Flexible Glass/Metal Foil Composite Articles and Production Process Thereof

Abstract

A flexible article made of glass and metal foil, as well as the production thereof, are provided. The flexible article is a multilayered structure having at least one glass layer and one metal foil layer, and the shear strength between glass and metal foil is above 1 MPa/mm.sup.2. The glass layer of said flexible article has high electrical resistivity at ambient temperature, low roughness, low thickness, good adherence to metal foil, and the glass in the glass layer has high temperature stability and low flowing temperature, and the thermal expansion coefficient (20 to 300 C.) is 110.sup.6/K to 2510.sup.6/K. The whole article is flexible and can be bent, and the curvature radius of the bent flexible article is above 1 mm.

Claims

1. A flexible article suitable for producing substrates of flexible devices, comprising: a multilayered structure including a layer of glass and a layer of metal foil, the glass being produced by high temperature melting and cooling in the absence of any precursor, wherein the glass has an electrical resistivity of above 510.sup.10 .Math.m at ambient temperature, a surface roughness of below 300 nm, a porosity of below 0.1% on the surface, a thickness of below 350 m, a flowing temperature of below 1200 C., and a softening temperature of above 350 C., wherein the layer of glass has a content of Na.sub.2O+SiO.sub.2+P.sub.2O.sub.5+B.sub.2O.sub.3+SO.sub.3+V.sub.2O.sub.5+TiO.sub.2+BaO+ZnO that is 10-95 wt. %, wherein the glass is aluminosilicate glass or soda lime glass, and wherein the layer of metal foil has a thickness below 1 mm; and wherein between the layer of glass and the layer of metal foil there is a shear strength above 1 MPa/mm.sup.2, the multilayered structure being curvable to a curvature radius of above 1 mm.

2. The flexible article according to claim 1, wherein the layer of glass comprises one of a top layer or a bottom layer of the multilayered structure, and wherein the multilayered structure further comprises another layer of glass that comprises another of the top layer or the bottom layer.

3. The flexible article according to claim 1, wherein the multilayered structure further comprises a layer formed from glass powder or glass slurry between the layer of glass and the layer of metal foil.

4. A flexible article suitable for producing substrates of flexible devices, comprising: a multilayer structure including a metal foil encapsulated by a shell of glass, wherein the glass has an electrical resistivity of above 510.sup.10 .Math.m at ambient temperature, a surface roughness of below 300 nm, a thickness of below 350 m, a flowing temperature of below 1200 C., a softening temperature of above 350 C., and a porosity of below 0.1% on a surface, wherein the glass has a content of Na.sub.2O+SiO.sub.2+P.sub.2O.sub.5+B.sub.2O.sub.3+SO.sub.3+V.sub.2O.sub.5+TiO.sub.2+BaO+ZnO that is 10-95 wt. %, wherein the glass is aluminosilicate glass or soda lime glass, wherein the metal foil has a thickness below 1 mm; and wherein between the shell of glass and the metal foil there is a shear strength above 1 MPa/mm.sup.2, wherein the metal foil encapsulated by the shell of glass is curvable to a curvature radius of above 1 mm.

5. The flexible article according to claim 4, wherein the softening temperature is above 400 C.

6. The flexible article according to claim 4, wherein the softening temperature is above 600 C. and the flowing temperature of below 950 C.

7. The flexible article according to claim 4, wherein the glass has a content of SiO.sub.2+P.sub.2O.sub.5+B.sub.2O.sub.3 that is 10-90 wt. %.

8. The flexible article according to claim 4, wherein the glass has a composition comprising 0-2 wt. % of a refining agent selected from the group consisting of As.sub.2O.sub.3, Sb.sub.2O.sub.3, SnO.sub.2, SO.sub.3, Cl, F, CeO.sub.2, and combinations thereof.

9. The flexible article according to claim 4, wherein the glass comprises lithium aluminosilicate glass having a composition, in weight percent, of: TABLE-US-00009 SiO.sub.2 55-69; Al.sub.2O.sub.3 19-25; Li.sub.2O 3-5; Na.sub.2O 0.5-15; the sum of Na.sub.2O + K.sub.2O 0.5-15; the sum of MgO + CaO + SrO + BaO 0-5; ZnO 0-4; TiO.sub.2 0-5; ZrO.sub.2 0-3; the sum of TiO.sub.2 + ZrO.sub.2 + SnO.sub.2 2-6; P.sub.2O.sub.5 0-8; F .sup.0-1; and B.sub.2O.sub.3 0-2.

10. The flexible article according to claim 9, wherein the composition further comprises one or more of: coloring oxides selected from the group consisting of Nd.sub.2O.sub.3, Fe.sub.2O.sub.3, CoO, NiO, V.sub.2O.sub.5, MnO.sub.2, TiO.sub.2, CuO, CeO.sub.2, and Cr.sub.2O.sub.3; 0-1 wt. % of rare earth oxides; and 0-2 wt. % of a refining agent selected from the group consisting of As.sub.2O.sub.3, Sb.sub.2O.sub.3, SnO.sub.2, SO.sub.3, Cl, F, CeO.sub.2, and combinations thereof.

11. The flexible article according to claim 4, wherein the glass comprises soda lime glass having a composition, in weight percent, of: TABLE-US-00010 SiO.sub.2 40-80; Al.sub.2O.sub.3 0-6; B.sub.2O.sub.3 0-5; the sum of Li.sub.2O + Na.sub.2O + K.sub.2O 5-30; the sum of MgO + CaO + SrO + BaO + ZnO 5-30; the sum of TiO.sub.2 + ZrO.sub.2 .sup.0-7; and P.sub.2O.sub.5 0-2.

12. The flexible article according to claim 11, wherein the composition further comprises one or more of: coloring oxides selected from the group consisting of Nd.sub.2O.sub.3, Fe.sub.2O.sub.3, CoO, NiO, V.sub.2O.sub.5, MnO.sub.2, TiO.sub.2, CuO, CeO.sub.2, and Cr.sub.2O.sub.3; 0-1 wt. % of rare earth oxides; 0-15 wt. % of black glass; and 0-2 wt. % of a refining agent selected from the group consisting of As.sub.2O.sub.3, Sb.sub.2O.sub.3, SnO.sub.2, SO.sub.3, Cl, F, CeO.sub.2, and combinations thereof.

13. The flexible article according to claim 4, wherein the glass comprises aluminosilicate glass having a composition, in weight percent, of: TABLE-US-00011 SiO.sub.2 40-75; Al.sub.2O.sub.3 10-30; B.sub.2O.sub.3 0-20; the sum of Li.sub.2O + Na.sub.2O + K.sub.2O 4-30; the sum of MgO + CaO + SrO + BaO + ZnO 0-15; the sum of TiO.sub.2 + ZrO.sub.2 .sup.0-15; and P.sub.2O.sub.5 0-10.

14. The flexible article according to claim 13, wherein the composition further comprises one or more of: coloring oxides selected from the group consisting of Nd.sub.2O.sub.3, Fe.sub.2O.sub.3, CoO, NiO, V.sub.2O.sub.5, MnO.sub.2, TiO.sub.2, CuO, CeO.sub.2, and Cr.sub.2O.sub.3; 0-1 wt. % of rare earth oxides; 0-15 wt. % of black glass; and 0-2 wt. % of a refining agent selected from the group consisting of As.sub.2O.sub.3, Sb.sub.2O.sub.3, SnO.sub.2, SO.sub.3, Cl, F, CeO.sub.2, and combinations thereof.

15. The flexible article according to claim 4, wherein the metal foil comprises a metal selected from the group consisting of Fe, Cu, Al, Cr, Co, Ag, Ni, and any alloys thereof.

16. The flexible article according to claim 4, wherein the metal foil comprises stainless steel.

17. The flexible article according to claim 4, wherein the glass has a thermal expansion coefficient in a temperature range of 20-300 C. from 110.sup.6/K to 2510.sup.6/K.

18. The flexible article according to claim 4, wherein the flexible article is subject to a treatment selected from the group consisting of cutting, milling, polishing, and drilling.

19. The flexible article according to claim 18, wherein the treatment is carried out in an atmosphere selected from the group consisting of air, a reducing atmosphere, an atmosphere with a small amount of oxygen, nitrogen, and a mixture of nitrogen and hydrogen.

20. The flexible article according to claim 4, wherein the glass has a surface that is chemically toughened and has a DoL of >1 m and a CS of >200 MPa.

21. The flexible article according to claim 4, wherein at least a portion of the glass is crystallized to a glass ceramic.

22. The flexible article according to claim 21, wherein the glass ceramic has a crystalline phase selected from the group consisting of a high quartz solid solution, lithium disilicate, barium disilicate, enstatite, wollastonite, stuffed -quartz, -spodumene, cordierite, mullite, potassium richterite, canasite, spinel solid solution, quartz, and borate.

23. The flexible article according to claim 4, wherein the glass has thickness below 300 m and/or a surface roughness below 1 nm.

24. A process for producing a flexible article, comprising: melting a glass at high temperature; cooling the glass; and laminating the glass with a metal foil.

25. The process according to claim 24, further comprising forming the glass into a thin glass prior to cooling.

26. The process according to claim 25, wherein the step of laminating comprises directly laminating the thin glass with the metal foil after the cooling step.

27. The process according to claim 25, wherein the step of laminating comprises adhering the thin glass to the metal foil by a binder comprising a glass slurry.

28. The process according to claim 27, wherein the glass slurry comprises a glass powder, the glass power comprising glass that has been high temperature melted and cooled.

29. The process according to claim 28, wherein the step of forming the glass into the thin glass comprises a process selected from the group consisting of an up drawing process, a down draw process, an overflow process, and a float process.

30. The process according to claim 24, further comprising: milling the glass into a powder after the cooling step; and mixing the powder with an organic solution to obtain a glass slurry, wherein the laminating step comprises coating the slurry on the metal foil.

31. The process according to claim 30, wherein the step of coating the slurry comprises a process selected from the group consisting of screen printing, dip coating, rolling coating, and spray coating.

32. The process according to claim 24, further comprising milling the glass into a powder after the cooling step, wherein the laminating step comprises electrostatic coating of the powder on the metal foil.

33. The flexible article according to claim 1, wherein the glass is aluminosilicate glass.

34. The flexible article according to claim 1, wherein the glass is soda lime glass.

35. The flexible article according to claim 1, wherein the glass is aluminosilicate glass.

36. The flexible article according to claim 1, wherein the glass is soda lime glass.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0089] FIG. 1 An embodiment of the flexible articles of the invention, wherein 10 is a glass layer, and 11 is a metal foil;

[0090] FIG. 2 An other embodiment of the invention, wherein 20 is a glass layer, 21 is metal foil, and 22 is a glass layer;

[0091] FIG. 3 An other embodiment of the invention, wherein 30 is a glass layer, and 31 is metal foil;

[0092] FIG. 4 An other embodiment of the invention, wherein 40 is a glass layer, 41 is a glass layer formed by glass powder or glass slurry, 42 is a metal foil, 43 is a glass layer formed by glass powder or glass slurry, and 44 is a glass layer;

[0093] FIG. 5 An other embodiment of the invention, wherein 50 is a glass layer, 51 is glass powder or glass slurry, and 52 is a metal foil;

[0094] FIG. 6 An other embodiment of the invention, wherein 60 is a glass ceramic layer, 61 is a glass layer, 62 is a glass ceramic layer, and 63 is metal foil;

[0095] FIG. 7 The surface of the metal foil SUS 430;

[0096] FIG. 8 The surface of the metal foil SUS 430 after glass coating and

[0097] FIG. 9 A glass/metal composite article that can be bent.

[0098] FIG. 10 Glass layer formed on the steel by using high temperature melting and cooling.

[0099] FIG. 11 Glass layer formed on the steel by using sol-gel.

DETAILED DESCRIPTION

[0100] The electric resistance is measured using the four point probe method.

[0101] The curvature radius that is measured in the current invention is the radius of the circular arc formed under the action of certain external force.

[0102] The shear strength is measured by the junction surface of a shearing sample of the composite steel plate being subjected to shearing with a corresponding shearing apparatus under the action of static pressure (tension) until its breaking.

TABLE-US-00008 TABLE 1 Glass compositions Composition/wt. % glass 1 glass 2 glass 3 glass 4 glass 5 glass 6 glass 7 glass 8 glass 9 glass 10 SiO.sub.2 18.96 37.35 36.82 0.52 0 36.82 30.76 74.42 40.29 32.99 Al.sub.2O.sub.3 0 1 26.77 0 0 10.55 14.32 0 3.21 0 B.sub.2O.sub.3 71.71 6.47 14.3 1.33 3.92 25.46 34.04 12.03 0 2.85 Na.sub.2O 9.33 0 12.47 0.52 11.05 12.47 10.49 5.62 13.46 15.3 K.sub.2O 0 0 3.65 0.55 0 3.65 0 3.2 7.68 5.11 CoO 0 0 0 0 0 0 0 0 0 0 NiO 0 0 0 0 0 0 0 0 0 0 Ni.sub.2O.sub.3 0 0 0 0 0 0 0 0 0 0 MnO 0 0 0 0 0 0 0 0 0 0 CaO 0 3.49 4.56 0.66 3.29 9.63 3.94 0 1.59 2.91 BaO 0 43.82 0 1.7 0 0 6.45 0 4.11 0 ZnO 0 4.98 0 1.7 33.42 0 0 0 0 0 ZrO.sub.2 0 2.49 0 0 0 0 0 0 0.21 0 MnO.sub.2 0 0 1.03 0 0 1.02 0 0 0 0 CeO 0 0.1 0.1 0 0 0.1 0 0 0 0 SnO.sub.2 0 0.3 0.3 0 0 0.3 0 0 0 0 Sb.sub.2O.sub.3 0 0 0 0 0 0 0 4.35 0.03 0.11 TiO.sub.2 0 0 0 0 0 0 0 0.38 25.2 29.16 P.sub.2O.sub.5 0 0 0 0 33.3 0 0 0 0 0 MgO 0 0 0 0 0 0 0 0 0 0 SrO 0 0 0 0 0 0 0 0 0 0 Li.sub.2O 0 0 0 0.89 0 0 0 0 0.2 2.89 Li.sub.2O + Na.sub.2O + K.sub.2O 9.33 0 16.12 1.96 11.05 16.12 10.49 8.82 21.34 23.3 SiO.sub.2 + B.sub.2O.sub.3 + P.sub.2O.sub.5 90.670 43.82 51.12 1.85 37.22 62.28 64.8 86.45 40.29 35.84 Nd.sub.2O.sub.5 0 0 0 0 0 0 0 0 4.02 8.68 V.sub.2O.sub.5 0 0 0 0.28 0 0 0 0 0 0 SO.sub.3 0 0 0 37.36 15.02 0 0 0 0 0 SnO 0 0 0 54.49 0 0 0 0 0 0 Properties T.sub.g ( C.) 383 734 550 322 357 547 525 498 524 508 CTE(10 /K) 8.2 9.86 8.96 9 13.14 8.47 7.47 7.3 11.1 11.1 AT ( C.) 437 840 629 386 397 500 577 546 580 547 Flowing temperature 600 920 890 560 580 870 850 890 750 720 ( C.) T13.6 (dPa .Math. s) T7.6 (dPa .Math. s) 657 625 602 T4 (dPa .Math. s) 924 782 745 wherein T13.6 represents the strain point of the glass; T7.6 represents the softening point of the glass; and T4 represents the working point of the glass. indicates data missing or illegible when filed

Example 1

[0103] According to the composition of glass 1 in Table 1, the raw materials used are oxides, hydroxides, carbonates, and nitrates, etc. After weighting and mixing the raw materials, the mixture is placed into a platinum crucible. The mixture is melted at 1550-1600 C. in an electric furnace, then made into a ribbon by a rotating device. The ribbon is milled into powder through a milling device. The medium grain size (D50) of the glass power is about 1-2 m. A slurry is prepared by mixing the glass powder and terpineol, and the viscosity of the slurry is about 410.sup.4.5 Pa.Math.s. Screen printing is used to coat the slurry on the stainless steel foil (SUS430, 190 m thick). It is pre-sintered at 400 C. for 30 min, and then treated at 850 C. for 2 hours. Finally, a glass layer is formed on the stainless steel foil. The surface roughness of the glass is 40 nm from peak to peak. The electrical resistivity is 610.sup.11 .Math.m. The curvature radius is 50 mm. The shear strength between the glass and the stainless steel foil is 120 MPa/mm.sup.2.

[0104] The original surface of the stainless steel used as shown in FIG. 7 is not smooth, and there are many strips on the surface. After coating a glass layer, the surface becomes smooth. A flexible article made of stainless steel foil coated with glass is shown in FIG. 8. The results of Example 1 show that, after forming a glass layer on the stainless steel foil, the surface roughness is reduced to below 100 nm.

Example 2

[0105] A thin glass (D263, SCHOTT product) with a thickness of 30 m and a size of 200 mm200 mm is prepared. The thin glass is placed on a stainless steel foil (SUS430, 150 m thick), and it is subjected to heat treatment at 900 C. for 2.5 hours, and then cooled, thereby obtaining a flexible article made of thin glass and stainless steel foil. The surface roughness is 30 nm from peak to peak. The electrical resistivity is 1.610.sup.8 .Math.m. The curvature radius is 100 mm. The shear strength between the glass and the stainless steel foil is 220 MPa/mm.sup.2.

Example 3

[0106] According to glass 3 in Table 1, the raw materials used are oxides, hydroxides, carbonates, and nitrates, etc. After weighting and mixing, the resultant mixture is placed into a platinum crucible. The mixture is melted at 1550-1600 C. in an electric furnace, then made into ribbon by a rotating device. The ribbon is milled into glass powder through a milling device. The medium grain size (D50) of the glass power is about 1-2 m. A slurry is prepared by mixing the glass powder, terpineol and ethyl cellulose. The stainless steel foil used comprises about 12 wt % of chromium, 3.5 wt % of aluminum, 1 wt % of titanium, about 0.35 wt % of manganese, about 0.3 wt % of silicon, and about 0.025 wt % of carbon, the remaining component is iron. The stainless steel has a thickness of 90 m. Screen printing is used to coat the glass slurry on the first surface of the stainless steel foil. It is pre-sintered at 100 C. for 30 min, and then screen printing is used to coat the slurry on the second surface of the stainless steel foil, and it is pre-sintered at 100 C. for 30 min, then treated at 850 C. for 3 hours. Finally, two attached thin glass layers are formed on the stainless steel foil. The surface roughness of the glass is 45 nm from peak to peak. The electrical resistivity is 510.sup.12 .Math.m. The curvature radius is 150 mm. The shear strength between the glass and the metal foil is 90 MPa/mm.sup.2.

Example 4

[0107] According to glass 6 in Table 1, the glass slurry is prepared by alkali boroaluminosilicate glass. The viscosity is about 3000 Pa.Math.s. The stainless steel foil (SUS430) with a thickness of 120 m is dipped into the slurry totally, and the stainless steel foil is drawn at a speed of 3 mm/min. After taking the stainless steel foil out, it is pre-sintered at 400 C. for 40 min, then treat at 850 C. for 1 hour, thereby obtaining a glass encapsulated flexible article made of glass and stainless steel foil. The surface roughness of the glass is 32 nm from peak to peak. The electrical resistivity is 710.sup.11 .Math.m. The curvature radius is 130 mm. The shear strength between the glass and the stainless steel foil is 220 MPa/mm.sup.2.

Example 5

[0108] A thin glass with a thickness of 30 m and a size of 200 mm200 mm is prepared. Firstly, the glass powder (produced from glass 1) is placed on the stainless steel foil, then the thin glass is placed on the top of the glass powder. The stainless steel foil is SUS304 with a thickness of 100 m. The sample is pre-sintered at 800 C. for 4 hours to obtain a three layered flexible article made of glass, glass powder and stainless steel foil. The surface roughness of the glass is 30 nm from peak to peak. The electrical resistivity is 1.510.sup.12 .Math.m. The curvature radius is 90 mm. The shear strength between the glass and the stainless steel foil is 250 MPa/mm.sup.2.

Example 6

[0109] Two thin glasses with a thickness of 30 m and a size of 200 mm200 mm are prepared. The glass slurry (produced from glass 9 in Table 1) is coated on the top and bottom surface of the stainless steel foil, then the thin glass is placed on the top of the glass slurry. The stainless steel foil is SUS301 with a thickness of 120 The sample is pre-sintered at 100 C. for 30 min, and sintered at 830 C. for 3 hours, thereby obtaining a five layered flexible article made of glass, glass slurry, stainless steel foil, glass slurry and glass. The surface roughness of the glass is 25 nm from peak to peak. The electrical resistivity is 1.510.sup.12 .Math.m. The curvature radius is 200 mm. The shear strength between the glass and the stainless steel foil is 300 MPa/mm.sup.2.

Example 7

[0110] According to the composition of glass 4 in Table 1, the raw materials used are oxides, hydroxides, carbonates, and nitrates, etc. After weighing out and mixing the raw materials, the mixture is placed into a platinum crucible, melting at 1550-1600 C. in an electric furnace with the melt made into a ribbon by a rotating device. The ribbon is milled into powder through a milling device. The medium grain size (D50) of the glass power is about 0.5-1 m. A slurry is prepared by mixing the glass powder and terpineol, and the viscosity of the slurry is about 410.sup.4.5 Pa.Math.s. Screen printing is used to coat the slurry on the stainless steel foil (SUS430, 190 m thick). It is pre-sintered at 100 C. for 30 min, and then is treated at 850 C. for 2 hours. Finally, a glass layer is formed on the stainless steel foil. The surface roughness of the glass is 40 nm from peak to peak. The electrical resistivity is 410.sup.11 .Math.m. The curvature radius is 60 mm. The shear strength between the glass and the stainless steel foil is 140 MPa/mm.sup.2.

Example 8

[0111] According to glass 9 in Table 1, the raw materials used are oxides, hydroxides, carbonates, and nitrates, etc. After weighting and mixing, the resultant mixture is placed into a platinum crucible. The mixture is melted at 1550-1600 C. in an electric furnace, then made into ribbon by a rotating device. The ribbon is milled into powder through a milling device. D50 is about 2-3 m. A slurry is prepared by mixing the glass powder and terpineol, and the viscosity of the slurry is about 4.510.sup.4.5 Pa.Math.s. Screen printing is used to coat the slurry on stainless steel foil. The stainless steel foil is stainless steel grade 430 with a thickness of 180 m. It is pre-sintered at 100 C. for 30 min, then treated at 850 C. for 2 hours, and then treated at 700 C. for 4 hours to form crystallite layers on the top surface and the bottom surface of the glass layer. Finally, a glass layer with crystallite layers on the top surface and the bottom surface is formed on the stainless steel foil. The surface roughness of the glass is 70 nm from peak to peak. The electrical resistivity is 810.sup.11 .Math.m. The curvature radius is 100 mm. The shear strength between the glass and the stainless steel foil is 180 MPa/mm.sup.2.

[0112] FIG. 10 is the sample prepared according to Example 1. The glass layer is formed by high temperature melting and cooling in the absence of any precursor. The surface is smooth and shining without small holes and cracks. The glass surface is dense with a thickness of about 10 m.

[0113] FIG. 11 is the sample prepared according to the sol-gel method by using precursor. The filtered glass precursor composition (0.1 ml) was rod-coated onto a stainless steel and dried at 150 C. for 1 min to form a dried glass precursor layer on the stainless steel. After drying, the coated substrates were calcined to 600 C. for 30 min at a heating rate of 8 C. per minute, thereby obtaining the glass layer of lower than 0.3 m. The surface is neither smooth nor shining with some small holes on the surface. It has been noticed that cracks occur on the glass surface.