Glass microstructure evaluations using high temperature mechanical spectroscopy measurements

This paper compares the microstructures of several glasses by measuring the Young’s modulus and internal friction as a function of temperature, using the impulse excitation technique (IET). IET is based on the analysis of the resonant vibration of a solid material sample, induced by an impulse excitation. IET determines the mechanical resonant frequencies (f_r) from which the elastic moduli can be calculated, and for each f_r the corresponding internal friction (Q⁻¹). It was found that the stiffness of quartz and borosilicate glasses increases with temperature. The stiffness of soda-lime and alumino-silicate glasses decreases with the increase of temperature. The change of stiffness of quartz and alumino-silicate glasses during heat-treatment is reversible, but that of borosilicate and soda-lime glasses is not. Explanations for the irreversibility are suggested based on the Q⁻¹-features of the glasses. Diffusion of network modifier ions in the glass network holes is proposed to cause a non-reversible stiffness change, whereas localised anelastic relaxation of network modifier ions leads to a reversible stiffness change.     

Crack bridging mechanism for glass strengthening by organosilane water-based coatings

We used an epoxysilane/aminosilane coating deposited from an aqueous solution to strengthen flat glass. We studied film formation, interfacial and mechanical properties of the film. The film is highly cross-linked with a 6 GPa Young’s modulus and good adhesion. Our results suggest that crack face bridging accounts for most of the 75% reinforcement in this system.     

Epoxy based coatings on glass: strengthening mechanisms

Glass may be strengthened by epoxy coatings although the strengthening mechanisms remain unclear. Possible strengthening mechanisms are reviewed and are used to analyse strength data for both a solvent based and a water based coating system. The coatings either fill (solvent based coatings), or partially fill (water based coatings) surface cracks and it is shown that closure stresses arising from the thermal expansion mismatch of the coating within these cracks can account for the observed degrees of strengthening. It is also demonstrated that other suggested mechanisms such as flaw healing cannot fully account for the observed degree of strengthening.     

Photosensitive erbium doped tin-silicate glass

Erbium doped tin-silicate samples were prepared by sol-gel method. Optical absorption, infrared photoluminescence at 1.5 μm from ⁴I_13/2-⁴I_15/2 Er³⁺ electronic transition and data of refractive index change after exposure to 266 nm pulsed radiation were collected. The results show that Er-doped tin-silicate can be produced by the proposed sol-gel method with photosensitivity comparable to that of only tin-doped silica, showing refractive index changes up to 4×10⁻⁴.     

Ion exchange equilibria between glass and molten salts

It is shown that interaction between the ions undergoing ion exchange leads to a sigmoidal equilibrium curve. A negative interaction in the glass causes the ratio of concentration of the two ions to be more nearly equal to unity in the glass than it is in the molten salt. It is further shown that the Rothmund-Kornfeld parameter is a measure of the non-ideality of the system. A value of the parameter greater than unity indicates a negative interaction energy.     

Critical parameters in the processing of engineered stress profile glasses

A new approach to chemical strengthening is to move the maximum residual compression below the glass surface. With appropriate processing, this approach leads to strengthening and a decrease in the strength variability. This improvement in mechanical reliability is accomplished by introducing stable crack growth into the glass, which leads to multiple cracking of the glass surface prior to failure. In the current study, a fracture mechanics analysis is presented that uses a simple form for the stress profile. By determining the effect of this stress profile on the apparent fracture toughness of the material, it is possible to identify the conditions when spontaneous cracking occurs, the stress for the onset of multiple cracking and the ultimate strength of the glass. In particular, it is shown there is an important interplay between the depth of the maximum compression, the stress gradient and the magnitude of the maximum compressive stress. The current analysis is then used to define a strategy for the processing of glasses with engineered stress profiles.     

Atomistic understanding of the network dilation anomaly in ion-exchanged glass

Chemically strengthened glasses are of increasing technological importance for personal electronic devices, tablet computers, and a variety of other applications. However, there are many unexplained phenomena associated with the physics of the ion exchange process used for strengthening. One of the most puzzling of these is the anomalous behavior of the network dilation coefficient, i.e., the parameter governing the amount of linear strain of the glass per unit of alkali ions exchanged, which is inevitably a factor of 2–4 higher for as-melted glasses as compared to chemically strengthened versions of the same glass compositions prepared via ion exchange. In this paper, we investigate the atomistic origin of this discrepancy between as-melted and ion-exchanged glasses based on molecular dynamics simulations of a series of alkali tetrasilicate glasses, viz., xNa₂O·(20 ? x)K₂O·80SiO₂ (mol%). The network dilation coefficient of the ion-exchanged glasses is dependent on composition and ranges from 30% to 54% of the ideal value obtained from the as-melted glasses. This anomalous behavior of the network dilation coefficient is explained in terms of different local environments between sodium and potassium sites in the glass network and a two-stage relaxation process of the local potassium environment after ion exchange.     

Water diffusion into a silica glass optical fiber

The diffusion coefficient and solubility of water in silica glass optical fiber cladding were measured in the temperature range of 600-800 °C and were compared with the corresponding values of bulk silica glasses. It was found that the diffusion coefficient was slightly lower and the solubility was appreciably higher in optical fiber, especially at low temperatures, compared with those in bulk silica glasses. The observed trend was consistent with the expected effect of fictive temperature.     

The effect of photo-irradiation in hydrolysis and condensation of silicon alkoxide

A silicon alkoxide-water-ethanol mixed solution was irradiated with ultraviolet rays, and the change of the silicon alkoxide molecular structure was evaluated by ²⁹Si nuclear magnetic resonance and Fourier transform infrared spectroscopies. Silicon alkoxide was hydrolyzed and the Si-OH bonds were produced by UV irradiation without any chemical catalyst for hydrolysis. The Si-O-Si bonds were also produced, and viscosity of the alkoxide solution became higher due to condensation of alkoxide.     

Optical basicity, interpreted by means of Ce 5d level spectroscopy in ionic crystals

The concept of optical basicity based on spectroscopy of Tl⁺, Pb²⁺, and Bi³⁺ energy levels in oxidic media like glasses and molten salts will be tested against information and theoretical knowledge available on Ce³⁺ in oxide ionic crystals. The redshift of the 4f → 5d transition of Ce³⁺ does not provide a basis for determining optical basicity. It will be shown that the proper basis is provided by the shift of the whole 5d configuration. Reasons why optical basicity can be based on the redshift of the ¹S₀ → ³P₁ transition in Tl⁺, Pb²⁺, and Bi³⁺ will be discussed. The theory on the centroid shift in Ce³⁺ provides new insights in the relation between optical basicity and physical properties like anion polarizability and refractive index. An alternative method to calculate optical basicity from the chemical composition of a compound will be proposed both for oxide and fluoride compounds.     

Precipitation of silver particles by femtosecond laser pulses inside silver ion doped glass

We report on photosensitivities in silver ion doped glasses. We succeeded in precipitation control of silver particles without heat treatment by the irradiation of femtosecond laser pulses. The silver particles can be precipitated in a given location. Therefore it is possible to process a three-dimensional structure. This result should be applicable to functional optical devices.     

Colloidal silver formation at the surface of float glass

The formation of colloidal silver during the heating in air of silver films on float glass has been observed. The presence of colloidal silver gives to a yellow color and an absorption band centered at 400–420 nm. The results of this study indicate that the formation of colloidal silver is strongly dependent upon the concentration of stannous tin in the glass. The optical density of the absorption band induced in the glass is much greater for samples silvered on the tin-rich face of the glass and varies with the thermal history of the sample. Removal of the outer few micrometers of the glass surface results in a radical change in the amount of colloidal silver formed. Silver colloids are formed only if the sample is heated in an atmosphere containing oxygen, suggesting that the silver must be ionized before it will diffuse into the glass. The colloid formation process has an activation energy of approximately 30 kcal/mol, which is very near that reported for silver-sodium interdiffusion in similar glasses.     

The field-assisted penetration of a silver film into glass

The application of a DC field to a sodium-containing glass plate coated with a silver film causes Ag⁺ and Na⁺ ions to move toward the cathode, retaining the transparency of the glass. Characteristics of the process have been experimentally studied from various viewpoints: current and voltage versus time, fluorescence generation/annihilation, refractive index increase, spectral reflectivity characteristics, internal strain generation, volume increase, the weight of penetrated silver versus transported electric charge and concentration profiles. The dynamics of the process have been shown to be approximately linear. The linearity is considered to come from the following: (1) the resistance of a Ag-penetrated layer is much smaller than that of the whole of a glass plate and (2) Na⁺ ions are not piled up in the vicinity of the cathode-side surface.     

Optical and lasing properties of fluorophosphate glass

Neodymium-doped fluorophosphate glass is a laser material newly-developed for use in high power laser fusion systems. The low refractive index (n_d ～ 1.45) and low dispersion (Abbe number ～90) of fluorophosphate glasses give them the properties of low nonlinear refractive indices and long Nd³⁺ fluorescence lifetimes, which are desirable for the high power laser applications. We have measured the intensity gain of 1.052 and 1.064 nm laser light produced by flashlamp-pumped fluorophosphate glass amplifiers, varying in size from 4–34 clear aperture. The measured gains are compared with those measured in other laser glass types and with those predicted from the spectroscopic properties of Nd³⁺. We estimate that the peak cross section for the ${}^4\text{F}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{→}{}^4\text{I}{}_{\mathrm{<mtext>11</mtext><mtext>12</mtext>}}$ transition in commercial fluorophosphate laser glasses is ～2.2 × 10^?20 cm².     

A square-wave voltammetric study on the diffusivities of polyvalent elements in CaO/BaO/Al2O3/SiO2 glass melts

Diffusion coefficients of various polyvalent ions (Sn²⁺, As³⁺, As⁵⁺, Sb³⁺, Sb⁵⁺, Cr³⁺, Ti⁴⁺, V⁴⁺, V⁵⁺ and Fe³⁺) were measured in melts with the basic compositions of 10CaO·10 BaO·10Al₂O₃·70SiO₂ and 10CaO·10BaO·15Al₂O₃·65SiO₂ by means of square-wave voltammetry. At temperatures in the range of 1300-1600 °C, linear correlations between logD and 1/T were observed. At 1400 °C, the diffusion coefficients obtained are compared with those obtained from other glass melt compositions.     

The refractive index distribution of Tl+–Na+ ion-exchanged glass waveguide optical splitter in branch district

The buried waveguide optical splitter is fabricated by Tl⁺–Na⁺ ion-exchange technology on BK7 glass substrates, and the refractive index distribution in branch district is analyzed by the interference method technology. The shape of the same refractive index distribution of the six successive different points in branch district is changed little by little from a semicircle to a half ellipse gradually, and finally separates into two semicircles. We also compare the experiment data by the interference method with the mathematical solution by two-dimensional diffusion equation. And the refractive index distribution is the ‘improved’ Gauss function.     

Structural investigation of sodium borate glasses and melts by Raman spectroscopy. III. Relation between the rearrangement of super-structures and the properties of glass

The structure of the intermediate range order (IRO) of sodium borate glasses and melts were quantitatively investigated by the analysis of high-temperature Raman scattering spectra. Raman bands at the middle frequency region of 700-950 cm⁻¹ were normalized using the bands at high frequency spectra and their intensities were compared among the spectra collected from the melts with different composition at various temperature. Bands at 805, 780, 750 and 720 cm⁻¹ were focused and their intensity changes were quantified. The exceeds of temperature over the glass transition temperature did not necessarily cause the decrease of all the band intensities. At Na₂O<15 mol%, 805 cm⁻¹ band was the most sensitive to temperature, while at 15<Na₂O<30, it was switched to 780 cm⁻¹ band and 805 cm⁻¹ band became insensitive. When Na₂O concentration exceeded 30 mol%, 750 and 720 cm⁻¹ bands were decreased with temperature. Accompanying the previous analysis on the structures of short range-order (SRO) of boron atoms [J. Non-Cryst. Solids, in this issue], some models of the structural rearrangement along with temperature were proposed. The combination of the obtained structural informations of IRO and SRO was found to explain the mechanisms causing various characteristic properties of borate glasses and melts, especially immiscibility and boron oxide anomaly of thermal expansion coefficient from the microscopic and dynamic points of view of the vitrification process in melt.     

Stress relaxation of a soda lime silicate glass below the glass transition temperature

Stress relaxation is an important effect in the ion-exchange procedure of glasses, as it controls the stress profile and the strength. Creep and stress relaxation tests have been performed to study the viscoelastic behavior of soda-lime silicate glass at typical ion-exchange temperatures. The experimental data of these tests can be fitted well by the Burger model and a comparison between the viscosity data from both tests was made. The strain and temperature dependences of the stress relaxation process were studied and the glass exhibited a non-linear viscoelastic behavior and an anomalous temperature dependence. In addition, it was found there is a relationship between the glass density and the stress relaxation behavior.