US2015368148A1PendingUtilityA1

Glasses having non-frangible stress profiles

Assignee: CORNING INCPriority: Jun 19, 2014Filed: Jun 12, 2015Published: Dec 24, 2015
Est. expiryJun 19, 2034(~7.9 yrs left)· nominal 20-yr term from priority
C03C 3/085C03C 3/083C03C 3/095C03C 3/087C03C 2204/00C03C 3/097C03C 3/093C03C 4/18C03C 3/091C03C 21/002
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Claims

Abstract

A glass exhibiting non-frangible behavior in a region where substantially higher central tension is possible without reaching frangibility is provided. This region allows greater extension of the depth of compression in which fracture-causing flaws are arrested, without rendering the glass frangible despite the presence of high central tension region in the sample.

Claims

exact text as granted — not AI-modified
1 . A glass having a compressive layer extending from a surface of the glass to a depth of compression DOC and under a maximum compressive stress CS, a central region having a maximum physical central tension CT at a center of the glass, the central region extending outward from the center to the depth of compression, and a thickness t in a range from about 0.3 mm to about 1.0 mm, wherein DOC≧0.08·t and CT−CS≦350 MPa. 
     
     
         2 . The glass of  claim 1 , wherein the glass exhibits non-frangible behavior when the surface having the compressive layer is subjected to a point impact force sufficient to create at least one new crack at the surface and extend the crack through the compressive layer to the central region. 
     
     
         3 . The glass of  claim 2 , wherein the glass has a frangibility index of less than 3. 
     
     
         4 . The glass of  claim 2 , wherein CT A  is the central tension CT as determined by FSM, wherein CT A (MPa)=CT 1 ≧57(MPa)−9.0(MPa)·ln(t)+49.3(MPa)·ln 2 (t)(mm) when the thickness t is less than or equal to 0.75 mm, and wherein CT A  and wherein CT A =CT 3 ≧−38.7(MPa)×ln(t)+48.2(MPa) when t is greater than 0.75 mm. 
     
     
         5 . The glass of  claim 1 , wherein DOC≧0.09·t and the thickness t is greater than 0.5 mm. 
     
     
         6 . The glass of  claim 1 , wherein DOC≧0.1·t. 
     
     
         7 . The glass of  claim 6 , wherein DOC≧0.15·t. 
     
     
         8 . The glass of  claim 1 , wherein the thickness t is greater than 0.75 mm. 
     
     
         9 . The glass of  claim 1 , wherein the glass has an average elastic energy density of less than 200 J/m 2 ·mm. 
     
     
         10 . The glass of  claim 9 , wherein the glass has an average elastic energy density of less than 140 J/m 2 ·mm. 
     
     
         11 . The glass of  claim 10 , wherein the glass has an average elastic energy density of less than 120 J/m 2 ·mm. 
     
     
         12 . The glass of  claim 1 , wherein the glass is strengthened by ion exchange. 
     
     
         13 . The glass of  claim 12 , wherein the compressive stress CS is at least about 150 MPa. 
     
     
         14 . The glass of  claim 12 , wherein the compressive stress CS is less than about 250 MPa. 
     
     
         15 . The glass of  claim 1 , wherein CT−CS≦334 MPa. 
     
     
         16 . The glass of  claim 1 , the glass has a total normalized elastic energy less than or equal to 37.5×10 3  MPa 2  μm. 
     
     
         17 . The glass of  claim 1 , wherein the thickness t is 0.4 mm and wherein the glass has a normalized elastic energy less than or equal to 15×10 6  MPa 2  μm. 
     
     
         18 . The glass of  claim 17 , wherein the normalized stored elastic energy per unit thickness is less than about 19×10 3  MPa 2  μm. 
     
     
         19 . The glass of  claim 1 , wherein the glass is an alkali aluminosilicate glass. 
     
     
         20 . The glass of  claim 19 , wherein the alkali aluminosilicate glass comprises: from about 60 mol % to about 70 mol % SiO 2 ; from about 6 mol % to about 14 mol % Al 2 O 3 ; from 0 mol % to about 15 mol % B 2 O 3 ; from 0 mol % to about 15 mol % Li 2 O; from 0 mol % to about 20 mol % Na 2 O; from 0 mol % to about 10 mol % K 2 O; from 0 mol % to about 8 mol % MgO; from 0 mol % to about 10 mol % CaO; from 0 mol % to about 5 mol % ZrO 2 ; from 0 mol % to about 1 mol % SnO 2 ; from 0 mol % to about 1 mol % CeO 2 ; less than about 50 ppm As 2 O 3 ; and less than about 50 ppm Sb 2 O 3 ; wherein 12 mol %≦Li 2 O+Na 2 O+K 2 O≦20 mol % and 0 mol %≦MgO+CaO≦10 mol %. 
     
     
         21 . The glass of  claim 19 , wherein the alkali aluminosilicate glass comprises: at least about 50 mol % SiO 2 ; at least about 10 mol % R 2 O, wherein R 2 O comprises Na 2 O; Al 2 O 3 , wherein −0.5 mol %≦Al 2 O 3 (mol %)−R 2 O(mol %)≦2 mol %; and B 2 O 3 , and wherein B 2 O 3 (mol %)−(R 2 O(mol %)−Al 2 O 3 (mol %))≧4.5 mol %. 
     
     
         22 . The glass of  claim 19 , wherein the alkali aluminosilicate glass comprises: the alkali aluminosilicate glass is ion exchangeable and comprises: at least about 50 mol % SiO 2 ; at least about 10 mol % R 2 O, wherein R 2 O comprises Na 2 O; Al 2 O 3 ; and B 2 O 3 , wherein B 2 O 3 −(R 2 O−Al 2 O 3 )≧3 mol %. 
     
     
         23 . The glass of  claim 19 , wherein the alkali aluminosilicate glass comprises at least about 4 mol % P 2 O 5  and from 0 mol % to about 4 mol % B 2 O 3 , and wherein 1.3<[(P 2 O 5 +R 2 O)/M 2 O 3 ]≦2.3, where M 2 O 3 ═Al 2 O 3 +B 2 O 3 , and R 2 O is the sum of monovalent cation oxides present in the alkali aluminosilicate glass. 
     
     
         24 . The glass of  claim 19 , wherein the alkali aluminosilicate glass comprises: from about 50 mol % to about 72 mol % SiO 2 ; from about 12 mol % to about 22 mol % Al 2 O 3 ; up to about 15 mol % B 2 O 3 ; up to about 1 mol % P 2 O 5 ; from about 11 mol % to about 21 mol % Na 2 O; up to about 5 mol % K 2 O; up to about 4 mol % MgO; up to about 5 mol % ZnO; and up to about 2 mol % CaO, wherein Na 2 O+K 2 O−Al 2 O 3 ≦2.0 mol %, B 2 O 3 −(Na 2 O+K 2 O−Al 2 O 3 )>4 mol %, and 24 mol %≦RAlO 4 ≦45 mol %. 
     
     
         25 . The glass of  claim 19 , wherein the alkali aluminosilicate glass further comprises up to about 10 mol % Li 2 O. 
     
     
         26 . The glass of  claim 19 , wherein the glass is substantially free of lithium. 
     
     
         27 . A glass having a compressive layer extending from a surface of the glass to a depth of compression DOC and under a maximum compressive stress CS, a central region having a maximum physical central tension CT at a center of the glass, the central region extending outward from the center to the depth of compression into the glass, and a thickness t in a range from about 0.3 mm to about 1.0 mm, wherein:
 a. the depth of compression DOC is greater than or equal to 0.08·t; and   b. the glass has an average elastic energy density of less than about 200 J/m 2 ·mm.   
     
     
         28 . The glass of  claim 27 , wherein the glass exhibits non-frangible behavior when the surface having the compressive layer is subjected to a point impact force sufficient to create at least one new crack at the surface and extend the crack through the compressive layer. 
     
     
         29 . The glass of  claim 28 , wherein the glass has a frangibility index of less than 3. 
     
     
         30 . The glass of  claim 27 , wherein CT A  is the central tension CT as determined by FSM, wherein CT A (MPa)=CT 1 ≧57(MPa)−9.0(MPa)·ln(t)+49.3(MPa)·ln 2 (t)(mm) when the thickness t is less than or equal to 0.75 mm, and wherein CT A  and wherein CT A =CT 3 ≧−38.7(MPa)×ln(t)+48.2(MPa) when t is greater than 0.75 mm. 
     
     
         31 . The glass of  claim 27 , wherein the thickness t is greater than 0.75 mm. 
     
     
         32 . The glass of  claim 31 , wherein the glass has an average elastic energy density of less than 140 J/m 2 ·mm. 
     
     
         33 . The glass of  claim 32 , wherein the glass has an average elastic energy density of less than 120 J/m 2 ·mm. 
     
     
         34 . The glass of  claim 27 , wherein the glass is strengthened by ion exchange. 
     
     
         35 . The glass of  claim 34 , wherein the compressive stress CS is at least about 150 MPa. 
     
     
         36 . The glass of  claim 35 , wherein the compressive stress CS is less than about 250 MPa. 
     
     
         37 . The glass of  claim 27 , wherein CT−CS≦334 MPa. 
     
     
         38 . The glass of  claim 27 , wherein the glass is an alkali aluminosilicate glass. 
     
     
         39 . The glass of  claim 38 , wherein the alkali aluminosilicate glass comprises: from about 60 mol % to about 70 mol % SiO 2 ; from about 6 mol % to about 14 mol % Al 2 O 3 ; from 0 mol % to about 15 mol % B 2 O 3 ; from 0 mol % to about 15 mol % Li 2 O; from 0 mol % to about 20 mol % Na 2 O; from 0 mol % to about 10 mol % K 2 O; from 0 mol % to about 8 mol % MgO; from 0 mol % to about 10 mol % CaO; from 0 mol % to about 5 mol % ZrO 2 ; from 0 mol % to about 1 mol % SnO 2 ; from 0 mol % to about 1 mol % CeO 2 ; less than about 50 ppm As 2 O 3 ; and less than about 50 ppm Sb 2 O 3 ; wherein 12 mol %≦Li 2 O+Na 2 O+K 2 O≦20 mol % and 0≦mol % MgO+CaO≦10 mol %. 
     
     
         40 . The glass of  claim 38 , wherein the alkali aluminosilicate glass comprises: at least about 50 mol % SiO 2 ; at least about 10 mol % R 2 O, wherein R 2 O comprises Na 2 O; Al 2 O 3 , wherein −0.5 mol %≦Al 2 O 3 (mol %)−R 2 O(mol %)≦2 mol %; and B 2 O 3 , and wherein B 2 O 3 (mol %)−(R 2 O(mol %)−Al 2 O 3 (mol %))≧4.5 mol %. 
     
     
         41 . The glass of  claim 38 , wherein the alkali aluminosilicate glass comprises: the alkali aluminosilicate glass is ion exchangeable and comprises: at least about 50 mol % SiO 2 ; at least about 10 mol % R 2 O, wherein R 2 O comprises Na 2 O; Al 2 O 3 ; and B 2 O 3 , wherein B 2 O 3 −(R 2 O−Al 2 O 3 )≧3 mol %. 
     
     
         42 . The glass of  claim 38 , wherein the alkali aluminosilicate glass comprises at least about 4 mol % P 2 O 5  and from 0 mol % to about 4 mol % B 2 O 3 , and wherein 1.3<[(P 2 O 5 +R 2 O)/M 2 O 3 ]≦2.3, where M 2 O 3 ═Al 2 O 3 +B 2 O 3 , and R 2 O is the sum of monovalent cation oxides present in the alkali aluminosilicate glass. 
     
     
         43 . The glass of  claim 38 , wherein the alkali aluminosilicate glass comprises: from about 50 mol % to about 72 mol % SiO 2 ; from about 12 mol % to about 22 mol % Al 2 O 3 ; up to about 15 mol % B 2 O 3 ; up to about 1 mol % P 2 O 5 ; from about 11 mol % to about 21 mol % Na 2 O; up to about 5 mol % K 2 O; up to about 4 mol % MgO; up to about 5 mol % ZnO; and up to about 2 mol % CaO, wherein Na 2 O+K 2 O−Al 2 O 3 ≦2.0 mol %, B 2 O 3 −(Na 2 O+K 2 O−Al 2 O 3 )>4 mol %, and 24 mol %≦RAlO 4 ≦45 mol %. 
     
     
         44 . The glass of  claim 38 , wherein the alkali aluminosilicate glass further comprises up to about 10 mol % Li 2 O. 
     
     
         45 . The glass of  claim 38 , wherein the glass is substantially free of lithium. 
     
     
         46 . A glass, the glass comprising:
 a. a compressive layer extending from a surface of the glass to a depth of compression DOC, the compressive surface layer having a maximum compressive stress CS;   b. a central region having a maximum physical central tension CT at a center of the glass, the central region extending outward from the center of the glass to the depth of compression;   c. a thickness t in a range from about 0.3 mm to about 1.0 mm, wherein DOC≧0.08·t and CT−CS≦350 MPa; and wherein:
 i. the physical central tension CT is greater than 0.681×(57−9.0×ln(t)+49.3×(ln(t)) 2 ) when 0.3 mm≦t≦0.5 mm; 
 ii. the physical central tension CT is greater than 0.728×(57−9.0×ln(t)+49.3×(ln(t)) 2 ) when 0.5 mm≦t≦0.7 mm; and 
 iii. the physical central tension CT is greater than 
   
       
         
           
             
               0.755 
               × 
               
                 ( 
                 
                   
                     
                       - 
                       38.7 
                     
                      
                     
                       ( 
                       
                         MPa 
                         mm 
                       
                       ) 
                     
                     × 
                     
                       ln 
                        
                       
                         ( 
                         t 
                         ) 
                       
                     
                      
                     
                       ( 
                       mm 
                       ) 
                     
                   
                   + 
                   
                     48.2 
                      
                     
                       ( 
                       MPa 
                       ) 
                     
                   
                 
                 ) 
               
             
           
         
       
       when 0.7 mm<t≦1.0 mm. 
     
     
         47 . The glass of  claim 46 , wherein:
 a. the physical central tension CT is greater than 0.728×(57−9.0×ln(t)+49.3×(ln(t)) 2 ) when 0.3 mm≦t≦0.5 mm;   b. the physical central tension CT is greater than 0.751×(57−9.0×ln(t)+49.3×(ln(t)) 2 ) when 0.5 mm≦t≦0.7 mm; and   c. the physical central tension CT is greater than   
       
         
           
             
               0.768 
               × 
               
                 ( 
                 
                   
                     
                       - 
                       38.7 
                     
                      
                     
                       ( 
                       
                         MPa 
                         mm 
                       
                       ) 
                     
                     × 
                     
                       ln 
                        
                       
                         ( 
                         t 
                         ) 
                       
                     
                      
                     
                       ( 
                       mm 
                       ) 
                     
                   
                   + 
                   
                     48.2 
                      
                     
                       ( 
                       MPa 
                       ) 
                     
                   
                 
                 ) 
               
             
           
         
       
       when 0.7 mm<t≦1.0 mm. 
     
     
         48 . The glass of  claim 46 , wherein the glass has an average elastic energy density of less than 200 J/m 2 ·mm. 
     
     
         49 . The glass of  claim 48 , wherein the glass has an average elastic energy density of less than 140 J/m 2 ·mm. 
     
     
         50 . The glass of  claim 49 , wherein the glass has an average elastic energy density of less than 120 J/m 2 ·mm. 
     
     
         51 . The glass of  claim 46 , wherein the compressive stress CS is at least about 150 MPa. 
     
     
         52 . The glass of  claim 35 , wherein the compressive stress CS is less than about 250 MPa. 
     
     
         53 . The glass of  claim 46 , wherein the glass is an alkali aluminosilicate glass. 
     
     
         54 . The glass of  claim 46 , wherein the glass is an alkali aluminosilicate glass. 
     
     
         55 . A glass, the glass comprising:
 a. a compressive layer extending from a surface of the glass to a depth of compression DOC, the compressive surface layer having a maximum compressive stress CS;   b. a central region having a maximum physical central tension CT at a center of the glass, the central region extending outward from the center of the glass to the depth of compression, wherein the glass has an average elastic energy density of less than 200 J/m 2 ·mm;   c. a thickness t in a range from about 0.3 mm to about 1.0 mm, wherein DOC≧0.08·t and; and wherein:
 i. the physical central tension CT is greater than 0.681×(57−9.0×ln(t)+49.3×(ln(t)) 2 ) when 0.3 mm≦t≦0.5 mm; 
 ii. the physical central tension CT is greater than 0.728×(57−9.0×ln(t)+49.3×(ln(t)) 2 ) when 0.5 mm≦t≦0.7 mm; and 
 iii. the physical central tension CT is greater than 
   
       
         
           
             
               0.755 
               × 
               
                 ( 
                 
                   
                     
                       - 
                       38.7 
                     
                      
                     
                       ( 
                       
                         MPa 
                         mm 
                       
                       ) 
                     
                     × 
                     
                       ln 
                        
                       
                         ( 
                         t 
                         ) 
                       
                     
                      
                     
                       ( 
                       mm 
                       ) 
                     
                   
                   + 
                   
                     48.2 
                      
                     
                       ( 
                       MPa 
                       ) 
                     
                   
                 
                 ) 
               
             
           
         
       
       when 0.7 mm<t≦1.0 mm. 
     
     
         56 . The glass of  claim 46 , wherein:
 a. the physical central tension CT is greater than 0.728×(57−9.0×ln(t)+49.3×(ln(t)) 2 ) when 0.3 mm≦t≦0.5 mm;   b. the physical central tension CT is greater than 0.751×(57−9.0×ln(t)+49.3×(ln(t)) 2 ) when 0.5 mm≦t≦0.7 mm; and   c. the physical central tension CT is greater than   
       
         
           
             
               0.768 
               × 
               
                 ( 
                 
                   
                     
                       - 
                       38.7 
                     
                      
                     
                       ( 
                       
                         MPa 
                         mm 
                       
                       ) 
                     
                     × 
                     
                       ln 
                        
                       
                         ( 
                         t 
                         ) 
                       
                     
                      
                     
                       ( 
                       mm 
                       ) 
                     
                   
                   + 
                   
                     48.2 
                      
                     
                       ( 
                       MPa 
                       ) 
                     
                   
                 
                 ) 
               
             
           
         
       
       when 0.7 mm<t≦1.0 mm. 
     
     
         57 . The glass of  claim 48 , wherein the glass has an average elastic energy density of less than 140 J/m 2 ·mm. 
     
     
         58 . The glass of  claim 49 , wherein the glass has an average elastic energy density of less than 120 J/m 2 ·mm. 
     
     
         59 . The glass of  claim 27 , wherein the glass is strengthened by ion exchange. 
     
     
         60 . The glass of  claim 34 , wherein the compressive stress CS is at least about 150 MPa. 
     
     
         61 . The glass of  claim 35 , wherein the compressive stress CS is less than about 250 MPa. 
     
     
         62 . The glass of  claim 27 , wherein the glass is an alkali aluminosilicate glass.

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