Stress Relaxation and Refractive Index Change of As2S3 in Compression Molding

As₂S₃ is one of the chalcogenide glasses that have attracted increasing interests for compression molding applications. This article aimed to evaluate the stress relaxation behavior of As₂S₃ above its glass transition temperature and calculate its refractive index change during cooling. First, creep tests were conducted with cylinder glass specimens at three different temperatures, in order to deduce the shear stress relaxation function by using the relationship with creep compliance function. In addition, the shift factor for thermo-rheological simplicity using Williams–Landel–Ferry equation was obtained. Then, finite element simulation was implemented to verify the calculated shear stress relaxation function. The acquired shear stress relaxation function needs to be modified to compensate the influence of friction on the thickness change in the experiments, so that the simulation results using the modified shear stress relaxation would match the experiments better. Finally, the refractive index changes of As₂S₃ at different cooling rates were modeled by using the Tool–Narayanaswamy–Moynihan (TNM) model for structural relaxation behavior. It is confirmed that the slower the cooling rate is, the less the refractive index drop will be. It was also demonstrated that the refractive index drop is strictly dependent on the cooling rate logarithmically by using TNM model. In summary, the results presented in this article can provide reliable references for viscoelastic characterization of As₂S₃ glass, crucial for compression molding or similar applications.     

Finite Element Calculation of Refractive Index in Optical Glass Undergoing Viscous Relaxation and Analysis of the Effects of Cooling Rate and Material Properties

In this research, a methodology based on a numerical simulation model is presented to predict refractive index change introduced to two low T_g optical glasses, namely, P-SK57 and P-LASF47, by cooling. To model the structural relaxation behavior of glass around glass transition temperature, the Tool–Narayanaswamy–Moynihan (TNM) model is used. In addition, the fictive temperature of the glass samples during cooling is discussed. The effect of cooling rate on the fictive temperature of the glass samples is also presented. This study demonstrated that finite element method is capable of predicting refractive index of optical glass undergoing viscous relaxation. The simulated results in this study confirm that a higher cooling rate leads to a lower refractive index and a larger variation of refractive index in glass optics. The results also suggest that for glass, materials with high thermal conductivity and low heat capacity are preferred for compression molding process.     

Glass Formation and Properties in the System Calcia-Gallia-Germania

The critical cooling rate for glass formation, R^c, was measured for four compositions in the system calcia-gallia-germania. The activation energy, E, and frequency factor, u, for the crystallization process were determined by reheating the glasses at varied constant heating rates and measuring the temperature of crystallization. Both E and v increased, with increasing germania content of the glass, whereas R^c decreased. The density, refractive index, and Abbe number were also measured; all decreased with increasing GeO² content. These results are compared with those for calcia-gallia-silica glasses of comparable compositions.     

Heat Capacity and Structural Relaxation of Enthalpy in As2Se3 Glass

The evolution of enthalpy of As₂Se₃ glass during structural relaxation in the glass transition region was measured via differential scanning calorimetry for two types of time-temperature programs: rate-heating at 10 K/min following a cool at a constant rate (-20 to -0.31 K/min) and isothermal annealing following a temperature step from an equilibrium state. The rate-heating data yield kinetic parameters for the structural relaxation which predict accurately the evolution of the enthalpy during isothermal annealing. The glass heat capacities were independent of cooling rate within experimental precision (≤0.2%). In this respect, As₂Se₃ is unlike previously studied glasses whose heat capacities are more dependent on thermal history.     

High-precision molding simulation prediction of glass lens profile for a new lanthanide optical glass

Precision glass lens molding (PGLM) is a recently developed method for fabricating glass optical components with high precision in large volumes. Lanthanum optical glasses are extensively used as optical materials owing to their superior optical properties, such as high refractive index, low dispersion, and high transparency. However, the transformation temperature of currently available high refractive index glass is generally above 650 °C and poses a challenge in manufacturing ultra-hard molds, durable coatings, and high-temperature molding equipment using PGLM. In this study, a preparation method for obtaining high refractive index, low -melting -point lanthanide optical glass (B-ZLaT198) used in PGLM was developed to reduce the transformation temperature. The developed method also characterizes the glass refractive indices and thermal-mechanical properties. To achieve the high-precision prediction of a molding shape in a simulation, a viscoelastic constitutive model of glass was established based on a micro-deformation uniaxial compression creep test. Moreover, by solving the Tool-Narayanasway-Moynihan model parameters based on the specific heat capacity fitting of optical glass at different heating and cooling rates, the input parameters of the structural relaxation model (SRM) for simulation prediction of aspheric glass lens profile deviation in the annealing stage were obtained. Finally, the profile deviation of the aspheric lens was predicted using a finite element model simulation. The results showed that the simulation’s predicted profile of an aspheric lens using the SRM model was in good agreement with that of experimental molding profile. In addition, using the SRM provided a higher prediction accuracy than that of the thermal expansion model in the annealing stage. Adopting the SRM was necessary for the annealing simulations of molding pressing and also verified the accuracy of the proposed viscoelastic characterization method for calculating the thermomechanical parameters of optical glasses.     

Thermooptic Coefficients of Some Standard Reference Material Glasses

The thermooptic coefficients, i.e., the change in refractive index with temperature (d n /d T ), of four National Institute of Standards and Technology standard reference material (SRM) glasses have been measured over the range of 25° to 125°C. The thermooptic coefficients of all four glasses, NBS-710 (a soda-lime silicate), SRM-711 (a lead silicate), SRM-717 (a borosilicate), and SRM-739 (silica) are positive and range in value from 2 × 10⁻⁶/K to 9.8 × 10⁻⁶/K. The differences in the d n /d T of these glasses arise from differences in the coefficient of thermal expansion and the temperature coefficient of the electronic polarizability.     

Is the structural relaxation of glasses controlled by equilibrium shear viscosity?

Knowledge of relaxation processes is fundamental in glass science and technology because relaxation is intrinsically related to vitrification, tempering as well as to annealing and several applications of glasses. However, there are conflicting reports—summarized here for different glasses—on whether the structural relaxation time of glass can be calculated using the Maxwell equation, which relates relaxation time with shear viscosity and shear modulus. Hence, this study aimed to verify whether these two relaxation times are comparable. The structural relaxation kinetics of a lead metasilicate glass were studied by measuring the refractive index variation over time at temperatures between 5 and 25 K below the fictive temperature, which was initially set 5 K below the glass-transition temperature. Equilibrium shear viscosity was measured above and below the glass-transition range, expanding the current knowledge by one order of magnitude. The Kohlrausch equation described very well the experimental structural relaxation kinetics throughout the investigated temperature range and the Kohlrausch exponent increased with temperature, in agreement with studies on other glasses. The experimental average structural relaxation times were much longer than the values computed from isostructural viscosity, as expected. Still, they were less than one order of magnitude higher than the average relaxation time computed through the Maxwell equation, which relies on equilibrium shear viscosity. Thus, these results demonstrate that the structural relaxation process is not controlled by isostructural viscosity and that equilibrium shear viscosity only provides a lower boundary for structural relaxation kinetics.     

Effect of Thermal History on Glass Expansion Characteristics

Thermal expansion data are presented for two glasses for both heating and cooling at constant rates. Heating data were taken on samples with varying thermal histories brought about by either constant-rate cooling or by constant-temperature stabilization before the expansion test. The fictive temperature concept is discussed in regard to these data. Expansion data are correlated with density and refractive index at room temperature for a variety of heat-treatments.     

Dependence of the Fictive Temperature of Glass on Cooling Rate

An equation derived by Ritland relating the cooling rate and fictive temperature for glasses without memory is extended to those with memory, i.e. those which exhibit a spectrum of relaxation times. Provided that the spectrum of relaxation times is temperature-independent, the limiting fictive temperature, T'_f , obtained when a glass is cooled through the transition region, is shown to be related to the cooling rate, q , by d In | q |/ d (1/ T'f )=-Δ h ★/ R
where R is the ideal gas constant and Δ h ★ the activation enthalpy for the relaxation times controlling the structural relaxation. Values of T'_f vs q obtained from enthalpy measurements by differential scanning calorimetry are presented for B₂O₃, 0.4Ca(NO₃)₂—0.6KNO₃, and borosilicate crown glasses; Δ h ★ is equal, within experimental error, to the activation enthalpy for shear viscosity. Values of T'_f from volume and enthalpy measurements obtained at the same cooling rate for the borosilicate crown glass are equal.     

Photosensitivity of barium germano-gallate glasses under femtosecond laser direct writing for Mid-IR applications

Barium germano-gallate glasses are attractive glass hosts for photonic applications in the mid-infrared region up to 6 μm. In this work, we investigate the photosensitivity of such glasses under femtosecond laser, with an emphasize on the formation of refractive index changes. Six glasses with varying compositions (including addition of K, Na, Y, and La) were studied. We observed several transformation regimes in the pulse energy – repetition rate landscape: Type I (isotropic refractive index change) and a spatial broadening regime with a phase shift Δϕ > 2π rad at 550 nm. This translates into refractive index changes Δn > 10⁻² and is comparable to values obtained in most chalcogenide glasses. The effect of glass composition on Δϕ appears correlated to the number of non-bridging oxygen presented in the glass and is brought to evidence by monitoring the Cations/GaO_3/2 ratio. This provides a way to design a range of germano-gallate glasses suitable to imprinting high refractive index contrast.     

Structural relaxation dynamics of a silicate glass probed by refractive index and ionic conductivity

Relaxation occurs spontaneously in all glasses and is a fundamental step of important technological processes, such as annealing, crystal nucleation, and chemical strengthening by ion exchange. Despite extensive studies over the past decades, there are still conflicting results on whether the kinetics of structural relaxation depends on the analyzed property. Thus, in this study, we used a lithium disilicate glass as a model composition to determine the structural relaxation kinetics during physical aging experiments by measuring the time evolution of the refractive index and ionic conductivity down to 35 K below the initial fictive temperature. In all cases, variations in these properties were adequate to capture the structural changes throughout the aging experiments. At each temperature, the experimental relaxation data fit quite well with the classical stretched exponential relation. We also found that the relaxation process starts faster when probed by ionic conductivity than by refractive index; however, they show similar average relaxation times. These very small structural rearrangements are always the same, but ionic conductivity changes faster than refractive index at the beginning of the process. Our comprehensive results strongly indicate that relaxation dynamics is indeed dependent on the analyzed property.     

Influence of plasticizers and cryogenic grinding on the high‐cooling‐rate solidification behavior of PBT/PET blends

Two structurally different plasticizers (cyclic and linear) and the effect of cryogenic grinding on the solidification behavior at high cooling rates by a continuous cooling transformation approach of poly(butylene terephthalate)/poly(ethylene terephthalate), PBT/PET, blends are described. The solidification curve (density versus cooling rate) is confirmed as an effective tool to compare the differences in crystallization behavior under conditions mimicking processing. In comparison to the bulky cyclic plasticizer, the linear oligomeric one was found to have a more pronounced influence on the crystallization behavior. A 60/40 by weight PBT/PET blend shows a drop‐off of density at ～50 K/s. In the plasticized sample, the long‐range crystalline order appears up to a cooling rate of ～250K/s, making the blend comparable to pure PBT. Grinding the components before blending further improves crystallizability and synergy to the addition of the plasticizer. The results suggest the important role of local chain mobility in the solidification behavior at high cooling rates. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43083.     

Optical properties,thermal stability,and forming region of high refractive index La2O3–TiO2–Nb2O5 glasses

The high refractive index La₂O₃–TiO₂–Nb₂O₅ glasses were prepared by containerless processing, and the glass‐forming region was determined. The refractive index showed the range from 2.20 to 2.32, and the values were much higher than those of most optical glasses. The completely miscible 30LaO_3/2–(70?x)TiO₂–xNbO_5/2 (0 ≤ x ≤70) system was fabricated to study the compositional dependence of refractive index and optical transmittance. The crucial determinants of the refractive index of oxide glasses, oxygen molar volume, and electronic polarizability of oxygen ions were calculated. The principle of additivity of glass properties was suitable for the calculation of refractive index between glass and compositional oxides. All the glasses were colorless and transparent in the visible to 6.5 μm middle infrared (MIR) region. These results are useful for designing new optical glasses with high refractive index and low wavelength dispersion in wide optical window.     

Enthalpy and Anisotropy Relaxation of Glass Fibers

Optical birefringence and calorimetric studies have been conducted with respect to structural relaxation of E-glass (a type of calcium–alumosilicate glass system) fibers. Upon fiber drawing, the liquid of E-glass is thermally hyperquenched and mechanically stretched. Hyperquenching (cooling rate >10⁶ K/min) leads to higher enthalpy state of liquids, and thereby, to a higher fictive temperature than normal quenching (20 K/min), whereas stretching results in structural anisotropy of glasses, i.e., a certain degree of preferred structural orientation (stretched network) along the axial direction of the fibers, which is quantified by the optical birefringence. Simultaneous relaxation of both anisotropy and excess enthalpy (relative to the enthalpy of a glass cooled at the standard rate of 20 K/min) upon static annealing and dynamic heating is observed, both of which can be described using the Kohlrausch function. However, there is a striking difference between the birefringence and the excess enthalpy relaxations. The birefringence decays much faster than does the excess enthalpy during annealing. These observations imply that the birefringence decay results from fast relaxation of the local structure, while the enthalpy relaxation results from slow relaxation of larger domains of the network.     

Refractive-Index Dispersion of Tellurite Glasses in the Region from 0.40 to 1.71 μm

The refractive index of binary tellurite glasses with various modifiers was measured down to the fifth decimal place in the wavelength range of 0.40–1.71 μm using the minimumedeviation method. An empirical equation based on the single-oscillator Drude–Voigt dispersion equation. n _d²= A·Nf λ₀²+ B , is obtained, where n _d is the refractive index at 0.5876 μm, N is the number of molecules in a unit volume, f is the average oscillator strength, λ₀ is the average resonance wavelength, and A and B are constants. The refractive index n _d of tellurite glasses is substantially determined by the resonance wavelength at the ultraviolet region, which is affected by the main constituent, TeO₂.     

Glass formation in the LiF-ZnSO<Subscript>4</Subscript> system

The glass-forming ability is investigated in the LiF-ZnSO₄ binary system. It is found that, upon cooling melts at a rate of 10³ K/s, the glass formation is observed in the concentration range 30–60 mol % ZnSO₄. The characteristic temperatures are determined using differential thermal analysis. The density of glasses is measured by hydrostatic weighing. The experimental results obtained are used to calculate the molar volumes and the thermal stability parameters of lithium-containing fluorosulfate glasses.Original Russian Text Copyright © 2005 by Fizika i Khimiya Stekla, Nepomiluev, Reznitskikh.     

GexAs20Se80-x玻璃的化学组成对结构和物理性质的影响

本文制备了一系列Ge_xAs₂₀Se_80-x硫系玻璃,旨在了解化学组成和平均配位数对其结构和物理性质的影响。采用棱镜耦合法测量玻璃的折射率,采用分光光度法测量玻璃透射率并根据透射谱得到玻璃的光学带隙。研究发现,当玻璃组成满足完全化学计量配比之前,随着Ge含量的增加,玻璃的折射率随之减小,而光学带隙随之增大。通过测量拉曼光谱并对其进行分解,发现随着玻璃化学组成的改变,其结构中异极键相对数量的变化是合理的;而同极键的数量则与光学带隙和折射率的变化密切相关,主要是由于同极键形成的带尾可以降低玻璃的光学带隙。另一方面,玻璃的各个结构单元及物理性质在满足完全化学计量配比的玻璃组成上出现转变行为,由此可以断定,Ge_xAs₂₀Se_80-x硫系玻璃的化学组成主导着其结构和物理性质。     

Influence of pressure on the refractive index and relative density of glasses in the CaO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript> system

The pressure dependences of the refractive index for aluminosilicate glasses of the compositions 0.167CaO · 0.167Al₂O₃ · 0.666SiO₂ and 0.157CaO · 0.177Al₂O₃ · 0.666SiO₂ at pressures up to 6.0 GPa are determined using a polarizing interference microscope and an apparatus with diamond anvils. The compressibilities of the glasses are calculated from the measured refractive indices within the framework of the theory of photoelasticity. The structural-chemical parameters NBO/T (where NBO is the number of gram-ions of nonbridging oxygen atoms and T is the total number of gram-ions of network formers) are calculated for the glasses under investigation with allowance made for the formation of triclusters and highly coordinated aluminum.     

Heats of Solution, Density, and Refractive Index Changes in Sodium Borate Glasses Subjected to High Pressure

The densification produced in sodium borate glasses by pressures to 40 kbars at 25° and 250°C was measured. At a constant temperature and pressure, the densification decreased with increasing alkali content. For specimens pressed at 40 kbars and 250°C, the densification ranged from 14.2% for B₂O₃ to 6.3% for the 33.3 mole % Na₂O composition. Under the same conditions, the refractive index increase ranged from 4.8 to 1.1%, and the decrease of the molar refraction of the oxygen ions ranged from 2.5 to 1.5%. The heats of solution of the pressed glasses were more negative than those of the corresponding unpressed glasses. The heats of solution of both the pressed and unpressed glasses pass through a minimum near 20 mole % Na₂O. A decrease in density was observed at room temperature for all pressed specimens. Electron micrographs were made of two of the pressed specimens. The results could be explained on the basis of a repacking of structural units.     

7Li Nuclear Magnetic Resonance in (7Li,6Li) and (Li, Na) Triborate Glasses

Spin-lattice relaxation times for ⁷Li were measured as a function of temperature in two mixed-isotope (⁷Li,⁶Li) triborate glasses and one mixed-alkali (Li, Na) triborate glass. The rapid increase in relaxation rate above 400 K is believed to result from localized alkali motion. A mixed-alkali effect was observed for such a motion, but it is shown not to be a mass effect.