# US 8,772,189 B2 · Glass frit compositions for enamels > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 8,772,189 B2 - Document ID: US8772189B2 - Status: Granted - Kind: B2 - Application number: 13/100,399 - Filed: 2011-05-04 - Published: 2012-11-08 - Granted: 2014-07-08 - Earliest claimed: 2011-05-04 - Assignees: Ferro Corporation - Applicants: Sandeep K. Singh; George E. Sakoske; David A. Klimas - Inventors: Sandeep K. Singh; George E. Sakoske; David A. Klimas - Web page: https://patentgrep.com/patent/US8772189B2 ## CPC - C03C 8/06: containing halogen - C03C 3/068: containing rare earths - C03C 3/093: containing zinc or zirconium - C03C 3/095: containing rare earths - C03C 3/118: containing aluminium - C03C 8/04: containing zinc - C03C 8/14: Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions - C03C 8/18: containing free metals - C03C 8/20: containing titanium compounds; containing zirconium compounds - C03C 17/04: by fritting glass powder - 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 ## Abstract This invention relates to glass and enamel compositions. The glass compositions comprise SiO2, Cs2O, Na2O, ZnO, B2O3, and TiO2, and optionally Bi2O3 and F. The resulting compositions can be used to form an enamel on a substrate, for example, to decorate and/or protect the substrate. ## Claims ### Claim 1 An enamel composition comprising a solid portion comprising a frit portion, the frit portion comprising, prior to firing: about 30 to about 50 wt % of SiO2; about 4.5 to about 20.2 wt % of Cs2O; about 6.1 to about 11.5 wt % of Na2O; about 6.5 to about 20.2 wt % of B2O3; about 8 to about 25 wt % of ZnO; about 3.4 to about 12.3 wt % of TiO2; about 0 to about 40 wt % of Bi2O3; and about 0 to about 7 wt % of F. ### Claim 2 (depends on 1) The enamel composition of claim 1, wherein the frit portion comprises: about 32 to about 48 wt % of SiO2; about 5.5 to about 18.5 wt % of Cs2O; about 7.5 to about 11.3 wt % of Na2O; about 7.5 to about 18.5 wt % of B2O3; about 9 to about 23 wt % of ZnO; about 4.3 to about 11.3 wt % of TiO2; about 5 to about 35 wt % of Bi2O3; and about 1.5 to about 6.5 wt % of F. ### Claim 3 (depends on 1) The enamel composition of claim 1, wherein the frit portion comprises: about 34 to about 38 wt % of SiO2; about 6.5 to about 16.5 wt % of Cs2O; about 8.5 to about 11.1 wt % of Na2O; about 8 to about 16.5 wt % of B2O3; about 10 to about 20 wt % of ZnO; about 5.5 to about 10.3 wt % of TiO2; about 10 to about 20 wt % of Bi2O3; and about 2.5 to about 5.5 wt % of F. ### Claim 4 (depends on 1) The enamel composition of claim 1, wherein the frit portion further comprises at least one selected from the group consisting of: about 0.1 to about 1 wt % of La2O3; about 0.1 to about 1 wt % of Nb2O5; about 0.1 to about 1 wt % of MnO2; about 0.1 to about 1 wt % of CeO2; about 0.1 to about 1 wt % of MoO3; and about 0.1 to about 1 wt % of WO3, and a total amount of the oxides is about 0.1 to about 5 wt % of the frit portion. ### Claim 5 (depends on 1) The enamel composition of claim 1, wherein the frit portion further comprises at least one selected from the group consisting of: about 0.1 to about 4 wt % of Al2O3; and about 0.1 to about 3 wt % of BaO. ### Claim 6 (depends on 1) The enamel composition of claim 1, further comprising at least one crystalline seed material selected from the group consisting of zinc borates, zinc silicates, zinc titanates, bismuth silicates and combinations thereof. ### Claim 7 (depends on 1) The enamel composition of claim 1 further comprising pigments. ### Claim 8 (depends on 1) The enamel composition of claim 1, wherein the enamel composition is lead-free and cadmium-free. ### Claim 9 (depends on 1) The enamel composition of claim 1, wherein the frit portion has about 8.5×10−6° C.−1 or less of thermal expansion coefficient. ### Claim 10 (depends on 1) The enamel composition of claim 1, wherein the frit portion has about 1100° F. or less of firing temperature. ### Claim 11 (depends on 1) The enamel composition of claim 1, wherein the solid portion comprises: about 60 to about 85 wt % of the frit portion; about 0.1 to about 30 wt % of pigments; about 0.1 to about 15 wt % of crystalline materials; about 10 to about 60 wt % of silver; and optionally about 0.1 to about 5 wt % of reducing agents. ### Claim 12 A method of forming an enamel composition, comprising: combining: about 30 to about 50 wt % of SiO2; about 4.5 to about 20.2 wt % of Cs2O; about 6.1 to about 11.5 wt % of Na2O; about 6.5 to about 20.2 wt % of B2O3; about 8 to about 25 wt % of ZnO; about 3.4 to about 12.3 wt % of TiO2; about 0 to about 40 wt % of Bi2O3; and about 0 to about 7 wt % of F. ### Claim 13 (depends on 12) The method of claim 12, further comprising: combining at least one selected from the group consisting of: about 0.1 to about 1 wt % of La2O3; about 0.1 to about 1 wt % of Nb2O5; about 0.1 to about 1 wt % of MnO2; about 0.1 to about 1 wt % of CeO2; about 0.1 to about 1 wt % of MoO3; and about 0.1 to about 1 wt % of WO3. ### Claim 14 (depends on 12) The method of claim 12, further comprising: combining at least one selected from the group consisting of: about 0.1 to about 4 wt % of Al2O3; and about 0.1 to about 3 wt % of BaO. ### Claim 15 (depends on 12) The method of claim 12, further comprising: combining pigments; crystalline materials; optionally silver; and optionally reducing agents. ### Claim 16 A method of forming an enamel on a substrate, comprising: providing an enamel composition on the substrate, the enamel composition comprising a solid portion, the solid portion comprising a frit portion, the frit portion comprising, prior to firing: about 30 to about 50 wt % of SiO2; about 4.5 to about 20.2 wt % of Cs2O; about 6.1 to about 11.5 wt % of Na2O; about 6.5 to about 20.2 wt % of B2O3; about 8 to about 25 wt % of ZnO; about 3.4 to about 12.3 wt % of TiO2; about 0 to about 40 wt % of Bi2O3; and about 0 to about 7 wt % of F; and firing the enamel composition and the substrate at a temperature sufficient to adhere the enamel composition to the substrate. ### Claim 17 (depends on 16) The method of claim 16, wherein the frit portion further comprises at least one selected from the group consisting of: about 0.1 to about 1 wt % of La2O3; about 0.1 to about 1 wt % of Nb2O5; about 0.1 to about 1 wt % of MnO2; about 0.1 to about 1 wt % of CeO2; about 0.1 to about 1 wt % of MoO3; and about 0.1 to about 1 wt % of WO3, and a total amount of the oxides is about 0.5 to about 5 wt % of the frit portion. ### Claim 18 (depends on 16) The method of claim 16, wherein the frit portion further comprising at least one selected from the group consisting of: about 0.1 to about 4 wt % of Al2O3; and about 0.1 to about 3 wt % of BaO. ### Claim 19 (depends on 16) The method of claim 16 wherein said enamel composition is bismuth-free.