Patent GB-1216273-A (GB)
Title: Improvements relating to the preparation of vitreous and vitro-crystalline products
Inventor: PLUMAT EMILE
IPC: C03C21/00
Filed: 1968-04-01
Abstract: 1,216,273. Chemical tempering. GLAVERBEL. 1 April, 1968 [25 April, 1967], No. 15494/68. Heading C1M. A glass or vitrocrystalline article, e.g. a sheet, rod, tube or hollow ware article has external layers which have been placed in a state of compression by a chemical tempering treatment in which ions, e.g. Li<SP>+</SP>, entered the glass in exchange for larger ions, e.g. Na<SP>+</SP>, during a primary forming treatment, e.g. a glass drawing operation, wherein the molten or plastic glass is contacted with an ionized medium, before the article has assumed its final shaping. The ionexchange preferably occurs while the molten glass is above the dilatometric softening point and thus at least commences during the glass drawing operation before or while any given portion of drawn glass forms the meniscus at the position where the glass is drawn from the surface of the bath of molten glass. A film of the ion-exchange medium may be cooled as a coating on the glass to terminate the ionexchange. The first ion-exchange may be followed by a second one in which ions introduced into the glass by the first ion-exchange, e.g. Li<SP>+</SP>, are replaced by larger ions, e.g. K<SP>+</SP> or Na<SP>+</SP> while the glass is below the annealing point, and preferably commences before the glass leaves the drawing machine. The distribution of the smaller ions in the glass cross-section can be made more uniform by heating the internal layers to a temperature at which stress relaxation therein can occur, e.g. above the annealing point, while keeping the surface layers below the annealing point so that stress relaxation does not occur, by, for example exposing the glass body to thermal radiation while the glass body is in contact with a heated gaseous medium below the annealing point temperature. The article may then be subsequently re-heated and subjected to a low temperature chemical tempering treatment involving the replacement of ions in the glass, e.g. Li<SP>+</SP> or Li<SP>+</SP> and Na<SP>+</SP> ions by larger ions, e.g. K<SP>+</SP> from a contacting medium. In the apparatus described, glass is drawn upwardly from a bath 8 forming a meniscus 18 through drawing chamber 1, passing between coolers 24 and catch pans 21 into tower section 22 housing pairs of drawing rollers 23. Vapours of Li 2 SO 4  are fed into compartment 26 and layers 32 and 33 of molten salts, e.g. Li 2 CO 3  6%, LiCl 4%, NaN0 3  90% by weight float on the surface of bath 8. As the glass drawing proceeds the forward current 9 is directly enriched with lithium from compartment 26, as well as from the molten salt layer 33 while the glass in the forward current 12 acquires lithium from molten salt layer 32. Films of the salts which adhere to the glass surfaces as it rises into the meniscus are solidified by coolers 44, 45 and the ion-exchange ceases by the time the glass reaches the level 19. In. the upper part of tower section 22 where the temperature is below the annealing point a pair of rollers 40, 41 are supplied with a mixture of molten salts comprising KNO 3  and KNO 2  for effecting the second ion-exchange.