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.     

Study on shape deviation and crack of ultra-thin glass molding process for curved surface

The demands towards high precision and surface quality of ultra-thin glass for curved screens are continuously rising in the field of smart mobile terminals. Although the ultra-thin glass molding process (UTGMP) has the advantage of the shorter production cycle and higher efficiency, there are still typical forming defects in the molding process, namely crack, shape deviation, and large surface roughness. This paper aimed to investigate the influence mechanism of UTGMP molding temperature and pressure on the shape deviation, crack area, and surface quality of ultra-thin glass. In this study, a finite element model (FEM) was established to study typical forming defects of curved surfaces, and the effects of molding temperature and pressure on the shape deviation and crack area for ultra-thin glass were studied by the FEM simulation method. The simulation results revealed the molding temperature has a significant effect on the shape deviation, crack area and surface quality, while the molding pressure is only strongly correlated with shape deviation and crack area. In addition, the reliability of the model was verified by a series of five-level single factor experiments, and the shape deviation and crack area of ultra-thin glass were discussed in detail. Under the appropriate molding pressure and temperature range (0.45 MPa, 802–806 °C), the accuracy of curvature was improved by 33%, the roughness was reduced by 21%, and the probability of crack was also reduced. Thus, this study contributes to improving UTGMP's molding accuracy and reducing molding defects, and plays a positive role in reducing production costs and improving production efficiency.     

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.     

Creep and relaxation behavior of woven glass/epoxy substrates for multilayer circuit board applications

The creep behavior of a common woven glass/epoxy composite substrate for multilayer circuit board applications was characterized using dynamic mechanical analysis (DMA). The creep compliance was measured in both the warp and fill directions of the composite over a temperature range of 30°C to 155°C. The creep compliance of the neat FR-4 epoxy matrix was also characterized for comparison with the composite response. Master creep curves were obtained for the neat resin and the composite in the warp and fill directions assuming thermorheologically simple behavior and applying the time-temperature superposition principle. The creep data was fit to a Prony series and then converted to relaxation data in the Laplace domain. Micromechanical models were developed to predict the relaxation behavior of the woven glass/epoxy composite from the elastic properties and the geometry of the glass fabric and relaxation behavior of the neat resin. Model predictions were compared with experimental data.     

Preparation of transparent Bi2O3-ZnO-B2O3 glass by conventional sintering at low temperatures

Glass components fabricated by the sintering route have wide-ranging applications. However, one issue is that the crystallization tendency of glass powders often leads to residual pore-glass interfaces and crystal-glass interfaces, thereby causing strong light scattering and rendering the sintered glass opaque. This issue is particularly pronounced in glasses with a low glass transition temperature (T_g) due to their weak bonding and thus high crystallization tendency. In the present study, a Bi₂O₃-ZnO-B₂O₃ glass with a low T_g of 364°C was fabricated using the conventional sintering method to explore whether transparent glass materials can be obtained. The temperature range of crystallization of the glass powders was analyzed using differential scanning calorimetry. X-ray diffraction was employed to analyze the crystalline phases formed in the sintered glasses. The microstructure of the sintered glasses was examined using scanning electron microscopy. The optical transmittance of the sintered glasses was measured using ultraviolet-visible spectroscopy. The results show that transparent sintered glasses with the highest transmittance of 54% at the wavelength of 650 nm can be obtained by using a coarser initial particle size, lower forming pressure, and an appropriate sintering temperature/time (430°C/30 min). It is suggested that this combination of processing parameters can suppress glass crystallization while maintaining a low glass viscosity during sintering.     

A comprehensive study on frictional dependence and predictive accuracy of viscoelastic model for optical glass using compression creep test

Compression creep tests (CCTs) have been widely used in phenomenological characterization of viscoelastic materials such as glasses. However, disturbed by specimen-tool interface friction, the real stress-strain data regarding the pure viscoelastic deformation are frequently misestimated in conventional CCTs, causing decreased accuracies of the derived viscoelastic parameters. This study proposes a comprehensive CCT-based approach to develop a viscoelastic model with weakened frictional disturbance and enhanced predictive accuracy. An integrated calculation procedure is first built to mathematically characterize the frictional and viscoelastic behaviors of glass during compression. Uniaxial CCTs of a typical borosilicate glass (L-BAL42) are then performed at varied frictional conditions. The quantified coefficients of interface friction indicate that a minor frictional disturbance is achieved when Nickel foils are used as interfacial layers, whereby a more realistic viscoelastic constitutive relation of the glass is derived. The obtained frictional and viscoelastic constants are further incorporated into computational modeling of the CCT and precision molding processes. The demonstrated consistencies between the simulated and measured results (creep displacement and molding force) suggest that, by technically slashing the interface friction and theoretically correcting the friction-involved stress in CCTs, the frictional disturbance to experimental stress-strain data can be effectively weakened, and a viscoelastic model of enhanced predictive accuracy can be thus developed.     

Volume relaxation in a borosilicate glass hot compressed by three different methods

The temperature dependence of glass relaxation has been intensively studied; however, the effect of an imposed pressure history on relaxation behavior is poorly understood. In this study, we subjected SCHOTT N-BK7^® borosilicate glasses to isostatic compression in a Paterson press (PP) and a gas pressure chamber (GPC). The pressure ranged from 0.1 GPa to 2 GPa for various dwell temperatures and times near the glass transition region. Comparison with our recent results on the same glass using the piston-cylinder apparatus (PC, 0.5-1.5 GPa) reveals that the density of a glass, which has been quenched from the equilibrium state under high pressure at 2 K/min (pressure quench), increases approximately linearly with increasing pressure up to 2 GPa. Considering the volume recovery results at ambient pressure, we assert that the preceding high-pressure treatment in PC (uniaxial loading) generates a similar isostatic pressure effect on N-BK7 glass as those of PP and GPC treatments. Finally, we verify the previously proposed two-internal-parameter relaxation model on the volume recovery data using the three different compression methods. With a new set of parameters in the model, we can account for the pressure and temperature dependence of volume relaxation even for the samples quenched from nonequilibrium states at high pressure.     

The effect of glass composition on the reactivity of synthetic glasses

The reactivity of synthetic glasses depends on their chemical compositions. In far from equilibrium dissolution experiments, the reactivity of Ca‐rich glasses with compositions similar to blast‐furnace slag is found to be much higher (up to ~60 wt.% after 7 days) compared to Si‐rich glasses with compositions similar to type F fly ash (up to ~20 wt.% after 7 days). Isothermal calorimetry and TGA experiments conducted on model systems containing portlandite and calcite and on glass‐blended Portland cement confirmed the higher reactivity of the Ca‐rich glasses. The degree of glass reaction after 91 days ranged from 7 to 20 wt.%. The results showed also a higher reactivity of the glasses containing more aluminum (both for Ca‐rich and Si‐rich glasses) indicating that not only calcium but also aluminum acted rather as network modifier than as network former. The results confirm a strong dependence of the glass reactivity on the degree of polymerization of the glass network.     

Mechanical characterization of epoxy moulding compound in pressurized steam

Epoxy Molding Compounds (EMCs), commonly based on epoxy resin, are used widely for encapsulation of chips in electronic devices for protection against mechanical, environmental, and chemical attack. The thermo-mechanical properties of these compounds are important for the assessment of package reliability. These properties are highly dependent on the temperature and moisture.EMCs absorb water when exposed to a humid environment. The trapped water generates steam in the compounds during the soldering reflow part of the packaging assembly process, which may drastically change the viscoelastic and adhesion behavior of the compound.The present research focuses on the characterization of mechanical properties of an epoxy molding compound in steam at elevated pressure (temperature above 100 °C and relative humidity equal to 100%). A special steam chamber with a highly accurate tensile setup for force and displacement measurements is designed and manufactured. The chamber is equipped with a 3 Point Bending (3PB) loading setup. The setup can also be modified to mixed mode bending for investigating the effect of temperature and steam on the molding compound-to-lead frame interface strength.In this paper, the viscoelastic creep compliance of a molding compound in dry and wet environment is measured in 3 point bending mode. It is shown that steam significantly affects the thermo-mechanical properties of the molding compound. The glassy and rubbery modulus of the molding compound were seen to decrease almost by 20%. Furthermore the glass transition temperature decreased by about 30 °C and the creep process was seen to be about a factor 40 faster in a hot steam environment.     

Transition in deformation mechanism of aluminosilicate glass at high pressure and room temperature

Deformation experiments for 20(MgO or Na₂O)-20Al₂O₃-60SiO₂ glasses were performed in simple shear geometry at 1.5-5 GPa and room temperature. An abrupt change in the thinning rate and the turning of the birefringence azimuth at a shear strain of γ = 1-2 indicate a transition of deformation mechanism from uniaxial compression aided by densification to shear flow in the glasses. The high-dense magnesium aluminosilicate glass showed strain softening controlled by the rearrangement of the tetrahedral network. On the other hand, low-dense sodium aluminosilicate glass deformed by packing-induced flow associated with densification and via the rearrangement of the tetrahedral network at lower and higher strains, respectively. The transition of the deformation mechanism was triggered by the limitations of the densification of the tetrahedral network. The difference of deformation mechanism brought about higher strain in magnesium aluminosilicate glass than sodium aluminosilicate glass at the same stress condition. Easiness of remarkable deformation, which relaxed residual stress, and high deformability contributed to the high ductility of the MgO-aluminosilicate glass.     

Internal pressure behavior of polymers above and below the glass temperature

It has been well established in the literature that the internal pressure, P_i = (?E/?V)_T, of a polymer in the glassy state is about half the value expected from the behavior of the polymer just above the glass temperature, Tg. Consideration of this behavior in terms of a recent analysis of factors affecting internal pressures leads to the conclusion that the expression for the total energy of a glass must include a volume-dependent stored energy term, a term not present above Tg. This stored energy could be associated with actual bond and segment deformations in the glassy state. Brittleness and solvent cracking behavior of glasses will be strongly dependent on this stored elastic energy which can be modified by altering the molding conditions under which the glass is formed.     

Effect of pressure and temperature on viscosity of a borosilicate glass

During industrial glass production processes, the actual distribution of stress components in the glass during scribing remains, to date, poorly quantified, and thus continues to be challenging to model numerically. In this work, we experimentally quantified the effect of pressure and temperature on the viscosity of SCHOTT N‐BK7^® glass, by performing in situ deformation experiments at temperatures between 550 and 595°C and confining pressures between 100 and 300 MPa. Experiments were performed at constant displacement rates to produce almost constant strain rates between 9.70 × 10^?6 and 4.98 × 10^?5 s^?1. The resulting net axial stresses range from 81 to 802 MPa, and the finite strains range from 1.4% to 8.9%. The mechanical results show that the SCHOTT N‐BK7^® glass is viscoelastic near the glass transition temperature at 300 MPa of confining pressure. To elucidate the data, we incorporated both 1‐element and 2‐element generalized Maxwell viscoelastic models in an inversion approach, for which we provide MATLAB scrips. Results show that the 2‐element Maxwell model fits the experimental data well. The stress decreases with increasing temperature at 300 MPa and the temperature dependence yields a similar activation energy (601 ± 10 kJ mol^?1 or ?H/R = 7.2 × 10⁴ K) to a previously reported value at 1‐atm (615 kJ mol^?1 or ?H/R = 7.4 × 10⁴ K). The SCHOTT N‐BK7^® glass shows a limited linear increase in viscosity with increasing pressure of ~0.1 log₁₀ (Pa·s)/100 MPa, which is in agreement with the most recent 2‐internal‐parameter relaxation model (based on experiments).     

Optimized structural and mechanical properties of borophosphate glass

A series of phosphate glasses composed of (65-x)P₂O₅–15BaO–5Al₂O₃–5ZnO–10Na₂O-xB₂O₃ (x = 0, 2, 4, 6, and 8 mol%) were successfully prepared using the melt-quenching method. The effects of the addition of boron trioxide (B₂O₃) on the physical, structural, and mechanical properties of the glasses were investigated. As the added content of B₂O₃ increased from 0 to 6 mol%, the glass exhibited increased density and transition temperature, and decreased molar volume, indicating optimization of the glass stability. Raman spectroscopy revealed that the introduction of B₂O₃ transformed the glass from a chain structure to a three-dimensional network structure, which enhanced the chemical stability of the glass by the cross-linking of long phosphate chains with boron ions. Regarding the mechanical properties, when the boron content was 6 mol%, the flexural strength of the glass was 41% higher than that of the undoped boron, while the Vickers hardness and Knoop hardness values increased by 20.58% and 7.05%, respectively, and the fracture toughness was slightly decreased. In general, improving the mechanical properties of phosphate glass is of great significance for increasing the applications of this glass.     

The effect of molding time and temperature on the modulus and glass transition of phenolics

The effects of molding time and temperature on the dynamic mechanical behavior of a novolak phenolic molding compound were measured using the DuPont Dynamic Mechanical Analyzer. Large differences were found in the modulus-temperature response over the range of curing times (10 to 1800 s.) and temperatures (132 to 218°C) employed. Glass transition temperatures increased well beyond cure temperatures at long cure times. In the asmolded condition, samples cured at lower temperature had higher room temperature modulus than those cured at higher temperatures, and the lower modulus corresponded to lower density. Postbaking by steps up to 232°C increased the glass transition above 280°C, and also served to normalize the modulus differences found in as-molded samples.     

Enhanced luminescence of manganese in singly doped white light zinc phosphate glass

On the basis of a kind of zinc phosphate oxynitride glass matrix with a broadband blue light, a series of manganese single-doped glasses were obtained. A broader red emission with the higher intensity belonging to the Mn²⁺ ion was observed in this glass matrix. The mechanism of the emission from Mn²⁺ ions was clarified through Mn³⁺ as an “energy acquisition probe” to replace complex dynamic luminescence discussion, which was a fit explanation for the differences in luminescence behavior of Mn ions in prepared glasses at different degrees of redox. The research results indicated that the prepared manganese-doped glass was a potential candidate as phosphor-converted white-light-emitting diodes. An encapsulated white-light-emitting diode device based on this glass with 276 nm ultraviolet chip was achieved. It showed the CIE values of (0.33, 0.35), high CRI (Ra = 86), and low color temperature (5228 K).     

Dilatometric fragility and prediction of the viscosity curve of glass-forming liquids

Viscosity and coefficient of thermal expansion (CTE) are both crucial properties in the design of new glasses for various applications. In this work, we extend the application of dilatometry to measure two important parameters governing the viscosity of glass-forming systems, viz., glass transition temperature and fragility index. We also describe a method to determine the dilatometric fictive temperature (T_f,DIL) and present data for five unique glass compositions covering a range of fragilities spanning 38-96, which are subjected to cooling and reheating rates in the range 1-30 K/min. The results show that the glass transition temperature obtained from the dilatometric method at 10 K/min (T_g,DIL) is consistent with both viscosity-based (T_g,vis) and DSC-based measurements (T_g,DSC). It is shown that the fragility of a liquid (m_vis) can be determined by calibrating the dilatometric fragility (m_DIL) with the same empirical model as in the calorimetric approach. Put together, we have developed a reliable method to measure the fragility and predict the viscosity curves of glass-forming liquids over a wide range (eg, 10¹-10¹⁶ Pa·s) without direct viscosity measurements, while simultaneously obtaining the CTE of the glass. However, this method is not suitable for glasses with a strong tendency toward phase separation or crystallization.     

Role of MgO in lowering glass transition temperature and increasing hardness of lithium silicate glass and glass-ceramics

The effect of variation of MgO (1.5, 4.5 and 7.5 mol%) content on glass structure, crystallization behavior, microstructure and mechanical properties in a Li₂O–K₂O–Na₂O–CaO–MgO–ZrO₂–Al₂O₃–P₂O₅–SiO₂ glass system has been reported here. Increased amount of MgO enhanced the participation of Al₂O₃ as a glass network former along with [SiO₄] tetrahedra, reducing the amount of non-bridging oxygen (NBO) and increasing bridging oxygen (BO) amount in glass. The increased BO in glass resulted in a polymerized glass structure which suppressed the crystallization and subsequently increased the crystallization temperature, bulk density, nano hardness, elastic modulus in the glasses as well as the corresponding glass-ceramics. MgO addition caused phase separation in higher MgO (7.5 mol%) containing glass system which resulted in larger crystals. The nano hardness (～10 GPa) and elastic modulus (～127 GPa) values were found to be on a much higher side in 7.5 mol% MgO containing glass-ceramics as compared to lower MgO containing glass-ceramics.     

Thermal strengthening of low-expansion glasses and thin-walled glass products by ultra-fast heat extraction

Thermal strengthening remains the primary method for enhancing the practical strength of commodity glass products, however, the process is limited in terms of applicable glass thickness and coefficient of thermal expansion. The primary reasons for this limitation are the achievable heat transfer coefficient when using conventional gas cooling, and the occurrence of transient surface tension in the early stages of rapid quenching. We revisit this problem for the case of thin borosilicate glass sheet. Using liquid gallium as the cooling medium, ultra-fast heat extraction is achieved, with a heat transfer coefficient exceeding 5000 Wm⁻² K⁻¹. The low vapor pressure of gallium even at high temperatures enables preheating to a wide range of sheet entrant temperatures. We demonstrate thermal strengthening of low-expansion borosilicate glass with persistent surface compression of up to 85 MPa, and quenching to a fictive temperature of ~190 K above the glass transition temperature. Glass sheet obtained in this way exhibits notably enhanced surface defect resistance to sharp indentation. In addition to thermal strengthening, the extraordinarily high heat extraction rates achieved by liquid metal immersion enable exploitation of high-T_f glass properties beyond small and thin sample geometry.     

Structural origin of the weak germanate anomaly in lead germanate glass properties

Binary PbO–GeO₂ glasses have been studied in detail from 5 to 75 mol% PbO using high-resolution neutron diffraction, high-energy X-ray diffraction, 207-Pb NMR, pycnometry, and thermal analysis. The Ge–O coordination number displays a broad maximum n_GeO = 4.14(3) close to 27 mol% PbO. This is smaller than the maximum n_GeO = 4.3 reported in CaO–GeO₂ glasses but occurs at a similar composition. This structural behavior appears to explain the relatively weak germanate anomaly manifest in lead germanate glasses, for example as a maximum in the measured atom number density and a plateau in the glass transition temperatures. The structural role of Pb(II) is complex. On the one hand, short covalent Pb–O bonds and small Pb–O coordination numbers of ∼3 to 4 indicate glass network former character for Pb(II), associated with a stereochemically active electron lone pair. On the other hand, the presence of some GeO₅ or GeO₆ units, in addition to the majority GeO₄ tetrahedral species, indicates some modifier character of Pb(II) at low PbO contents, giving rise to the observed weak germanate anomaly, as well as elongation and enhanced ionicity of the Pb–O bonds. Overall, the observed structural behavior of Pb(II) in lead germanate glasses appears as intermediate between that observed in lead silicate and lead borate glasses. Despite rapid quenching, at low PbO contents, the glasses studied exhibited nanoscale heterogeneity, evidenced by small-angle X-ray scattering consistent with the early stages of spinodal decomposition.