# US 7,410,921 B2 · High thermal expansion cyclosilicate glass-ceramics

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- Number: US 7,410,921 B2
- Document ID: US7410921B2
- Status: Granted
- Kind: B2
- Application number: 11/708,242
- Filed: 2007-02-20
- Published: 2007-10-11
- Granted: 2008-08-12
- Earliest claimed: 2006-04-11
- Assignees: Corning Incorporated
- Inventors: Linda Ruth Pinckney; Steven Alvin Tietje
- Web page: https://patentgrep.com/patent/US7410921B2

## CPC

- C03C 8/24: 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
- C03B 19/06: by sintering, {e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction}
- C03C 8/02: Frit compositions, i.e. in a powdered or comminuted form
- C03C 8/04: containing zinc
- C03C 10/0009: {containing silica as main constituent}
- C03C 10/0036: {containing SiO2, Al2O3 and a divalent metal oxide as main constituents}
- C03C 10/0045: {containing SiO2, Al2O3 and MgO as main constituents}
- C03C 29/00: Joining metals with the aid of glass
- C04B 35/16: based on silicates other than clay {(zircon C04B35/48)}
- C04B 35/22: rich in calcium oxide {, e.g. wollastonite (C04B35/195 takes precedence)}
- C04B 35/653: Processes involving a melting step
- C04B 37/005: {consisting of glass or ceramic material}
- C04B 37/025: {consisting of glass or ceramic material}
- C23C 24/08: by application of heat or pressure and heat (C23C24/04 takes precedence)
- C23C 24/082: {without intermediate formation of a liquid in the layer}
- H01M 8/0282: Inorganic material
- C03C 2207/02: containing ingredients for securing a good bond between the vitrified enamel and the metal
- C04B 2235/3206: Magnesium oxides or oxide-forming salts thereof
- C04B 2235/3213: Strontium oxides or oxide-forming salts thereof
- C04B 2235/3215: Barium oxides or oxide-forming salts thereof
- C04B 2235/3217: Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B 2235/3225: Yttrium oxide or oxide-forming salts thereof
- C04B 2235/3251: Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
- C04B 2235/3272: Iron oxides or oxide forming salts thereof, e.g. hematite, magnetite
- C04B 2235/3284: Zinc oxides, zincates, cadmium oxides, cadmiates, mercury oxides, mercurates or oxide forming salts thereof
- C04B 2235/3445: Magnesium silicates, e.g. forsterite
- C04B 2235/3454: Calcium silicates, e.g. wollastonite
- C04B 2235/80: Phases present in the sintered or melt-cast ceramic products other than the main phase
- C04B 2235/9607: Thermal properties, e.g. thermal expansion coefficient
- C04B 2237/10: Glass interlayers, e.g. frit or flux
- H01M 2008/1293: {Fuel cells with solid oxide electrolytes}
- Y02E 60/50: Fuel cells
- 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
- C03B: MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C04B: LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE {(roofing granules E04D7/005)}; CERAMICS (devitrified glass-ceramics C03C10/00); REFRACTORIES; TREATMENT OF NATURAL STONE
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## Abstract

The invention is directed to highly crystalline, frit-sintered glass-ceramic compositions having a coefficient of thermal expansion in the range of 85-115×10−7° C. The primary crystal phases of the glass-ceramics of the invention possess a cyclosilicate structure. The glass-ceramic of the invention are useful as metal-to-metal, metal-to-ceramic and ceramic-to-ceramic sealing agents, and also as high-performance coating for metals and ceramics. In their broadest composition the glass-ceramic contain, in weight percent, 30-55% SiO2, 5-40% CaO, 0-50% BaO, 0.1-10% Al2O3, and 0-40% SrO, wherein the sum of CaO+BaO+SrO is in the range of 35-65 wt. %. Optionally, the glass-ceramic compositions may contain at least one from the group of >0-15 wt. % MgO and >0-10 wt. % ZnO. Also optionally, the glass ceramic compositions may contain >0-10 wt. % of at least one transition metal or rare earth metal oxide.

## Claims

### Claim 1

Glass-ceramic compositions having at least one cyclosilicate crystalline component, said glass-ceramics comprising in weight percent (wt. %):
30-55% SiO2,
5-40% CaO,
0-50% BaO,
0.1-10% Al2O3, and
0-40% SrO,
wherein the sum of CaO+BaO+SrO is in the range of 35-65 wt. % and said glass-ceramic has a crystalline phase containing at least one cyclosilicate crystalline component, and
wherein said compositions are boron-free.

### Claim 2 (depends on 1)

The glass-ceramic according to claim 1, wherein said glass ceramic has a glass phase and a crystalline phase containing at least one cyclosilicate crystalline component selected from the group consisting of the walstromite, cyclo-wollastonite and μ-(Ca,Sr)SiO3.

### Claim 3 (depends on 1)

The glass-ceramic compositions according to claim 1, wherein said glass-ceramic compositions further comprise at least one oxide selected from the group consisting of:
>0-16 wt. % MgO, and
>0-10 wt. % ZnO,
wherein the sum of CaO+BaO+SrO+MgO is in the range of 35-65 wt. %.

### Claim 4 (depends on 3)

The glass-ceramic according to claim 3, wherein said glass ceramic has a glass phase and a crystalline phase containing at least one cyclosilicate crystalline component selected from the group consisting of the walstromite, cyclo-wollastonite and μ-(Ca,Sr)SiO3.

### Claim 5 (depends on 1)

The glass ceramic compositions according to claim 1, wherein said glass-ceramic compositions >0-16 wt. % MgO and >0-10 wt. % of at least one metal oxide selected from the group consisting of transition metal and rare earth metal oxides.

### Claim 6 (depends on 5)

The glass ceramic compositions according to claim 5, wherein said at least one metal oxide is a transition metal or rare earth metal oxide selected from the group consisting of Nb2O5, Ta2O5, Y2O3, Yb2O3, La2O3, and Fe2O3.

### Claim 7 (depends on 1)

The glass-ceramic compositions according to claim 1, wherein said glass-ceramic have a coefficient of thermal expansion in the range of 85-115×10−7/° C.

### Claim 8

A glass-ceramic composition having at least one cyclosilicate crystalline component, said glass-ceramics comprising in weight percent (wt. %):
38-50% SiO2,
20-40% CaO,
0-20% BaO,
2-6% Al2O3, and
0-25% SrO,
wherein the sum of CaO+BaO+SrO is in the range of 35-65 wt. % and said glass-ceramic has a crystalline phase containing at least one cyclosilicate crystalline component and
wherein said composition is boron free.

### Claim 9 (depends on 8)

The glass ceramic-composition according to claim 8, wherein said glass-ceramic further comprises at least one oxide selected from the group of:
>0-16 wt. % MgO and
>0-5 wt. % ZnO,
therein the sum of CaO+BaO+SrO+MgO or CaO+BaO+SrO+ZnO is in the range of 35-65 wt. %.

### Claim 10 (depends on 8)

The glass ceramic compositions according to claim 8, wherein said glass-ceramic compositions comprise >0-16 wt. % MgO, and >0-10 wt. % of at least one metal oxide selected from the group consisting of transition metal and rare earth metal oxides.

### Claim 11 (depends on 10)

The glass ceramic compositions according to claim 10, wherein said at least one metal oxide is a transition metal or rare earth metal oxide selected from the group consisting of Nb2O5, Ta2O5, Y2O3, Yb2O3, La2O3, and Fe2O3.

### Claim 12 (depends on 8)

The glass-ceramic compositions according to claim 8, wherein said glass-ceramics have a coefficient of thermal expansion in the range of 85-115×10−7/° C.

### Claim 13

A glass-ceramic composition having at least one cyclosilicate crystalline component, said glass-ceramic comprising
45-55% SiO2,
25-40% CaO,
0-25 wt. % SrO
3-6% Al2O3, and
4-15% MgO,
wherein the sum of CaO+MgO or CaO+MgO+SrO is in the range 38-50 wt. % and said glass-ceramic has a crystalline phase having at least one cyclosilicate crystalline component selected from the group consisting of the cyclosilicates walstromite, cyclo-wollastonite and μ-(Ca,Sr)SiO3 and
wherein said composition is boron-free.

### Claim 14 (depends on 13)

The glass-ceramic composition according to claim 13, wherein said composition further comprises 4-8 wt. % ZnO, wherein the sum of CaO+MgO is in the range of 38-50 wt. %.

### Claim 15 (depends on 13)

The glass ceramic compositions according to claim 13, wherein said glass-ceramic compositions comprise >0-10 wt. % of at least one metal oxide selected from the group consisting of transition metal and rare earth metal oxides.

### Claim 16 (depends on 15)

The glass ceramic compositions according to claim 15, wherein said at least one metal oxide is a transition metal or rare earth metal oxide selected from the group consisting of Nb2O5, Ta2O5, Y2O3, Yb2O3, La2O3, and Fe2O3.

### Claim 17 (depends on 13)

The glass-ceramic composition according to claim 13, wherein the crystalline crystalline phase of said glass-ceramic further comprises at least one crystalline component selected from the group consisting of diopside, åkermanite, and hardystonite.