Patent GB-1223607-A (GB)
Title: Method for strengthening vitreous materials
Inventor: PLUMAT EMILE
IPC: C03C17/02
Filed: 1968-03-04
Abstract: 1,223,607. Strengthening glass or glassceramics. GLAVERBEL. 4 March, 1968 [27 April, 1967], No. 10459/68. Heading C1M. A vitreous or vitrocrystalline body is strengthened by forming on at least part of the body an adherent vitreous or vitrocrystalline coating whose chemical composition differs from that of the body, and allowing or causing a solid-solid phase-transformation to occur in the coating, resulting in the presence of at least one more vitreous phase than was initially present. The body may be a flask, bottle, insulator, ampule, a flat or curved glass sheet, or a ribbon of drawn glass to which the coating constituents may be applied while the ribbon is still soft; the phasetransformation may continue during the cooling of the drawn glass, the ribbon being cut into sheets before completion of the phase-transformation; the sheet may be coated on one or both sides and/or one or both edges and/or the edge margins of the major surfaces. The coating after phase-transformation may comprise one or more vitreous phases formed by oxides of Pb, Bi or Ti. The final coated material may have increased surface hardness. The phase-transformation may be performed (a) by thermal treatments, including cooling schedules such that phase transformation occurs during or after solidification and becomes apparent during or after cooling; and/or (b) by sound wave or ultrasonic (e.g. at 10<SP>4</SP>-10<SP>7</SP> or more cycles/sec.) treatment, e.g. using electrostriction, e.g. by use of Ba titanate, piezoelectric processes, magnetostriction, e.g. at 50-3000 watts/m.<SP>2</SP> and/or (c) by X-rays. Doping agents may be included to promote phase-transformation. These may be oxides of elements in a valency state differing from that of the cation(s) of the phase(s) to be produced by the transformation, e.g. Ti, Mn, Cu, Co, Cd, Ni, Al, Zr, Rb, Fe, Mg, Be, V, rare earths, and precious metals. These agents may, according to the treatment schedule, become associated with other components in complex phases in the final state of the film, or they may form distinct phases. To form the coating, at least one constituent may be applied to the surface, whether cool or still soft, by dipping, e.g. as a molten salt; by sprinkling powdered material on the softer surface; by contacting the body with the constituent in atomized or vapour form, e.g. by vacuum deposition or by sputtering. Other constituents can be applied simultaneously or subsequently by the same or different methods, e.g. sputtering with SiO and CaSiO 3 , followed by immersion in a suspension of AgCl+NaOH, which on thermal treatment at 550 C. yields a phototropic coating. The coating in its initial state may be amorphous, vitreous, or vitrocrystalline. In examples: (I) In glass drawing kiln 1 glass ribbon 8 is drawn upwards past cooler 15 with gas flames 18 and then past the discharge end of shoot 37 and similar symmetrically disposed apparatus, not shown, on the right-hand side of the drawing chamber. The shoot is cooled by water-jacket 38 and vibrated by electric vibrator 41. From the shoot, powder is discharged on the surface of ribbon 8, forming adherent coating 42. The coated ribbon then passes coolers 19 with flames 22<SP>1</SP>. The glass at meniscus 7 is at 920 C., and in tower section 12 it is cooled, the temperature at the upper end (not shown) being 80 C.; during this cooling the phase-transformation starts. The glass may be cut after storage for one hour at ambient temperature, and the phase-transformation continues at that temperature. The coating is 100 Ám. thick. The ribbon glass has composition, in wt. per cent: SiO 2 , 70; Na 2 O, 12; CaO, 10; MgO, 3; Fe 1 O 3 , traces; Al 2 O 3 , 5. The coating powder (10-50 Ám.) is of glass of composition ZnO, 60; B 2 O 3 , 20; SiO 2 , 10; P 2 O 5 , 6; Al 2 O 3 , 2; Na 2 O, 2; on phase-transformation this yields a vitreous phase of zinc borate and a vitreous phase of aluminium phosphosilicate. Other coating powders consist of the above glass mixed with (a) 1% TiO 2  (<20Ám.) and (b) 1% TiO 2  ( <20 Ám.) and 5% Al 2 O 3  (<30 Ám.). After phase-transformation there is, in addition to the above vitreous phases, (a) a crystalline TiO 2  phase; (b) a corundum-rich crystalline phase. (II) A " phase-separation " or " demixing " glass containing 5% P 2 O 5  and 95% SiO 2 +MeO, where Me is a cation, e.g. Ba. This is coated on a glass substrate and cooled, with resultant phaseseparation of the coating.