Anomalous water diffusion into SiO 2 glass was observed in a low temperature range, below~850°C, under a constant water vapor pressure of 355 Torr (47.3 kPa). Both the effective water diffusion coefficient and water solubility exhibited an anomalous time dependence. For example, water solubility in the low temperature range increased initially, achieving much higher values than expected based on extrapolation from higher temperature data, and then decreased with time toward an equilibrium value. This phenomenon was reported earlier, but a complete explanation was not possible; a new model is presented based upon glass surface compressive stress generation and subsequent surface stress relaxation. Water diffusion can promote stress generation and stress relaxation, both of which affect the reaction between diffused molecular water and the glass structure. By considering these stress effects, the anomalous water diffusion behavior in silica glass is explained. Furthermore, the same model can account for the reversal of external tensile and compressive stress effects on water solubility and diffusivity in silica glass observed after a few hours of heat treatment at 650°C in 355 Torr water vapor pressure. K E Y W O R D Sdiffusion/diffusivity, silica, solubility, stress relaxation

The retardance of silica glass fibers was evaluated using photoelastic techniques. Here, surface birefringence in glass fibers is shown to be a consequence of surface stress relaxation for as‐received fibers drawn from Suprasil II. The surface features of the birefringent fibers were compared to a model of the residual axial stress profile resulting from a diffusion‐controlled surface stress relaxation. Additionally, a uniform birefringence in the fiber equivalent to a constant tensile stress was recognized and attributed to structural anisotropy produced during fiber drawing. The contribution of structural anisotropy to the observed birefringence remained constant as the surface features were successively etched away. Surface compressive stress generation was also observed, as retardance corresponding to a surface compressive stress was found to increase with applied tensile stress during short heat treatments. Significant features of the retardance profile in as‐received silica glass fibers, with a thin surface compressive stress layer and compensating interior tensile stress, agreed with the residual stress profiles predicted by the surface stress relaxation model after correcting for this observed structural anisotropy.

A constant angle of twist was applied to silica glass rods in order to produce a torsional shear strain and a reduction in torque representative of the stress state in the glass was measured as a function of time when rods were heat-treated in air at temperatures, 550-700°C, far below the glass transition temperature. The monotonic decrease of torque with time was explained by surface stress relaxation, which can be described by a relaxation of stress at the surface of glass which is promoted by water. The obtained surface stress relaxation diffusion coefficients were consistent with those obtained earlier from silica glass fiber bending under a similar water vapor pressure. The observed relaxation in torsion supports the mechanism of surface stress relaxation over the swelling-based mechanism for applications including glass fiber strengthening.

A novel potassium phospho-aluminosilicate composition is described that can be strengthened by water vapor to achieve deep compressive stress (CS) profiles.Water vapor treatment at (A) 85 • C and 85% relative humidity for 40 days results in a CS of 389 ± 20 MPa and a compressive depth of layer (DOL) of 18 ± 2 μm. When treated at (B) 160 • C and 0.1 MPa for 7 days, a CS of 245 ± 20 MPa and a DOL of 40 ± 2 μm is achieved. Glasses with hydration-induced stress profiles can provide high retained strength following flaw introduction compared with ionexchanged soda-lime silicate glass. Sample treatment B also has an exemplary Vickers indentation cracking threshold value greater than 20 kgf. The hydration profile determined by secondary ion mass spectrometry (SIMS) is shown to closely match the stress profile for these samples. SIMS analysis also shows that the depth of water enrichment correlates well with the depletion depth of phosphorus. The high tendency towards water-induced strengthening for this new type of glass even enables self-strengthening by the generation of a near-surface CS profile following exposure to ambient conditions.

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