturating and fully permeating) the sealing member 30. The infiltrated and/or treated sealing member (saturated mica paper) 30 was subsequently oven dried in air at a temperature of approximately 50° C. for between 0.5 and 1 hour to fix and stabilize the infiltrating material 32 in the matrix. At the drying temperature, boric acid converts to the oxide form (B2O3) within the matrix of the sealing (gasket) member 30. As illustrated in FIG. 1B, the infiltrating material 32 becomes fixed in a plurality of spaces 24 (voids, interstices, etc.) at critical interstitial contact points, necking areas, between, along, and around the original mica flakes 22 or filaments 22 within the sealing member 30 matrix. Preferably, the glass or melt forming material or oxide has a melting temperature of >450° C. At high temperatures, the infiltrating material effects blocking and/or sealing of three-dimensional leak paths making them discontinuous (as opposed to continuous) and limited in two dimensions (as opposed to three dimensions).

[0032] The sealing member 30 samples were subsequently leak tested following infiltration. Leak rates for the sealing member 30 were determined by incorporating the member 30 in a test mode hybrid multilayer seal 100 (e.g., sandwiched between two glass interlayers 40 pressed between an Inconel 600 pipe and an alumina substrate 50) and pressed at 100 psi using ultra-high purity Helium at a pressure gradient of 2 psi across the compressive seal 100. A detailed description of the leak testing protocol for a multilayer (hybrid) compressive seal has been detailed in [U.S. application, Ser. No. 10/134,072 filed Apr. 26, 2002], which disclosure is incorporated by reference.

[0033] Results

[0034] FIG. 3 compares normalized leak rates at 800° C. for two H3BO3 infiltrated paper (samples A and B) Phlogopite mica compressive seals 100 as a function of thermal cycles, tested under a compressive stress of 100 psi. TABLE 1 presents tabulated leak rate data, determined using ultra-high purity Helium at a pressure gradient of 2 psi across the mica seal 100.

TABLE 1
Normalized leak rates at 800° C. under a compressive stress of 100 psi
of an H3BO3-infiltrated mica-based compressive
seal as a function of thermal cycles.
			#A,
# cycles	#A, as-received	# cycles	infiltrated	# cycles	#B, infiltrated
0	0.0429	0	0.023	0	0.022
8	0.0244	1	0.0243	1	0.0217
9	0.0248	3	0.0188	3	0.0099
9	0.029	4		4	0.00595
13	0.0415	6	0.0116	6	0.00287
16	0.0279	7		7	0.0031
20	0.0227	9	0.00495	9
20	0.0255	12		12
24	0.0267	15	0.000554	15
24	0.0281	16		16	0.000164
36	0.024	18	0.00049	18
36	0.0236	21	0.00039	21
37	0.0217	24	0.000125	24
37	0.0228	25		25
40	0.0209	33		33
40	0.0234	36		36
44	0.0233	37	0.000125	37
44	0.0293	39	0.000125	39
48	0.0205	40		40	0.000269

[0035] As shown in TABLE 1, leak rates were stable after about 10 thermal cycles for both samples and leak rates for the subsequent ˜30 thermal cycles were very low (<0.001 sccm/cm). As compared to the Phlogopite mica paper without the H3BO3 (aq) infiltration (FIG. 2), the normalized leak rates for the infiltrated samples (FIG. 3) are approximately an order of magnitude better, at a minimum, than the non-infiltrated sample (FIG. 2) and several orders of magnitude better at a maximum.

EXAMPLE 2

[0036] In a second embodiment of the present invention, infiltration of the sealing member 30 was conducted as described in Example 1 with the substitution of Bi(NO3)3 in a liquid carrier as the infiltrating liquid, as described hereafter.

[0037] Experimental

[0038] The infiltrating liquid was prepared by introducing 20-26 g Bi(NO3)3 solid (98% Bi(NO3)3.5H2O, Alfa Aesar, Ward Hill, Mass.) in 50 mL of de-ionized water at room temperature. Formation of subnitrates (due to a more limited solubility of bismuth nitrate) in the aqueous medium was not found to compromise the beneficial infiltrating properties of the bismuth nitrate. Infiltration was subsequently conducted at room temperature, as described in Example 1. Following infiltration, the sealing member 30 was oven dried at 50° C. for between 0.5 and 1 hour to fix the infiltrating (glass forming) material 32 within the substrate of the sealing member 30. Heating of the bismuth nitrate converts it to the oxide form (Bi2O3) which has a melting point temperature of ˜815° C. At the operating temperature of a high temperature device (>450° C.), the presence of the glass or melt former effectively seals the plurality of spaces 24 (e.g., continuous flow paths, interstitial spaces, etc.) and/or voids 24 present in the sealing member 30 under compressive stress. Leak testing was subsequently conducted under a compressive stress of 100 psi in a hybrid multilayer assembly, e.g., the mica layer was sandwiched between two glass (G18) interlayers 40 and pressed alternately between three different metal couples 50: Inconel600 pipe/Inconel600 block, Inconel600 pipe/SS430 block, and Inconel600 pipe/Haynes230 block. Coefficients of thermal expansion (CTE) of the three metal couples 50 used were 16 to ˜17 ppm/° C. (Inconel600), ˜12.5 ppm/° C. (SS430), ˜14.8 ppm/° C. (Haynes230), respectively. The CTE of the Phlogopite mica 20 was about 10 ppm/° C. The three metal couples 50 represent a wide range of CTE mismatches by which to test the Phlogopite mica 20 and the infiltrated sealing member 30 compatibility. Any subnitrate residues remaining on the surface of the mica paper after infiltrating the mica substrate were found to penetrate into the matrix under the elevated temperatures and compressive stresses in the test mode assembly.

[0039] Results

[0040] FIG. 4 shows the effect of thermal cycling on the normalized 800° C. leak rates for the Bi(NO3)3 (aq) infiltrated Phlogopite mica seals 100, tested under a compressive stress of 100 psi. TABLE 2 presents the normalized leak rates for the Bi(NO3)3-infiltrated Phlogopite compressive mica seal 100 after 36 thermal cycles. As shown, leak rates were below 0.002 sccm/cm on average after 10 thermal cycles, and at best showed a leak rate of 6.0E-04 following 36 thermal cycles, demonstrating strong thermal cycle stability and effectively low leak rates in the Bi(NO3)3 (aq)-infiltrated mica seal 100 as compared to the non-infiltrated seals (FIG. 2).

TABLE 2
Normalized leak rates of the Bi(NO3)3 (aq)-infiltrated Phlogopite mica
pressed between various metal couples.
	Inconel/		Inconel/
	Inconel		SS430		Inconel/Haynes230
#cycles	sccm/cm	#cycles	sccm/cm	#cycles	sccm/cm
0	2.5E-03	0	4.7E-04	0	6.1E-04
1	1.7E-03	1	4.5E-04	9	1.6E-03
5	1.2E-03	4	6.0E-04	12	3.4E-04
11	2.5E-03	5	2.0E-03	36	6.0E-04
17	3.0E-03	8	2.3E-04
23	3.8E-03	9	7.0E-04
35	1.0E-03	12	1.0E-03
36	3.4E-03	13	6.0E-04
		24	2.0E-03
		25	2.2E-03
		28	1.8E-03
		29	6.0E-04
		33	2.6E-03
		36	1.4E-03

EXAMPLE 3

[0041] In yet another embodiment of the present invention, an infiltrated sealing (gasket) member 30 was formed, filled, and sealed with a composite material, a preferred material being a mica-glass (G-18) composite. More specifically, mica flakes 22 or particles 22 ranging in size from a few hundred microns to a few mm were premixed with a glass or melt forming material in a liquid carrier (aqueous or organic solvent(s)). An organic solvent(s) as a liquid carrier was preferred for mixing (e.g., MEK) over the aqueous alternative(s) given the excellent mixing in the composite mixture, the rapid evaporation of the solvent(s), and the faster drying times. Mixing was best effected using a ball-mill or comparable mixer. The sealing (gasket) member 30 was subsequently formed, defined, and/or otherwise applied using standard ceramic processing techniques known to those of ordinary skill in the art. Conventional ceramic processing methods include slip casting, tape casting, tape calendaring, die pressing, and like methods. In a preferred embodiment, an infiltrated sealing member 30 was prepared from a mica:glass composite comprising 90 v % Phlogopite mica and 10 v % glass (G18 glass powder), using tape cast processing as detailed below.

[0042] Experimental

[0043] 26.45 g mica flakes (Cogemica, PP120, Cogebi Inc., NH) were mixed with 3.55 g of G-18 glass powder (composition detailed in U.S. patents U.S. Pat. No. 6,430,966 and U.S. Pat. No. 6,532,769, hereby incorporated by reference), which was attrition milled to a particle size in the range from about 1 to ˜5 microns, in a solvent mixture containing 7.68 g ethanol and 31.48 g Methyl-Ethyl-Ketone (MEK). 0.30 g of a dispersant (EMPHOS PS-236, Witco Corporation, Tex.) was added to the solvent mixture. The materials were ball milled in a 250 ml plastic container for about 2 hours. Then, 5.11 g of a binder (Polyvinyl Butyral B-79, SOLUTIA Inc., MO) and 4.42 g of a plasticizer (Butyl-Benzyl-Phthalate, BBP, Monsanto, Mo.) were added to the mixture and ball milled at low speed for about 16 hours. The slurry was then tape cast on a polyester film (PET), the film being sold under the trademark MYLAR® (DuPont Packing and Industrial Polymers, Wellington Del.), and dried at room temperature in air for a period of from 12 to 24 hours. Thickness of the MYLAR® sheets was 2 mils (1 mil=0.001 in.), a standard for tape cast processing. The MYLAR® sheets were coated on one side with silicon to prevent tape casts from adhering during drying (annealing) of the sealing (gasket) member 30 and for ease of handling in the post annealing assembly of the compressive seal 100. Other suitable materials, handling, and/or processing techniques may be selected as necessary to accommodate commercial manufacturing purposes.

[0044] Results

[0045] FIG. 5 shows the leak rate results of the 90v % mica: 10 v % glass composite tape compressed at 100 psi in a compressive seal 100. The corresponding leak data are tabulated in TABLE 3. Results show that 1) leak rates are not increasing with number of thermal cycles, clearly showing the thermal stability, and 2) leak rates are again low relative to the non-infiltrated mica [0.0049 sccm/cm after 10 cycles vs. 0.029 sccm/cm], about an order of magnitude better than the non-infiltrated mica sample. In addition, leak rates of the mica:glass seal further decreased to 0.0012 sccm/cm after 74 thermal cycles.

TABLE 3
Normalized leak rates of the mica (90 v %)-glass(10 v %) composite
seals versus thermal cycles. Sample was pressed at 100 psi and leak tested
at 2 psig using ultra-high purity Helium. Multiple entries represent
independent readings for a given thermal cycle measurement, respectively.
# cycles sccmc/m
0        4.2E-03
0        2.6E-03
1        3.8E-03
1        4.1E-03
1        5.4E-03
10       4.9E-03
16       5.3E-03
16       5.4E-03
16       6.7E-03
32       4.7E-03
32       5.2E-03
32       5.4E-03
34       3.0E-03
45       1.2E-03
51       3.6E-03
51       3.4E-03
74       2.1E-03
74       1.2E-03

EXAMPLE 4

[0046] In yet another embodiment, a Phlogopite 80 v % mica and 20 v % glass (G18) mica:glass composite was prepared for infiltrating the mica sealing member 30 as follows.

[0047] Experimental

[0048] 21.51 g of mica flakes (Cogemica, PP120, Cogebi Inc., NH) were mixed with 6.26 g G-18 glass powder which was attrition milled to a particle size in the range from about 1 to ˜5 microns in 60 g de-ionized water. 4 g of a dispersant (Darvan C, R. T. Vanderbilt Co. Inc., Conn.) was also added to the water to disperse the powders. The materials were ball milled in a 250 ml plastic jar for about 2 hours. Then, 10.9 g of a binder (B-1050, Duramax, Rohm&Haas, PA) was added to the mixture and milled at low speed for ˜3 hours. Contents were then cast into tapes on a MYLAR® sheet. The cast tape was dried at room temperature in air as described previously.

[0049] Results

[0050] FIG. 6. shows results for the (80 v %) mica: (20 v %) glass composite tape compressed at a stress of 50 psi. Data are tabulated and listed in TABLE 4.

TABLE 4
Normalized leak rates of the mica (80 v %) glass (20 v %) composite
seals as a function of thermal cycles. Sample seals were pressed at 50 psi
and leak tested at 2 psig using ultra-high purity Helium. Multiple entries
represent independent readings for a given thermal cycle measurement,
respectively.
# cycles sccm/cm
0        5.7E-03
0        5.9E-03
8        4.4E-03
8        4.7E-03
9        3.9E-03
9        4.2E-03
12       2.6E-03
12       3.6E-03
13       4.2E-03
13       3.9E-03
16       1.4E-03
16       8.1E-04
17       3.2E-03
17       1.2E-03
20       1.7E-03
20       2.3E-03
21       3.7E-03
21       1.3E-03
24       1.4E-04
24       1.4E-05
25       1.6E-03
25       1.2E-03

[0051] In Example 4, leak rate data presented for the 80 v %:20 v % (mica:glass) composites indicate that leak rates 1) are not increasing with number of thermal cycles (again evidencing thermal stability), and 2) leak rates are again low relative to the non-infiltrated mica [˜0.0042 sccm/cm after 10 cycles vs. 0.029 sccm/cm for the non-infiltrated material], about an order of magnitude better than the non-infiltrated mica samples.

[0052] Closure

[0053] While the preferred embodiments of the present invention have been shown and described, it will be apparent to those skilled in the art that many changes and modifications may be made without departing from the invention in its broader aspects. The appended claims are therefore intended to cover changes and modifications as fall within the true spirit and scope of the invention.

Claims

1. An advanced sealing (gasket) member for sealing in high temperature devices, comprising: a mica based member wherein said member comprises an infiltrating material whereby low effective leak rates are obtained.

2. The sealing member of claim 1 wherein said mica based member comprises a mica selected from the group consisting of Phlogopite, Muscovite, Biotite, Fuchsite, Lepidolite, Zinnwaldite, paper, flakes, filaments, fragments, particles, and combinations thereof.

3. The sealing member of claim 1 wherein said infiltrating material is a member selected from the group consisting of H3BO3, Bi(NO3)3, B2O3, Bi2O3, glass former, melt former, glass, oxides, mica:glass composite(s), or combinations thereof.

4. The sealing member of claim 3 wherein said glass is G-18 glass.

5. The sealing member of claim 1 wherein leak rates are less than 1E-02 sccm/cm at operating temperatures in the range from 600° C. to about 850° C.

6. The sealing member of claim 1 wherein said member comprises a mica:glass composite having a mica-based concentration up to about 50% by volume.

7. The sealing member of claim 1 wherein said sealing member comprises a mica:glass composite having 90% by volume of a mica based material and 10% by volume of a glass forming material.

8. The sealing member of claim 1 wherein said sealing member comprises a mica:glass composite mixture of 80% by volume of a mica-based material and 20% by volume of a glass forming material.

9. The sealing member of claim 1 wherein said infiltrating material comprises a G-18 glass.

10. A multilayer (compressive) seal having superior thermal cycling stability for sealing in high temperature devices, the seal comprising: a sealing (gasket) member defining first and second opposing surfaces; a first compliant interlayer disposed adjacent with said first surface; a second compliant interlayer disposed adjacent said second surface; and, wherein said sealing member is infiltrated with at least one glass or melt forming material whereby a plurality of spaces within said member are effectively sealed and low effective leak rates are achieved.

11. The seal according to claim 10, wherein leak rates are less than 1E-02 sccm/cm at operating temperatures in the range from 600° C. to about 850° C.

12. The seal in accordance with claim 10 wherein the sealing (gasket) member comprises a mica selected from the group consisting of Phlogopite, Muscovite, Biotite, Fuchsite, Lepidolite and Zinnwaldite, paper, flakes, filaments, fragments, particles, and combinations thereof.

13. The seal in accordance with claim 10 wherein at least one of said first and second compliant interlayers comprises a member selected from the group consisting of a glass, a glass-ceramic, a mica glass-ceramic, a phase-separated glass, a glass composite, a cermet, a metal, a metal foil, a metal alloy, a metal composite, a mica-glass composite, or combinations thereof.

14. The seal in accordance with claim 10 wherein said sealing member comprises a mica:glass composite having a mica-based concentration up to about 50% by volume.

15. The seal in accordance with claim 10 wherein said sealing member comprises a mica:glass composite having 90% by volume of a mica based material and 10% by volume of a glass forming material.

16. The seal in accordance with claim 10 wherein said sealing member comprises a mica:glass composite mixture of 80% by volume of a mica-based material and 20% by volume of a glass forming material.

17. The seal in accordance with claim 15 wherein said glass forming material comprises a G-18 glass.

18. The seal in accordance with claim 16 wherein said glass forming material comprises a G-18 glass.

19. A process for making a sealing (gasket) member exhibiting superior thermal cycle stability and low effective leak rates, the steps comprising: providing an infiltrating liquid at a first temperature; infiltrating a plurality of spaces in a sealing (gasket) member with said liquid; and fixing said material at a second temperature within said member whereby low effective leak rates are obtained.

20. The process in accordance with claim 19 wherein said spaces comprise a member selected from the group consisting of voids, spaces, flow paths, leak paths, gaseous flow paths, continuities, necking areas, interstitial spaces, three-dimensional spaces, and combinations thereof.

21. The process in accordance with claim 19 wherein said infiltrating liquid comprises at least one material selected from the group consisting of H3BO3, Bi(NO3)3, B2O3, Bi2O3, glass former, melt former, glass, mica:glass composite(s), or combinations thereof.

22. The process in accordance with claim 19 wherein said liquid further comprises materials having a melting point below about 850° C.

23. The process in accordance with claim 19 wherein said member comprises a mica selected from the group consisting of Phlogopite, Muscovite, Biotite, Fuchsite, Lepidolite and Zinnwaldite, paper, flakes, filaments, fragments, particles, and combinations thereof.

24. The process in accordance with claim 19 wherein said first temperature is in the range from 1° C. to about 90° C.

25. The process in accordance with claim 19 wherein said second temperature is in the range from about 50° C. to 150° C. for a period of from 0.5 to 1 hour.

26. The process in accordance with claim 19 wherein said leak rates are less than 1E-02 sccm/cm at operating temperatures in the range from 600° C. to 850° C.

27. A process for making a sealing (gasket) member exhibiting superior thermal cycle stability, the steps comprising: providing an infiltration material at a first temperature; forming a sealing (gasket) member comprising said infiltration material; and fixing said material in said sealing member at a second temperature whereby a plurality of spaces within said member are made discontinuous and low effective leak rates are obtained.

28. The process of claim 27, wherein said first temperature is in the range from 1° C. to about 90° C.

29. The process of claim 27, wherein said second temperature is in the range from about 50° C. to 150° C. for a period of from 0.5 to 1 hour.

30. The process of claim 27 wherein said leak rates are less than 1E-02 sccm/cm at operating temperatures in the range from 600° C. to 850° C.

31. The process of claim 27 wherein said infiltration material comprises a mica:glass composite having a glass-based concentration up to about 50% by volume.

32. The process of claim 27 wherein said infiltration material comprises a mica:glass composite having 90% by volume of a mica based material and 10% by volume of a glass forming material.

33. The process of claim 27 wherein said material is a composite mixture comprising 80% by volume of a mica-based material and 20% by volume of a glass forming material.

34. The process of claim 32 wherein said mica-based material is selected from the group consisting of Phlogopite, Muscovite, Biotite, Fuchsite, Lepidolite and Zinnwaldite, paper, flakes, filaments, fragments, particles, and combinations thereof.

35. The process of claim 33 wherein said mica-based material is selected from the group consisting of Phlogopite, Muscovite, Biotite, Fuchsite, Lepidolite and Zinnwaldite, paper, flakes, filaments, fragments, particles, and combinations thereof.

36. The process of claim 27 wherein said spaces comprise a member in the group consisting of voids, flow paths, leak paths, three dimensional spaces, interstices, continuities, necking areas, and combinations thereof.

37. A process for making a multi-layer (compressive) seal having superior thermal cycle stability for high-temperature electrochemical applications and structures, comprising: providing a sealing (gasket) member comprising an infiltration material wherein said member defines first and second generally flat opposing surfaces; and applying a compliant material to said first and second surfaces to form first and second compliant interlayers;

38. The process in accordance with claim 37 wherein said providing comprises a material selected from the group consisting of glass forming material(s), melt forming material(s), mica:glass composite(s), or combinations thereof.

39. The method of claim 37, wherein said member comprises at least one glass or melt forming material selected from the group consisting of H3BO3, Bi(NO3)3, B2O3, Bi2O3, glass forming material(s), melt forming material(s), composite(s), mica:glass composite(s), and combinations thereof.

40. The method of claim 37 wherein said materials has a melting point below about 850° C.

41. The method in accordance with claim 37 wherein said providing comprises a member selected from the group consisting of slip casting, tape casting, tape calendaring, die pressing, or combinations thereof.

42. The method in accordance with claim 37 wherein at least one of the first and second compliant interlayers comprises a member selected from the group consisting of a glass, a glass-ceramic, a mica glass-ceramic, a phase-separated glass, a glass composite, a cermet, a metal, a metal foil, a metal alloy a metal composite, or combinations thereof.

43. The method in accordance with claim 37 wherein said sealing member has a thickness of from about 25 microns to about 1 millimeter.

44. The method in accordance with claim 37 wherein each of the first and second compliant interlayers has a thickness of from about 0.005 millimeters to about 1 millimeter.

45. A method for making a multi-layer seal having superior thermal cycle stability for high-temperature electrochemical applications and structures, comprising: providing a sealing (gasket) member wherein said member defines first and second generally flat opposing surfaces. applying a compliant material to said first and second surfaces to form first and second compliant interlayers; and wherein said member is infiltrated with at least one glass or melt forming material.

46. The method in accordance with claim 45 wherein said glass (or melt) forming material is selected from the group consisting of H3BO3, Bi(NO3)3, B2O3, Bi2O3, glass, mica:glass composite(s), or combinations thereof.

47. The method of claim 45 wherein said glass forming material comprises a G-18 glass.

48. The method in accordance with claim 45 wherein said providing comprises a member selected from the group consisting of dip-coating, painting, screen printing, deposition, sputtering, tape casting and sedimentation.

49. A method for making a multi-layer (compressive) seal having superior thermal cycle stability for high-temperature electrochemical applications and structures, comprising: providing a glass infiltrated sealing (gasket) member defining first and second generally flat opposing surfaces; applying a compliant material to said first and second surfaces to form first and second compliant interlayers; and, wherein said seal is under a compressive stress.

50. An electrochemical device, comprising: a plurality of components, said components forming at least one boundary between diverse gaseous streams and defining at least one junction therebetween; a multi-layer compressive seal positioned at the junction, the seal composed of a sealing (gasket) member comprising an infiltrating material said sealing member disposed between two compliant interlayers, wherein each compliant interlayer is disposed between the sealing member and one of said components; and a compression member for exerting a compressive force to the components and the sealing member.

51. The electrochemical device in accordance with claim 50 wherein the sealing (gasket) member comprises an infiltrated mica.

52. The electrochemical device in accordance with claim 50 wherein at least one of said compliant interlayers comprises glass.

53. The electrochemical device in accordance with claim 50 wherein at least one of said compliant layers comprises a metal.

54. The electrochemical device in accordance with claim 50 wherein the glass has a softening point lower than or equal to the operating temperatures of the device.

55. The electrochemical device in accordance with claim 50 wherein the glass is non corrosive to surfaces of the components in contact with the glass under operating conditions.

56. The electrochemical device in accordance with claim 50 wherein the metal is resistant to oxidation under operating conditions of the device.

57. The electrochemical device in accordance with claim 50 wherein the compliant interlayer is a metallic foil having a thickness of from about 0.005 millimeters to about 1 millimeters prior to heating.

58. The electrochemical device in accordance with claim 50 wherein the compressive force is a force of from about 5 to about 500 psi.

59. The electrochemical device in accordance with claim 50 wherein said sealing (gasket) member has a thickness of from about 25 microns to about 2 millimeters.

60. The electrochemical device in accordance with claim 50 wherein each of said compliant layers has a thickness of from about 0.005 millimeters to about 1 millimeter prior to heating.

61. The electrochemical device in accordance with claim 50 wherein the electrochemical device comprises a member selected from the group consisting of a solid oxide fuel cell, a syngas membrane reactor, an oxygen generator.

62. A solid oxide fuel cell assembly for electrochemically reacting a fuel gas with a flowing oxidant gas at an elevated temperature to produce a DC output voltage, said solid oxide fuel cell comprising: a plurality of generally planar integral fuel cell units, each unit comprising a layer of ceramic ion conducting electrolyte disposed between a conductive anode layer and a conductive cathode layer, wherein said units are arranged one on another along a longitudinal axis perpendicular to said planar units to form a fuel cell stack; a multi-layer non-conducting seal disposed between the anode layer and the cathode layer of adjacent fuel cell units, wherein the seal is composed of an infiltrated sealing (gasket) member disposed between two compliant interlayers; and a compression member for exerting a compressive force along the longitudinal axis.

63. The assembly in accordance with claim 62 wherein the compressive force is in the range from about 5 to about 500 psi.

64. A method for sealing a junction between adjacent ceramic or metallic components of an electrochemical device, comprising: positioning between the adjacent components a multi-layer seal comprising a sealing member infiltrated with at least one glass forming material wherein said member is disposed between a first compliant interlayer and a second compliant interlayer, wherein each of the first and second compliant interlayers is positioned between the sealing member and one of the components; and applying a compressive force to the components and the seal.

65. The method in accordance with claim 64 wherein the sealing member comprises a member selected from the group consisting of melt forming materials, glass forming materials, glass, mica:glass composite materials, H3BO3, B2O3, Bi(NO3)3, Bi2O3, G-18 glass, or combinations thereof.

66. A solid oxide fuel cell assembly for electrochemically reacting a fuel gas with a flowing oxidant gas at an elevated temperature to produce a DC output voltage, said solid oxide fuel cell comprising: a plurality of generally planar integral fuel cell units, each unit comprising a layer of ceramic ion conducting electrolyte disposed between a conductive anode layer and a conductive cathode layer, wherein said units are arranged one on another along a longitudinal axis perpendicular to said planar units to form a fuel cell stack; a multi-layer non-conducting seal disposed between the anode layer and the cathode layer of adjacent fuel cell units, wherein the seal is composed of a sealing member infiltrated with at least one glass forming material or composite(s) disposed between two compliant interlayers; and a compression member for exerting a compressive force along the longitudinal axis.

67. The assembly in accordance with claim 66 wherein the compressive force is a force of from about 5 to about 500 psi.

68. The assembly in accordance with claim 66 wherein the anode layer is composed of a first porous ceramic material and the cathode layer is composed of a second porous ceramic material.