Patent GB-1399211-A (GB)
Title: Glasses and glass-ceramics and products made therefrom
IPC: C03C10/00
Filed: 1972-05-25
Abstract: 1399211 Glass ceramics; joining glass to glass OWENS-ILLINOIS Inc 25 May 1972 [25 May 1971 28 Feb 1972] 24579/72 Heading C1M A thermally crystallizable glass capable of being thermally in situ crystallized to a glassceramic which is thermally stable at temperatures of about 1500 F. for at least 1000 hours and maintains its modulus of rupture of at least 10,000 p.s.i. at such temperatures for said times, said glass being zinc oxide free and comprising 98-100% by weight of the following ingredients 55-80% SiO 2 , 12-27% Al 2 O 3 , Li 2 O 32-7À6, nucleating agent 3-9, the balance, if any, consisting of other compatible ingredients, each of said compatible ingredients not exceeding 0À5% by weight of the weight of the glass, said balance containing less than 0À1% by weight of the weight of the glass of fluorine and no more than 0À5% by weight of the weight of the glass of Na 2 O + K 2 O, wherein said nucleating agent is a mixture of TiO 2  + ZrO 2  and said ZrO 2  is present in an amount 0À5-2À8% by weight, wherein the SiO 2 /Al 2 O 3  molar ratio is 4-10, and wherein (a) when the SiO 2 /Al 2 O 3  molar ratio is from 4 or more but less than 5, the Li 2 O/Al 2 O 3  molar ratio is 0À75-0À97; and (b) when the SiO 2 /Al 2 O 3  molar ratio is 5-7À5, the Li 3 /Al 2 D 3  molar ratio is 0À65-0À97 and (c) when the SiO 2 /Al 2 O 3  molar ratio is more than 7À5 but less than 9, the Li 2 O/Al 2 O 3  molar ratio is 0À8-0À97; and (d) when the SiO 2 /Al 2 O 3  molar ratio is more than 9 and up to 10, the Li 2 O/Al 2 O 3  molar ratio is 0À87-0À97. The glass ceramic has a coefficient of linear thermal expansion of - 12 to + 12 x 10<SP>-7</SP> (0-700 C.). In examples additional ingredients specified are 0À3% Sb 2 O 3  and Fe 2 O 3  in amounts 0À45% and 0À10%. Comparative examples include 3% Li 2 O (24); 7À7% Li 2 O and 27À8% Al 2 O 3  (25); 2À4% Li 2 O (28); 3À15% Li 2 O (29); 0À5% Na 2 O and 0À2% K 2 O (30); 0À8% Na 2 O and 0À4% K 2 O (31); 0À3% F 2  and 1À7% Zn (32); and 0À2% F 2  (33). The glasses are formed into glass rods prior to heat-treatment for forming glassceramics. The rods are heated to their nucleating temperature (1350 F.) at 300 F. per hour and held at that temperature for 8 hours after which they are heated to the finishing temperature which may be 2100 or 2200 F. and held there for 2 hours. All the rods were then cooled at 25 F. per hour to 1500 F. and then cooled to room temperature at about 300 F. A cellular matrix is formed of tubes of the glass ceramic fused together to provide a series of smooth-walled longitudinal passages the walls of which have an average coefficient of thermal expansion of - 12 to + 12 x 10<SP>-7</SP>/ C. (0-700 C.) wherein (a)the inner diameter of said passageways is at least 3 times the wall thickness through portions of said walls common to adjacent fused tubes and (b) the open fronted or cross-sectional area of each face of the matrix containing passageways is at least 32% of the cross-sectional area across such face. Such matrices can withstand temperatures of at least 1500 F. for at least 1000 hours and will have dimensional stability of less than 250 p.p.m. Further matrices may have a thermal conductivity at 400 C. of less than 0À01 cal./cm./sec./ cm.<SP>2</SP>/ C. and an open fronted cross-sectional area of at least 60%. The cellular matrix may be made of a mould lined with a layer of heatresistant alumina-silica paper. The assembly is heated to produce a glass-ceramic matrix, in like manner to the above, the heat treatment fusion bonding the walls of each tube to those of adjacent tubes and reforming each tube to substantially hexagonal shape. Alternatively a plurality of layers of tubes are superimposed one above the other in successive parallel planes, the tubes within each plane being essentially parallel to each other and transverse to tubes in adjacent layers.