Correlation between the dimensionality and the constants of elasticity of rare-earth doped borate glasses

This work was devoted to explore the correlation between the dimensionality and the computed theoretically constants of elasticity of borate based glasses doped with rare-earth oxides. The dimensionality of the glassy network has been calculated in terms of the d ratio which is equal to 4 C ₄₄/K _e and discussed in terms of the cross-link density and number of network bonds per unit volume of these glasses. Constants of elasticity were calculated in terms of the bond compression model and the Makishima-Mackenzie model. The average cross-link density, the number of network bonds per unit volume, the average stretching-force constant, and the ratio of the estimated bulk modulus (K _bc) to the experimentally determined (K _e) have been calculated and discussed in terms of the bond-compression model. Young??s modulus, the packing density, and the dissociation energy have been calculated and analyzed in terms of the Makishima-Mackenzie model. The results showed that the computed elastic moduli and the dimensionality of the borate glasses containing La₂O₃ or Gd₂O₃ are strongly dependent on the concentration of the structural units of the constituent oxides and types of bonds between these units.     

Revealing structural role of ZrO2 in silicate glasses from macroscale property by rigid-unit packing fraction method

The structural role of an oxide as a former and modifier can have significant effects on the chemical durability and mechanical properties of the glass. Some oxides with high-field strength cations, for example, MgO and ZrO₂, are often labeled as a third group—intermediate, due to their either undetermined or dual structural roles dependent on the glass compositions. Based on our recent modification of the Makishima–Mackenzie (MM) model using the rigid-unit Packing Fraction (RUPF), we analyzed a series of novel zirconia-containing bioactive glasses. The RUPF-based MM-model provides better prediction of the elastic moduli of these new glasses in comparison to experimental measurements. At the same time, the structural role of zirconia can be determined by comparison with calculations by assuming various structural roles and those from experiments. We reveal that ZrO₂ acts as the network former in phosphosilicate glasses, which leading to significant increase in packing fraction and consequent increase in Young's modulus. The recent experimental and atomistic simulation results support the glass former role of zirconia in silicate glasses. This method is general and applicable to other oxides in glasses.     

Influence of Boron Oxide on the Physicomechanical Properties of Glasses in the Li2O–B2O3–P2O5 System

The mechanical properties of glasses in the Li₂O–B₂O₃–P₂O₅ system are investigated as a function of the boron oxide content in the range from 5 to 30 mol % at a constant lithium oxide content of 45 mol %. It is demonstrated that, as the B₂O₃ content increases, the density of glasses passes through a maximum at 20 mol % B₂O₃ and the molar volume decreases gradually. The elastic modulus and the hardness of glasses monotonically increase with an increase in the B₂O₃ content. An increase in the B₂O₃ content leads to a decrease in the structural strength (measured using the method of three-point bending of fibers) and the fracture toughness (determined by the microindentation technique). The assumption is made that the decrease in the strength characteristics is caused by the phase separation developed in the structure of lithium phosphate glass with an increase in the B₂O₃ content.     

Effect of TiO2 addition on thermal and mechanical properties of Y-Si-Al-O-N glasses

Y-Si-Al-O-N glasses are intergranular phases in silicon nitride based ceramics in which the composition and volume fraction of oxynitride glass phases determine the sintering/shrinkage behaviour. Several investigations on oxynitride glass formation and properties have shown that addition of nitrogen increases glass transition and softening temperatures, viscosity, elastic modulus and hardness. In the present study, effect of TiO₂ addition on thermal and mechanical properties of Y-Si-Al-O-N glasses is investigated since the most typical Si₃N₄ ceramics for bearing applications are fabricated using a Si₃N₄-Y₂O₃-Al₂O₃-TiO₂-AlN system. Addition of TiO₂ is effective in preparing Y-Si-Al-O-N glasses with lower glass transition temperatures and with higher hardness.     

Surface Analysis of Cr2O3‐, CoO‐, and Al2O3‐Doped Iron–Phosphate Glasses at High Temperature

Surface structures of iron–phosphate glasses were examined using X‐ray photoelectron spectroscopy (XPS). Cr₂O₃, CoO, and Al₂O₃ were introduced to the glass by the replacement of a part of Fe₂O₃, and the simulated fission products are also added. The obtained glasses showed high chemical durabilities by MCC‐1 test. In situ high‐temperature and room‐temperature XPS measurements were conducted on the polished sample surfaces and also those after 1‐week chemical durability test. Unique trends were observed in XPS spectra on heating and after the chemical durability test, respectively. Nature of the glass surface of iron–phosphate glasses was explained from the point of view of surface energy, and the origin of high chemical durability and the effect of chromium ions were discussed based on the changes on surface composition and valence states of transition‐metal ions.     

Environment-dependent indentation recovery of select soda-lime silicate glasses

Indentations made on silicate glasses can easily be affected by the environment. In the present work, indentations were made on select commercial float glasses as well as on experimental soda-lime silicate glasses using a 1 mm diameter spherical tungsten carbide ball-mounted Brinell indenter. Recovery of indentations made on the glass samples was measured in different environments, namely, 100 °C, room temperature/room humidity and 100% relative humidity, as a function of time by using a Zygo laser non-contact profiliometer. Elastic (Young's modulus, bulk modulus, shear modulus and Poisson's ratio) and indentation (Vickers hardness, fracture toughness, brittleness and fracture surface energy) properties of the glasses were also determined by a pulse-echo and Vickers indentation methods, respectively, to correlate with the recovery of indentations. The elastic properties and Vickers hardness are directly proportional to the packing ions present in the glass structure and the strength of an individual bond, whereas the brittleness and fracture toughness more likely depend on molar volume of the glasses. According to the applied environment, a recovery rate of indentations follows the order: room temperature/room humidity <100% relative humidity <100 °C, regardless of glass composition. The reason for higher recovery rate of indentations is attributed to the structural relaxation, which is promoted by a thermodynamic driving force at 100 °C, and stored strain energy in deformation zone, allowing the indentations to regain their original configurations at certain points.     

Two-step sinter-crystallization of K2O–CaO–P2O5–SiO2 (45S5-K) bioactive glass

Bioactive glasses and glass-ceramics (GCs) effectively regenerate bone tissue, however most GCs show improved mechanical properties. In this work, we developed and tested a rarely studied bioactive glass composition (24.4K₂O-26.9CaO-46.1SiO₂-2.6P₂O₅ mol%, identified as 45S5-K) with different particle sizes and heating rates to obtain a sintered GC that combines good fracture strength, low elastic modulus, and bioactivity. We analyzed the influence of the sintering processing conditions in the elastic modulus, Vickers microhardness, density, and crystal phase formation in the GC. The best GC shows improved properties compared with its parent glass. This glass achieves a good densification degree with a two-step viscous flow sintering approach and the resulting GC shows as high bioactivity as that of the standard 45S5 Bioglass®. Furthermore, the GC elastic modulus (56 GPa) is relatively low, minimizing stress shielding. Therefore, we unveiled the glass sintering behavior with concurrent crystallization of this complex bioactive glass composition and developed a potential GC for bone regeneration.     

An Overview of the Structure and Properties of Silicon-Based Oxynitride Glasses

The silicon oxynitride glasses take advantage of nitrogen bonding to attain high elastic modulus, increased softening temperatures and viscosities, greater slow crack growth resistance, and modest gains in fracture resistance. Of the oxynitride glasses, the Si–Y–Al-based oxynitride glasses have been most extensively studied and a degree of success has been achieved in understanding how changes in glass composition affect structural parameters and their relationship with properties. More recent studies have focused on the Si–RE–Me oxynitride glasses, where Me is primarily Al or Mg and rare earth (RE) includes most of the lanthanide series elements. These glasses possess a range of elastic, thermal, mechanical, and optical properties, which can be correlated with the strength of the RE bond in terms of the cationic field strength. However, such correlations require knowledge of not only the RE valence state but also its coordination with the anions. Herein, the current state-of-the-art understanding of the properties and structural parameters of oxynitride glasses and their interrelationships are reviewed.     

Physical and Mechanical Behavior of Polymer Glasses. VI. the Role of Free Volume

Abstract

For various polymer glasses, the temperature-induced recovery of residual deformation was studied. The ratio between the low-temperature and high-temperature recovery components is controlled by the difference between deformation temperature and glass transition temperature T _g of polymer samples independently of their chemical structure. This ratio correlates with polymer macroscopic mechanical characteristics such as elastic modulus and yield stress. Experimental results were treated in terms of the dynamics of segmental mobility within different structural sublevels with different packing densities. To correlate this mechanical response with the structural state of glassy polymers, positron annihilation lifetime spectroscopy (PALS) was used. For different polymer glasses, the microscopic segmental mobility and resultant macroscopic mechanical properties were shown to be controlled only by the development of the adequate free volume content which depends on the difference between testing temperature and T _g . These results allowed us to propose the general correlation between microstructure, microscopic molecular mobility, and Macroscopic mechanical behavior of polymer glasses.     

Synthesis,FTIR, and mechanical as well as radiation shielding characteristics in Nd2O3-doped bismuth lithium borate glasses

A melt quenching method was applied to fabricate a series of bismuth lithium borate glasses with a chemical composition of 65(B₂O₅) + 20(Bi₂O₃) + (15 ? x)(Li₂O) + x(Nd₂O₃), where x = 0, 1, 2, 3, and 4 mol%. The structural changes in the fabricate glasses were studied via the Fourier transform infrared spectroscopy (FT-IR). The FT-IR spectra of the manufactured glasses indicated the transformation of the structural unit BO₄. The mechanical properties of the produced glasses were evaluated via the ultrasonic measurement (longitudinal and shear velocities) and the Makishima–Mackenzie modulus calculations. Furthermore, the role of Nd₂O₃ in improving mechanical properties was studied theoretically and experimentally and results showed that ultrasonic velocities and elastic moduli decreased with increasing the Nd₂O₃ content. The Young's modulus decreased from 68.47 to 50.61 GPa as the Nd₂O₃ content increased from 0 to 4 mol%, respectively. The gamma ray shielding properties of the studied glass samples were evaluated using the Monte Carlo simulations between 0.223 and 2.506 MeV. The simulated data showed that the fabricated glass without Nd₂O₃ has the highest linear attenuation coefficient, which varied between 0.210 and 0.212 cm^?1 for photons with energies ranging from 0.2234 to 2.506 MeV.     

Ionic Conductivity in Sodium–Alkaline Earth–Aluminosilicate Glasses

The effect of alkaline‐earth ions on Na transport in aluminosilicate glasses was studied by measuring ionic conductivity for a systematic compositional series of Na₂O–RO–Al₂O₃–SiO₂ glasses (R=Mg, Ca, Sr, Ba). The Na transport in aluminosilicate glass could be affected by compositional changes in aluminum coordination and nonbridging oxygen as well as physical properties such as dielectric constant, shear modulus, and ionic packing factor. Through careful experimental designs and measurements, the main determinants among these parameters were identified. ²⁷Al MAS‐NMR indicated that all aluminum species contained in these glasses are four‐coordinated. The activation energy for ion conductivity decreased with increasing aluminum content and decreasing ionic radii of the alkaline‐earth ion in the region where [Al] < [Na]. When the aluminum content exceeded the sodium content ([Al] > [Na]), the composition dependence of the activation energy depended on the specific alkaline earth. These results are explained based on variations in free volume and dielectric constant caused by structural changes around the AlO₄ charge compensation sites. These structure changes occur in response to the smaller size and higher field strength of the alkaline‐earth ions, and are most prevalent in the compositions which require bridging of two AlO₄ sites by the alkaline‐earth ion for charge compensation.     

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.     

Elastic properties of quaternaryTeO2–ZnO–Nb2O5–Gd2O3 glasses

Tellurite glass systems in the form 75TeO₂–15ZnO–(10−x)Nb₂O₅–xGd₂O₃ (x=0.0, 0.5, 1.0, 1.5, 2.0, 2.5 mol%) have been prepared by the melt quenching technique. Both longitudinal and shear ultrasonic velocities were measured by using the pulse-echo method at 5 MHz frequency and at room temperature. Elastic moduli (longitudinal modulus, shear modulus, Young׳s modulus, Bulk modulus), Poisson׳s ratio, Debye temperature, micro-hardness and softening temperature have been calculated. Quantitative analysis of elastic moduli based on the number of bond per unit volume, average crosslink and number of vibrating atoms per unit volume has been achieved.     

Improved Prediction of Young's Modulus of Fluorine‐Containing Glasses Using MAS‐NMR Structural Data

The model developed by Makishima and Mackenzie (M–M) may yield reasonable estimates for the E‐modulus of a range of glasses. In the M–M model the bonding enthalpy and packing densities present in the compounds that form the glass are taken as input for the calculation. This study shows that a more accurate estimate can be obtained by incorporating in the model structural information from MAS‐NMR data. Specifically, we have determined by means of the impulse excitation technique (IET) the E‐modulus for ionomer glasses with composition 4.5SiO₂–3Al₂O₃–1.5P₂O₅–3MO–2MF₂, where M denotes the alkaline earth metal (M = Mg, Ca, Sr, or Ba). The MAS‐NMR structural analysis shows that substitution of calcium by barium or strontium results in a disrupted network, whereas magnesium leads to a more packed network. In this study we will show how a higher coordination state of the aluminum as determined by ²⁷Al MAS‐NMR can be taken into account in the model. This leads to rather small corrections of the estimates for these particular glasses. In contrast, the ¹⁹F MAS‐NMR study shows the presence of Al–F–M(n) or Al–F and Si–F–M(n) types of environment in the glass network. Al–F and Si–F bonds are not accounted for in the E‐modulus estimate by the M–M model. We will show how by incorporating the new bonding of F with Al and Si a significantly improved estimate of the E‐modulus is obtained compared with the original model.     

Electret Properties of Radiation-Charged Phosphate Glasses

The process of formation of a surface charge in phosphate glasses depending on polarization conditions is investigated. A relationship is established between the chemical composition of glass and its capacity for forming internal electric fields under radiation for glasses of type 0.50P₂O₅ – 0.45RO – 0.05R₂O₃.     

Influence of the composition of high-lead phosphate glasses on the location of the UV transmission edge and technological quality

This paper reports on the results of an investigation into the influence of the purity of the initial materials used for preparing vitreous lead metaphosphate, the acidity of the phosphate matrix, and the contents of additives of Group I–III and V elements and the second glass-former on the location of the UV transmission edge of simple binary and ternary lead phosphate glasses. It is shown that, even for a binary glass of the composition (mol %) 50PbO · 50P₂O₅, the location of the UV transmission edge can be shifted by ～50 nm on the wavelength scale depending on the purity of the initial reactants. The shift of the UV transmission edge toward the UV spectral range for ternary glasses containing no variable-valence elements other than lead is considerably larger than that for the high-lead phosphate glass of the previously proposed composition involving antimony, niobium, and cerium oxides. It is established that the addition of niobium oxide Nb₂O₅ to lead phosphate glasses brings about a red shift of the UV transmission edge and a change in the crystallization ability of the glasses. Niobium oxide at a content up to 1.5 mol % increases the crystallization ability of the glass, whereas a change in the niobium oxide content from 1.5 to 3.1 mol % results in a decrease in the crystallization ability. It is demonstrated that the crystallization ability of high-lead phosphate glasses increases at a boron oxide content higher than 5 mol %.     

Elasticity,hardness, and fracture toughness of sodium aluminoborosilicate glasses

Due to an increasing demand for oxide glasses with a better mechanical performance, there is a need to improve our understanding of the composition-structure-mechanical property relations in these brittle materials. At present, some properties such as Young's modulus can to a large extent be predicted based on the chemical composition, while others—in particular fracture-related properties—are typically optimized based on a trial-and-error approach. In this work, we study the mechanical properties of a series of 20 glasses in the quartenary Na₂O–Al₂O₃–B₂O₃–SiO₂ system with fixed soda content, thus accessing different structural domains. Ultrasonic echography is used to determine the elastic moduli and Poisson's ratio, while Vickers indentation is used to determine hardness. Furthermore, the single-edge precracked beam method is used to estimate the fracture toughness (K_Ic) for some compositions of interest. The compositional evolutions of Vickers hardness and Young's modulus are in good agreement with those predicted from models based on bond constraint density and strength. Although there is a larger deviation, the overall compositional trend in K_Ic can also be predicted by a model based on the strength of the bonds assumed to be involved in the fracture process.     

The Influence of Silicon Oxide on the Mechanical Properties of Metaphosphate Glasses

The possibility of improving the mechanical properties of potassium aluminum metaphosphate glasses through the introduction of silicon oxide into the glass composition is analyzed. It is shown that the elastic moduli (Young modulus, shear modulus, Poisson ratio) and the hardness remain almost unchanged with an increase in the content of silicon oxide in the glass. At the same time, the structural strength increases by a factor of 1.7 and the fracture toughness increases by a factor of 1.3. The assumption is made that the observed increase in the structural strength is associated with the incorporation of silicon ions into the structure of the metaphosphate glass in the octahedral coordination.     

Influence of Residual Water in a Glass on Its Rheological and Relaxation Properties (by the Example of a 5Na2O · 95B2O3Glass)

Glasses of the 5Na₂O · 95B₂O₃(mol %) composition synthesized at a temperature of 1100°C for 180 and 20 min are studied. The temperature dependences of the viscosity and the thermal expansion of glasses are obtained. The thermal expansion coefficients and glass transition temperatures of the studied glasses are determined, and the parameters of structural relaxation (the constant characterizing the width of the spectrum of relaxation times, the relaxation modulus equal to the ratio of the viscosity to the relaxation time, and the relaxation time at zero reciprocal temperature) are calculated from the dilatometric curves measured at temperatures close to the glass transition range. The water content in the studied glasses is estimated by comparing the obtained dependence of the viscosity on the water content with the data available in the literature for glasses of a similar composition. The assumption is made that the structural relaxation time in sodium borate glass decreases with an increase in the water content.     

Integration Between Optical and Structural Behavior of Heavy Metal Oxide Glasses Doped with Multiple Glass Formers

Heavy metal oxide glasses (composition 60 PbO, 20 Bi₂O₃ mol%) and containing 20 mol% conventional glass formers SiO₂, B₂O₃, and P₂O₅ were prepared. Combined optical and Fourier transform infrared absorption spectra were measured for the prepared glasses to justify the role of glass formers in the optical spectra together with the network structural groups in such glasses. Also, the density and molar volume values were calculated to obtain some insight on the compactness and arrangement in the network. Optical measurements have been used to determine the optical band gap (E_g), Urbach energy (ΔE) and the refractive index (n). Optical spectra of all the samples reveal strong UV absorption which is related to the presence of unavoidable trace iron impurities (Fe ³⁺ ions) contaminated within the raw materials which were used for the preparation of the studied glasses. Additional near visible bands are observed in all prepared glasses due to characteristic absorption of Pb ²⁺ and Bi ³⁺ ions. Furthermore, The variations of the luminescence intensity, values of the optical band gap, band tail, and refractive index can be understood and related in terms of the structural changes that take place in the glass samples. The infrared absorption spectra of the prepared glasses show characteristic absorption bands related to the borate or silicate or phosphate network (BO₃, BO₄, SiO₄, PO₄ groups) together with vibrational modes due to Bi-O and Pb-O groups.