GB2035995A - Sodium-resistant Glass - Google Patents
Sodium-resistant Glass Download PDFInfo
- Publication number
- GB2035995A GB2035995A GB7922399A GB7922399A GB2035995A GB 2035995 A GB2035995 A GB 2035995A GB 7922399 A GB7922399 A GB 7922399A GB 7922399 A GB7922399 A GB 7922399A GB 2035995 A GB2035995 A GB 2035995A
- Authority
- GB
- United Kingdom
- Prior art keywords
- weight percent
- oxide
- sodium
- glass
- aluminoborate
- 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.)
- Granted
Links
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 title claims abstract description 52
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 52
- 239000011734 sodium Substances 0.000 title claims abstract description 52
- 239000011521 glass Substances 0.000 title claims abstract description 35
- 239000005394 sealing glass Substances 0.000 claims abstract description 56
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 35
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 34
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 27
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 17
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 15
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000292 calcium oxide Substances 0.000 claims abstract description 15
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract description 13
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 13
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims abstract description 6
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001947 lithium oxide Inorganic materials 0.000 claims abstract description 5
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001950 potassium oxide Inorganic materials 0.000 claims abstract description 5
- 229910001948 sodium oxide Inorganic materials 0.000 claims abstract description 5
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims description 7
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 4
- 238000010348 incorporation Methods 0.000 abstract description 2
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 14
- 238000007789 sealing Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000005388 borosilicate glass Substances 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 5
- 239000006060 molten glass Substances 0.000 description 5
- 239000004020 conductor Substances 0.000 description 4
- 238000004031 devitrification Methods 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000005368 silicate glass Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 229910000833 kovar Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000007496 glass forming Methods 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
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
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
- C03C3/145—Silica-free oxide glass compositions containing boron containing aluminium or beryllium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
- H01M50/19—Sealing members characterised by the material
- H01M50/191—Inorganic material
-
- 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
-
- 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
-
- 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
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
- H01M10/3909—Sodium-sulfur cells
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/10—Primary casings; Jackets or wrappings
- H01M50/183—Sealing members
- H01M50/19—Sealing members characterised by the material
- H01M50/198—Sealing members characterised by the material characterised by physical properties, e.g. adhesiveness or hardness
-
- 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
- Y02E60/10—Energy storage using batteries
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Glass Compositions (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Secondary Cells (AREA)
Abstract
A sodium resistant sealing glass has an aluminoborate glass composition in which glass stability is improved by the incorporation of calcium oxide, strontium oxide and/or barium oxide. The glass comprises 10-30 weight percent alumina, 35-50 weight percent boron oxide, 15-40 weight percent of a mixture of calcium oxide, barium oxide and/or strontium oxide, 0-20 weight percent of silica, and 0-5 weight percent of sodium oxide, lithium oxide, and/or potassium oxide.
Description
SPECIFICATION
Sodium Resistant Sealing Glass
This invention relates generally to sodium resistant sealing glasses and, more particularly, to such glasses with an aluminoborate glass composition with specific modifying oxides.
Such sodium resistant sealing glasses are useful for sealing a ceramic ring or flange to a solid electrolyte tube in a sodium-sulfur battery.
Such a sodium-sulfur battery employing a sealing glass in this manner is described in U.S. Patent 3,946,751-Breiter, et al, entitled "Cell Casing
With a Hermetic Mechanical Seal and a
Hermetically Sealed Sodium-Sulfur Cell".
The term solid electrolyte tube as used above in the discussion of a sodium-sulfur battery, includes ion-conductive materials such as betaalumina, beta"-alumina, mixtures thereof and related compounds.
In the above mentioned U.S. Patent No.
3,946,751-Breiter, et al, a cell casing and a hermetically sealed sodium-sulfur cell are disclosed and claimed wherein the cell casing includes a hermetic mechanical seal joining two opposed outer metallic casing portions to an electrically insulating ceramic ring supporting an inner casing of a solid ion-conductive material.
The hermetically sealed sodium-sulfur cell has the above type of casing with a sodium negative electrode in the inner casing end and a positive electrode of sulfur in conductive material in an outer casing portion surrounding the inner casing.
A glass seal seals a portion of the outer wall of the inner casing of the solid sodium ion-conductive material adjacent its open end within and to the ceramic ring.
In U.S. Patent 4,132,820, there is described and claimed a composite body with a glass coating which has sodium resistance, low alkali ion-conductance and a thermal expansion of 7.3 to 6.1 x 10-B inches"inch/0C. The glass coating compositions can be selected from the table set forth on page 6, the specific glass coatings set forth on page 7, or the table set forth on page 8 of the above-mentioned co-pending patent application. As opposed to the present invention, none of the glass coatings set forth in the aboveidentified copending application recite a combination of modifying oxides of calcium oxide, strontium oxide and barium oxide in a range of 1 5 to 40 weight percent of the glass composition.
The present invention provides a sodium resistant aluminoborate sealing glass comprising
10-30 weight percent alumina, 35-50 weight percent boron oxide, 1 5-40 weight percent of a mixture of alkali earth oxides of calcium oxide, barium oxide and strontium oxide, 0--20 weight percent of silica, and 0--5 weight percent of a mixture of alkali metal oxides of sodium oxide, lithium oxide, and potassium oxide.
Sodium-sulfur cells incorporate generally a sealing glass in the ceramic-to-ceramic seal between an electrically insulating flange and a solid ion-conductive electrolyte made generally of beta or beta"-alumina. In most sodium-sulfur cell designs, the sealing glass is in contact with molten sodium from the sodium compartment of the sodium-sulfur cell and, therefore, it must offer adequate resistance against sodium attack.
Further, substantial changes in the sealing glass composition are liable to occur during the sealing of the flange to the electrolyte due to ionic interdiffusion between the glass and the ceramic component. This effect of change in glass composition is particularly serious at the glasselectrolyte interface. Our studies have indicated that such changes lead to glass devitrification and deleterious thermal expansion mismatches between sealed components with resulting seal failures and termination of cell operation.
We have found an improved sodium resistant sealing glass which offers good sodium resistance as well as stability against interfacial reactions and devitrification. Our sealing glass has been selected from aluminoborate compositions containing a specific combination of alkali earth oxides. Ceramographic examinations of seals and results of seal tests for extended cycling indicated the excellent behavior of our improved sodium resistant sealing glass. The unique properties of our sealing glass makes it suitable for other types of seals where sodium resistance is desired.
Previously, silicate and borosilicate glasses have been used as sealing glasses in sodiumsulfur cells. For example, in U.S. patent 4,037,027, there is described a borosilicate glass of the composition having 70.36% SiO2, 1.88%
Al203, 19.56% 8203 and 8.20% Na2O. As opposed to silicate and borosilicate glasses, we employ an aluminoborate sealing glass with a specific combination of modifying alkali earth oxides of calcium oxide, strontium oxide and barium oxide, with resulting glass stability. These aluminoborate glass compositions are more resistant to sodium attack than silicate or borosilicate glasses. Thus, our improved sodium resistant sealing glass provides good sodium resistance and excellent glass stability.
We found that we could form a sodium resistant aluminoborate sealing glass which comprises 10-30 weight percent alumina, 3550 weight percent boron oxide, 1 5-40 weight percent of a mixture of alkali earth oxides of calcium oxide, barium oxide and strontium oxide, j 0--20 weight percent of silica, and 0--5 weight percent of a mixture of alkali metal oxides of sodium oxide, lithium oxide, and potassium oxide.
The resulting sealing glass had excellent sodium resistant properties and improved glass stability.
We found further that this sealing glass had a thermal expansion coefficient which matched closely that of both eta-aluminas and alphaalumina, which are employed generally as the ionconductive tube and the electrically insulating flange in a sodium-sulfur battery, respectively. We found two preferred sodium resistant aluminoborate sealing glasses within the composition range of our sealing glass. One sealing glass consisted of 19 weight percent alumina, 45 weight percent boron oxide, 6 weight percent calcium oxide, 12 weight percent barium oxide, 10 weight percent strontium oxide, and 8 weight percent silica. The other sealing glass consisted of 19 weight percent alumina, 45 weight percent boron oxide, 7 weight percent calcium oxide, 6 weight percent barium oxide, 13 weight percent strontium oxide, and 10 weight percent silica.
The sodium stability of our two preferred sealing glass compositions was clearly demonstrated in accelerated tests with virgin glasses. After 160 hours at 3500C in sodium vapor, both of our aluminoborate glass compositions exhibited little, if any, discoloration.
However, a high silica sealing glass consisting of 50 weight percent silica, 10 weight percent alumina, 30 weight percent barium oxide, and 10 weight percent boron oxide turned dark brown.
Discoloration effects, although qualitative, indicate the presence of metallic sodium in the glass and thus provide a measure of sodium permeability. Excess sodium migration within the sealing glass is generally accompanied by fracture processes which, in the case of sodium-sulfur batteries, leads to cell failure.
A second significant property of our sodium resistant aluminoborate sealing glass is the stability of the glass and its resistance to devitrification. That is, the sealing glass must be able to withstand slight changes in composition without crystallizing. The temperatures involved in the sealing operation enable ionic diffusion and even some dissolution to occur. If the local composition of the sealing glass is altered sufficiently during the sealing operation, a new phase may form which, because of thermal expansion mismatch may lead to fracture in the sealing area. Such a process would cause the sodium-sulfur cell to fail. We have provided glass stability thereby increasing its resistance to devitrification by the incorporation of a specific combination of modifying alkali earth oxides in a range from 15 weight percent to 40 weight percent of the glass composition.The specific combination of these modifying oxides are calcium oxide, barium oxide and strontium oxide.
The inclusion of this specific combination of modifying oxides insures that the glass composition remains in the glass forming region despite slight changes in composition during the sealing operation. Additionally, the thermal expansion coefficient of our sealing glass closely matches that of both the beta-aluminas and the alpha-alumina.
Our sodium resistant aluminoborate sealing glasses are also thermally compatible with various borosilicate glasses and a wide variety of metals, such as Kovar alloy, molybdenum, etc., developed for ceramic-to-metal seals. We have recently made successful ceramic-tometal seals of alpha-alumina to Kovar alloy and alphaalumina to molybdenum with our sodium resistant aluminoborate sealing glasses.
In the preparation of our sodium resistant aluminoborate sealing glasses, we mix together the chemicals which on melting, decomposing and reacting yield 10-30 weight percent alumina, 35-50 weight percent boron oxide, 1 5-40 weight percent of a mixture of alkali earth oxides of calcium oxide, barium oxide and strontium oxide,~0~20 weight percent of silica, and 0--5 weight percent of a mixture of metal alkali oxides selected from the group consisting of sodium oxide, lithium oxide, and potassium oxide.
The mixed batch is then melted in an air atmosphere at a temperature in a range from 10000C to 13000 C. The molten glass is poured into a mold to form the glass in a convenient shape such as a block. The glass is then cooled to room temperature to provide the sodium resistant aluminoborate sealing glass of our invention.
When such sealing glass is used for sealing together two components, for example, the flange and the outer wall of an ion-conductive tube in a sodium-sulfur battery, the glass is ground to reduce the above glass block to small particle size. A flange or ring of alpha-alumina is positioned around and adjacent the open end of the ion-conductive electrolyte tube of betaalumina. The flange has a lower inner portion which abuts against the outer wall of the tube while the inner, portion of the flange is recessed.
The flange and tube are held in position by a suitable fixture to form an assembly. The glass particles of the sealing glass are positioned in the recess between the outer surface of the tube and the upper portion of the adjacent flange. The tube and flange with the particles positioned therebetween as above described, are then heated to a temperature of about 9000C in an air atmosphere to melt the glass particles into a molten state. The assembly is then cooled to room temperature with a resulting sodium resistant aluminoborate sealing glass sealing the flange to the outer wall of the tube. A sodiumsulfur cell is then constructed in accordance, for example, with the above mentioned U.S. Patent
No. 3,946,751.
Examples of our sodium resistant aluminoborate sealing glass made in accordance with our invention are set forth below:
Example I
A sodium resistant aluminoborate sealing glass was formed by mixing together the chemicals which on melting, decomposing and reacting yield 19 weight percent alumina, 45 weight percent boron oxide, 6 weight percent calcium oxide, 12 weight percent barium oxide, 10 weight percent strontium oxide and 8 weight percent silica. This mixed batch was heated to a temperature of 1 000C in an air atmosphere to
provide molten glass. The molten glass was poured into a block-shaped mold and allowed to cool. The resultant block was a sodium resistant aluminoborate sealing glass made in accordance with our invention.
Example II A sodium resistant aluminoborate sealing glass was formed by mixing together the chemicals which on melting, decomposing and reacting yield 19 weight percent alumina, 45 weight percent boron oxide, 7 weight percent calcium oxide, 6 weight percent barium oxide, 13 weight percent strontium oxide, and 10 weight percent silica. This mixed batch was heated to a temperature of 1 000C in an air atmosphere to provide molten glass. The molten glass was poured into a block shaped mold and allowed to cool. The resultant block was a sodium resistant aluminoborate sealing glass made in accordance with our invention.
Example Ill
A block of sodium resistant aluminoborate sealing glass made in accordance with Example I, was subjected for 160 hours at 3500C in sodium vapor. The sealing glass exhibited little, if any, discoloration. For comparison purposes, a high silica sealing glass was prepared in a conventional manner, which glass consisted of 50 weight percent silica, 10 weight percent alumina, 30 weight percent barium oxide and 10 weight percent boron oxide. This high silica glass was subjected in the same manner as our sealing glass to sodium vapors for 160 hours at 35O0C. The high silica sealing glass turned dark brown indicating the presence of metallic sodium in the glass and thus providing a measure of sodium permeability.
Example IV
Blocks of sodium resistant aluminoborate sealing glass were prepared in accordance with
Example I. These blocks were ground to a small particle size. Fifty sodium beta ion-conductive tubes were each provided with an alpha-alumina flange around its outer surface and adjacent its open end. Each flange had a lower portion which abutted the outer wall of the respective tube while the upper portion provided a recess between the outer wall of the tube and the flange.
Sealing glass particles were positioned in each of these recesses. Each tube and its associated flange with sealing glass particles was held in position by a fixture to provide an assembly. Each assembly was heated to a temperature of 9000C in an air atmosphere after which it was cooled to room temperature resulting in a sodium resistant aluminoborate sealing glass seal between the exterior wall of the tube and the inner surface of the flange.
Example V
Fifty sodium-sulfur cells employing the fifty sealed tubes and flanges from Example IV were made in accordance with the above mentioned
U.S. Patent No. 3,946,751. These fifty cells were tested in actual operation for a period of six months. Subsequent investigation of these tubes showed no failures in the sodium resistant aluminoborate sealing glass seals. Further, such investigation showed that the sodium attack of the sealing glass was negligible during the cell testing.
Claims (4)
1. A sodium resistant aluminoborate sealing glass comprising 10-30 weight percent alumina, 35-50 weight percent boron oxide, 1 5-40 weight percent of a mixture of alkali earth oxides of calcium oxide, barium oxide and strontium oxide, 0-20 weight percent of silica, and 0-5 weight percent of a mixture of alkali metal oxides of sodium oxide, lithium oxide, and potassium oxide.
2. A sodium resistant aluminoborate sealing glass as claimed in claim 1 consisting of 19 weight percent alumina, 45 weight percent boron oxide, 6 weight percent calcium oxide, 12 weight percent barium oxide, 10 weight percent strontium oxide, and 8 weight percent silica.
3. A sodium resistant aluminoborate sealing glass as claimed in claim 1 consisting of 19 weight percent alumina, 45 weight percent boron oxide, 7 weight percent calcium oxide, 6 weight percent barium oxide, 13 weight percent strontium oxide, and 10 weight percent silica.
4. A sodium resistant aluminoborate glass as claimed in claim 1 substantially as hereinbefore described in any one of the Examples.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US95417778A | 1978-10-24 | 1978-10-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2035995A true GB2035995A (en) | 1980-06-25 |
| GB2035995B GB2035995B (en) | 1983-01-06 |
Family
ID=25495044
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7922399A Expired GB2035995B (en) | 1978-10-24 | 1979-06-27 | Sodium-resistant glass |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS5580741A (en) |
| DE (1) | DE2942538A1 (en) |
| FR (1) | FR2439753A1 (en) |
| GB (1) | GB2035995B (en) |
| IT (1) | IT1124612B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2207545A (en) * | 1987-07-28 | 1989-02-01 | Lilliwyte Sa | Glass seal for sodium-sulphur cells |
| US5380596A (en) * | 1990-05-18 | 1995-01-10 | Ngk Insulators, Ltd. | Glass joint body and method of manufacturing the same |
| US8043986B2 (en) | 2008-11-13 | 2011-10-25 | General Electric Company | Sealing glass composition, method and article |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ZA802231B (en) * | 1979-04-19 | 1981-09-30 | Chloride Silent Power Ltd | Glass for sealing beta-alumina in electro-chemical cells or other energy conversion devices, glasses for use in seals and cells or other energy conversion devices with such selas |
| DE3033130A1 (en) * | 1980-09-03 | 1982-04-01 | Brown, Boveri & Cie Ag, 6800 Mannheim | ELECTROCHEMICAL STORAGE CELL |
| US4717690A (en) * | 1986-02-12 | 1988-01-05 | Heraeus, Inc. Cermalloy Division | Overglaze inks |
| DE3736843A1 (en) * | 1987-10-30 | 1989-05-11 | Asea Brown Boveri | METHOD FOR JOINING METAL AND CERAMIC MATERIALS |
| DE3935227C1 (en) * | 1989-10-23 | 1991-04-11 | Schott Glaswerke, 6500 Mainz, De | |
| DE4309069A1 (en) * | 1993-03-20 | 1994-09-22 | Licentia Gmbh | Method of connecting the end faces of two ceramic parts in a vacuum-tight manner |
| EP0999191A1 (en) * | 1998-11-03 | 2000-05-10 | Corning Incorporated | Glasses compatible with aluminium |
| CN118405846B (en) * | 2024-07-03 | 2024-08-30 | 山东龙光天旭太阳能有限公司 | High-heat-resistance chemically-stable high borosilicate glass and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE513407A (en) * | 1951-08-15 | |||
| FR1336602A (en) * | 1961-10-27 | 1963-08-30 | Ass Elect Ind | Manufacturing process of a glass resistant to attack by alkali metal vapors |
| US3544330A (en) * | 1967-04-24 | 1970-12-01 | Du Pont | Glasses and capacitor dielectric compositions made therefrom |
| US4132820A (en) * | 1977-06-09 | 1979-01-02 | General Electric Company | Composite body with beta-alumina substrate and glass-coating thereon |
-
1979
- 1979-06-27 GB GB7922399A patent/GB2035995B/en not_active Expired
- 1979-10-18 IT IT26588/79A patent/IT1124612B/en active
- 1979-10-20 DE DE19792942538 patent/DE2942538A1/en active Granted
- 1979-10-23 FR FR7926219A patent/FR2439753A1/en active Granted
- 1979-10-23 JP JP13603279A patent/JPS5580741A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2207545A (en) * | 1987-07-28 | 1989-02-01 | Lilliwyte Sa | Glass seal for sodium-sulphur cells |
| US5380596A (en) * | 1990-05-18 | 1995-01-10 | Ngk Insulators, Ltd. | Glass joint body and method of manufacturing the same |
| US8043986B2 (en) | 2008-11-13 | 2011-10-25 | General Electric Company | Sealing glass composition, method and article |
Also Published As
| Publication number | Publication date |
|---|---|
| DE2942538C2 (en) | 1990-05-23 |
| GB2035995B (en) | 1983-01-06 |
| IT1124612B (en) | 1986-05-07 |
| FR2439753B1 (en) | 1983-05-27 |
| IT7926588A0 (en) | 1979-10-18 |
| JPS5580741A (en) | 1980-06-18 |
| DE2942538A1 (en) | 1980-05-08 |
| JPS5744616B2 (en) | 1982-09-22 |
| FR2439753A1 (en) | 1980-05-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19980627 |