Revealing the effect of medium-range structure on silicate glass hardness

Ying Shi, Binghui Deng, Jörg Neuefeind, Qi Zhou, Morten M. Smedskjaer, Stephen R. Elliott, and Mathieu Bauchy

Phys. Rev. Materials 7, 013602 – Published 4 January 2023

Abstract

Atomic structure determines physical properties, but for glassy materials, the nature of structure-property relationships remains ambiguous. Since glass properties are governed by both chemistry and structure, it is difficult to dissociate these two effects. Here, the sole effect of the structure on property is isolated by treating an industrial aluminosilicate glass with either thermal-annealing or pressure-quenching processes to produce glasses with varying densities and hardnesses (at constant composition). To explore the underlying structural origin of property changes, neutron total-scattering patterns of these glasses were measured. These results confirm the applicability of rigid-unit mode theory since the short-range tetrahedra were found to remain unaffected. In contrast, close correlations are derived between properties and medium-range structure (as encoded in various features of the first sharp diffraction peak). Overall, it reveals that the increase in the medium-range order is the structural origin of the extra extent of hardness increase beyond the densification effects.

Received 25 August 2022
Accepted 5 December 2022

DOI:https://doi.org/10.1103/PhysRevMaterials.7.013602

Physics Subject Headings (PhySH)

Hardness

Glasses

Neutron pair-distribution function analysis

Condensed Matter, Materials & Applied Physics

Authors & Affiliations

Ying Shi ^1,*, Binghui Deng ¹, Jörg Neuefeind², Qi Zhou³, Morten M. Smedskjaer ⁴, Stephen R. Elliott⁵, and Mathieu Bauchy³

¹Science and Technology Division, Corning Incorporated, Corning, New York 14831, USA
²Neutron Scattering Division, Spallation Neutron Source (SNS), Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA
³Physics of AmoRphous and Inorganic Solids Laboratory (PARISlab), Department of Civil and Environmental Engineering, University of California, Los Angeles, California 90095, USA
⁴Department of Chemistry and Bioscience, Aalborg University, Aalborg, Denmark
⁵Physical and Theoretical Chemistry Laboratory, University of Oxford, Oxford OX1 3QZ, United Kingdom

^*shiy3@corning.com

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Vol. 7, Iss. 1 — January 2023

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Images

Figure 1
Effects of thermal annealing (red) and pressure quenching (blue) on the change in (a) density $(ρ)$ and (b) hardness ( $H$ ). The relative change (%) is calculated by comparing the treated glass with the as-prepared one. Density does not notably change upon annealing but increases linearly with pressure for pressure-quenched glasses. Hardness increases upon both treatments. Both density and hardness data are from Ref. [14]. The errors in the density change are propagated from the density error of $\pm 0.004 g / c m^{3}$ , as reported in Ref. [17]. The errors in the hardness change are propagated from the errors of hardness values estimated from fig. 2 of Ref. [14].
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Figure 2
(a-1) and (a-2) Normalized reduced structure-factor functions $F (Q)$ and (b-1) and (b-2) Fourier-transformed reduced pair distribution functions $G (r)$ for thermal-annealed (top panel) and pressure-quenched (bottom panel) glasses. The same color schemes as labeled in the $F (Q)$ plots are used in the $G (r)$ plots. Insert: Zoomed low- $r$ region of $G (r)$ curves demonstrating the correct normalization of the $F (Q)$ scans, with similar slopes through the rippled $G (r)$ curves for the annealed glasses [insert of (b-1)] reflecting their comparable densities, whereas the higher negative slopes of the high pressure-quenched glasses [insert of (b-2)] reflect their higher density.
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Figure 3
First sharp diffraction peak (FSDP) deconvolution of thermally annealed glasses by the RingFSDP method [10]. $S_{\leq 4 − ring} (Q)$ (red) is the $Q$ -range component of $\leq 4$ rings with a corresponding real-space position of $3.15 Å$ ; $S_{5 − ring} (Q)$ (blue) and $S_{\geq 6 − ring} (Q)$ (black) have real-space positions of 3.70 and $4.30 Å$ , respectively. The sum of all three $S_{n − ring} (Q)$ functions (solid green curve) matches with the measured $S (Q) − FSDP$ with the background removed (dotted pink curve). The three fixed positions with the values of 2.00, 1.70, and $1.46 Å^{- 1}$ , are shown by the three straight vertical dotted lines, corresponding to the real-space characteristic periodicities of 3.15, 3.70, and $4.30 Å$ , respectively.
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Figure 4
(a-1) and (a-2) Zoomed $F (Q) - first$ sharp diffraction peak (FSDP) and (b-1) and (b-2) zoomed $G (r)$ with nearest atomic pairs of $A − O$ and O-O correlations from $A O_{4}$ tetrahedra for thermally annealed (top panel) and pressure-quenched (bottom panel) glasses. Differences are observed in the FSDPs for both treatment series, which are especially significant for pressure-quenched glasses. No observable differences are shown in the short-range $A O_{4}$ tetrahedral configuration in the $G (r)$ curves.
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Figure 5
Thermal-annealing (red) and pressure-quenching (blue) effects on the change in (a) average medium-range distance (ave. MRD) and (b) density $(ρ)$ . (c) highlights a linear property-structure correlation between $ρ$ and ave. MRD. The relative change (%) is calculated by comparing each treated glass with the same as-prepared glass. The ave. MRD does not change upon annealing but decreases linearly with pressure. The dotted lines in (a) and (b) are guides for the eye; that in (c) is a least-squares fit. The errors in the ave. MRD change are propagated from the difference of ave. MRD values obtained by two neutron total-scattering measurements performed on two separate samples of the same fused silica glass.
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Figure 6
Thermal-annealing (red) and pressure-quenching (blue) effects on the change of (a) integrated $S$ ( $Q$ )-first sharp diffraction peak (FSDP) area and (b) hardness ( $H$ ). (c) highlights a positive property-structure correlation between $H$ and the $S (Q) − FSDP$ area. The relative change (%) is calculated by comparing each treated glass with the as-prepared one. Two sets of hardness values are plotted in (c) for pressure-quenched glasses: the blue ones are from original hardness values, whereas the black ones are the modified hardness values, corrected to filter out densification effects. The errors in the $S (Q) − FSDP$ area change values are propagated from the difference of $S (Q)$ area values obtained by two neutron total-scattering measurements of two separate samples of the same fused silica glass.
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