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  1. Abstract

    The field strength (FS) effect of six different network modifiers on the elastoplastic properties of aluminoborosilicate glasses was explored using a volumetric recovery study. This work, in conjunction with Part I, explored the intersection of hardness, crack resistance, and other physical properties with glass elasticity. Results showed that (1) the elastic volume fraction decreased with FS for both the alkali and alkaline earth (AE) glasses; (2) the Poisson's ratio did not trend with pile‐up or shear flow volume fraction; (3) the elastic‐to‐plastic deformation ratio increased with applied load and decreased with modifier FS for both the alkali and AE glasses; and (4) an increase in plasticity correlated with increased hardness, crack resistance, and elastic moduli.

     
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  2. Abstract

    The modifier field strength (FS) is believed to play an important role in determining the elastic–plastic responses of aluminoborosilicate (ABS) glasses, but its effect is not well understood. Three novel alkali and three alkaline earth (AE) ABS compositions were created for this study which is the first part of two studies that explored the elastoplastic responses of these glasses. Six compositions were designed using different network modifiers (NWMs) to cover a range of cation FS. The glasses were also designed such that the concentrations of NWM and Al2O3were similar, which maximized the three‐coordinated boron fraction in the network. It is well known that modifier FS can affect the coordination number (CN) of Al and B in an ABS glass structure, for example, a higher FS modifier can promote B3 → B4and higher [Al5,6], but the degree of this depends on network former (NWF) ratios. Previous work used solid‐state NMR spectroscopic analysis on the current glasses to find that there was variation between [B4] and [Al4] between the two glass series (alkali vs. AE) but that was attributed to synthesis factors and no trend with FS was associated with the varying NWF CN. Further,29Si ssNMR showed no evidence of NBOs which made sense based on composition. The conclusion, therefore, was that there was a far greater correlation with modifier FS for the increased mechanical and physical properties rather than the CN of Al and B. Part I of the current work focused on the elastic moduli, Poisson's ratio, the indentation size effect (ISE), and the bow‐in parameter. This part laid out the foundation to investigate the intersection of these elastoplastic properties with hardness and crack resistance as a function of NWM FS. Results showed that: (i) the Young's, bulk, and shear moduli increased with modifier FS, whereas Poisson's ratio did not trend with FS; (ii) the alkali glasses had a significantly higher magnitudes of ISE compared to the AE glasses; and (iii) the bow‐in parameter was load dependent and decreased with modifier FS at the highest indentation load.

     
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  3. Abstract

    Ionic conductivity in silicate glasses is a major issue in the energy sector due to its detrimental effect on electric energy generation and storage and has received increasing attention over the past years. In this study, surface modification of soda–lime–silica (SLS) float glass via acid‐leaching treatment (pH 1) was implemented to understand the impact on ionic transport. The acid‐leaching treatment created a sodium‐depleted “silica‐like” structure in the near‐surface region with depths of 110 ± 20 nm for the air‐side and 93 ± 2 nm for the tin‐side of the SLS glass. Using the thermally stimulated depolarization current technique, two thermally activated relaxation peaks were found to be associated with different ion migration mechanisms. The first peak (P1) with activation energy of ∼0.85 eV was attributed to dc conduction of Na+ions through the glass bulk. A second overlapping peak (P2) at a higher temperature was found to be related to a more limited Na+ion migration through the acid‐leached structure, due to H+conduction, or a coupled contribution of both mechanisms.

     
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  4. Abstract

    Although the interactions among glass formers and modifiers, for example, connectivity and charge distribution, have been studied extensively in oxide glasses, the impact of a particular modifier species on the mechanical performance of aluminoborosilicate (ABS) glasses is not well understood. This work compares the indentation properties of six ABS glasses, each of which contains a different network modifier (NWM) with varying field strength (FS). Three alkali and three alkaline earth ABS glasses were designed with low NWM content and [NWM] ≈ [Al2O3], to test the modifier FS effect at low concentrations and to maximize three‐coordinated boron. It has been found that both hardness and crack resistance increase with increasing FS in these ABS systems, which is surprising in the context of historical reports. Using11B,27Al, and29Si solid‐state nuclear magnetic resonance, this work provides evidence of how charge distributions differ as a function of NWM species, and how this relates to the observed indentation behaviors.

     
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  5. Abstract

    Vibrational spectroscopy has been widely used to investigate various structural aspects of the glass network, and there are a plethora of papers reporting subtle but consistent changes in infrared and Raman spectral features of glass upon alterations of glass compositions, thermal histories, mechanical stresses, or surface treatments. However, interpretations of such spectral features are still obscured due to the lack of well‐established physical principles accurately describing vibrational modes of the non‐crystalline glass network. Due to the non‐equilibrium nature of the glass network, three‐dimensionally connected without any long‐range orders, vibrational spectral features of glass cannot be interpreted using the analogy with those of isolated molecular moieties or crystalline counterparts. This feature article explains why such comparisons are outdated and describes the recent advances made from theoretical calculations of vibrational spectral features of amorphous networks or comparisons of computational results with experimental data. For the interpretation of vibrational spectral features of silica and silicate glasses, the following empirical relationships are suggested: (i) the intensity‐weighted peak position of the Si‐O‐Si stretch mode negatively correlates with the weighted average of the Si‐O bond length distribution, and (ii) the broad band of the Si‐O‐Si bending mode negatively correlates with the Si‐O‐Si bond angle distribution. Selected examples of vibrational spectroscopic imaging of surface defects are discussed to deliberate the implication of these findings in the structure‐property relationship of silica and silicate glass materials. Unanswered questions and continuing research challenges are identified.

     
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  6. Abstract

    As a means to elucidate the mechanical stress effect on the durability of soda lime silicate (SLS) float glass, a thin glass plate under flexural stress was investigated with X‐ray photoelectron spectroscopy (XPS), specular reflectance infrared (SR‐IR) spectroscopy, nanoindentation, and tribo‐testing. A lab‐built four‐point bending rig was employed to create compressive or tensile stress (around 40 MPa) on the air‐side surface of SLS glass. XPS analysis showed that electric field‐induced sodium ion migration is greatly enhanced in both compressive and tensile stress surfaces. The SR‐IR analysis of the Si‐O‐Si stretch mode revealed that the structural distortion of the silicate network appears to be larger under compressive stress than tensile stress. The elastic and plastic responses of the SLS surface to nanoindentation were significantly altered under the flexural stress conditions even though the magnitude of the flexural stress was less than 0.7% of the applied indentation stress. Compared to the stress‐free surface, the resistance to mechanochemical wear at 90% relative humidity deteriorated under the compressive stress condition, while it just became more scattered under the tensile stress condition. Even though the applied flexural stress was very small, its impact on chemical and structural properties could be surprisingly large. Combining all results in this study and previously published works suggested that the changes observed in nanoindentation and mechanochemical wear behaviors may be associated with the strain in the Si‐O bonds of the silicate network.

     
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  7. Abstract

    Water or acid soaking surface treatments have been shown to increase the mechanical strength of soda‐lime silicate (SLS) glasses. This increase in strength has traditionally been attributed to effects related to residual stress or changes in fracture resistance. In this work, we report experimental data that cannot be explained based on the existing knowledge of glass surface mechanics. In dry environments, annealed and acid‐leached SLS surfaces have comparable crack initiation stress and fracture stress as measured by Hertzian indentation and biaxial bending tests, respectively. Yet, in the presence of humidity, acid‐leached surfaces have higher failure stress than the annealed surfaces. This apparent enhancement in the crack resistance of the acid‐leached surface of SLS glass in humid environments supports the hypothesis that acid‐leached surface chemistry can lower the transport kinetics of molecular water to critical flaws.

     
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  8. Abstract

    Glass for pharmaceutical packaging requires high chemical durability for the safe storage and distribution of newly developed medicines. In borosilicate pharmaceutical glasses which typically contain a mixture of different modifier ions (alkali or alkaline earth), the dependence of the chemical durability on alkaline earth oxide concentrations is not well understood. Here, we have designed a series of borosilicate glasses with systematic substitutions of CaO with MgO while keeping their total concentrations at 13 mol% and a fixed Na2O concentration of 12.7 mol%. We used these glasses to investigate the influence ofR = [MgO]/([MgO] + [CaO]) on the resistance to aqueous corrosion at 80°C for 40 days. It was found that this type of borosilicate glass undergoes both leaching of modifier ions through an ion exchange process and etching of the glass network, leading to dissolution of the glass surface. Based on the concentration analysis of the Si and B species dissolved into the solution phase, the dissolved layer thickness was found to increase from ~100 to ~170 nm asRincreases from 0 to 1. The depth profiling analysis of the glasses retrieved from the solution showed that the concentration of modifier ions (Na+, Ca2+, and Mg2+) at the interface between the solution and the corroded glass surface decreased to around 40%–60% of the corresponding bulk concentrations, regardless ofRand the leaching of modifier cations resulted in a silica‐rich layer in the surface. The leaching of Ca2+and Mg2+ions occurred within ~50 and <25 nm, respectively, from the glass surface and this thickness was not a strong function ofR. The leaching of Na+ions varied monotonically; the thickness of the Na+depletion layer increased from ~100 nm atR = 0 to ~200 nm atR = 1. Vibrational spectroscopy analysis suggested that the partial depletion of the ions may have caused some degree of the network re‐arrangement or re‐polymerization in the corroded layer. Overall, these results suggested that for the borosilicate glass, replacing [CaO] with [MgO] deteriorates the chemical durability in aqueous solution.

     
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