Infrared (IR) and Raman spectroscopic features of silicate glasses are often interpreted based on the analogy with those of smaller molecules, molecular clusters, or crystalline counterparts; this study tests the accuracy and validity of these widely cited peak assignment schemes by comparing vibrational spectral features with bond parameters of the glass network created by molecular dynamics (MD) simulations. A series of sodium silicate glasses with compositions of [Na2O]
The atomic‐scale cracking mechanism in clay is vital in discovering the cracking mechanism of clay at the continuum scale in that clay is a nanomaterial. In this article, we investigate mechanisms of modes I and II crack propagations in pyrophyllite and Ca‐montmorillonite with water adsorption through reactive molecular dynamics (MD) with a bond‐order force field. Clay water adsorption is considered by adding water molecules to the clay surface. During the equilibration stage, water adsorption could cause bending deformation of the predefined edge crack region. The relatively small orientating angle of water molecules indicates the formation of hydrogen bonds in the crack propagation process. The peak number density of adsorbed water decreases with the increasing strains. The atomistic structure evolution of the crack tip under loading is analyzed to interpret the nanoscale crack propagation mechanism. The numerical results show that the crack tip first gets blunted with a significant increase in the radius of the curvature of the crack tip and a slight change in crack length. The crack tip blunting is studied by tracking the crack tip opening distance and O–Si–O angle in the tetrahedral Si–O cell in modes I and II cracks. We compare bond‐breaking behaviors between Al–O and Si–O. It is found that Si–O bond breaking is primarily responsible for crack propagation. The critical stress intensity factor and critical energy release rate are determined from MD simulation results.
more » « less- NSF-PAR ID:
- 10411042
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- International Journal for Numerical and Analytical Methods in Geomechanics
- Volume:
- 47
- Issue:
- 7
- ISSN:
- 0363-9061
- Page Range / eLocation ID:
- p. 1103-1133
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract x [Al2O3]2[SiO2]98−x withx = 7, 12, 17, and 22 were synthesized and analyzed with IR and Raman. A silica glass substrate and a crystalline quartz were also analyzed for comparison. Glass structures with the same compositions were generated with MD simulations using three types of potentials: fixed partial charge pairwise (Teter), partial diffuse charge potential (MGFF), and bond order‐based charge transfer potential (ReaxFF). The comparison of simulated and experimental IR spectra showed that, among these three potentials tested, ReaxFF reproduces the concentration dependence of spectral features closest to the experimentally observed trend. Thus, the bond length and angle distributions as well as Si–Qn species and ring size distributions of silica and sodium silicate glasses were obtained from ReaxFF‐MD simulations and further compared with the peak assignment or deconvolution schemes—which have been widely used since 1970s and 1980s—(a) correlation between the IR peak position in the Si–O stretch region (1050‐1120 cm−1) and the Si–O–Si bond angle; (b) deconvolution of the Raman bands in the Si–O stretch region with theQn speciation; and (c) assignment of the Raman bands in the 420‐600 cm−1region to the bending modes of (SiO)n rings with different sizes (typically, n = 3‐6). The comparisons showed that none of these widely used methods is congruent with the bond parameters or structures of silicate glass networks produced via ReaxFF‐MD simulations. This finding invokes that the adequacy of these spectral interpretation methods must be questioned. Alternative interpretations are proposed, which are to be tested independently in future studies. -
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null (Ed.)Recent theoretical and computational progress has led to unprecedented understanding of symmetry-breaking instabilities in 2D dynamic fracture. At the heart of this progress resides the identification of two intrinsic, near crack tip length scales — a nonlinear elastic length scale ℓ and a dissipation length scale ξ — that do not exist in Linear Elastic Fracture Mechanics (LEFM), the classical theory of cracks. In particular, it has been shown that at a propagation velocity v of about 90% of the shear wave-speed, cracks in 2D brittle materials undergo an oscillatory instability whose wavelength varies linearly with ℓ, and at larger loading levels (corresponding to yet higher propagation velocities), a tip-splitting instability emerges, both in agreements with experiments. In this paper, using phase-field models of brittle fracture, we demonstrate the following properties of the oscillatory instability: (i) It exists also in the absence of near-tip elastic nonlinearity, i.e. in the limit ℓ→0, with a wavelength determined by the dissipation length scale ξ. This result shows that the instability crucially depends on the existence of an intrinsic length scale associated with the breakdown of linear elasticity near crack tips, independently of whether the latter is related to nonlinear elasticity or to dissipation. (ii) It is a supercritical Hopf bifurcation, featuring a vanishing oscillations amplitude at onset. (iii) It is largely independent of the phenomenological forms of the degradation functions assumed in the phase-field framework to describe the cohesive zone, and of the velocity-dependence of the fracture energy Γ(v) that is controlled by the dissipation time scale in the Ginzburg-Landau-type evolution equation for the phase-field. These results substantiate the universal nature of the oscillatory instability in 2D. In addition, we provide evidence indicating that the tip-splitting instability is controlled by the limiting rate of elastic energy transport inside the crack tip region. The latter is sensitive to the wave-speed inside the dissipation zone, which can be systematically varied within the phase-field approach. Finally, we describe in detail the numerical implementation scheme of the employed phase-field fracture approach, allowing its application in a broad range of materials failure problems.more » « less
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Abstract Understanding surface reactions of silicate glass under interfacial shear is critical as it can provide physical insights needed for rational design of more durable glasses. Here, we performed reactive molecular dynamics (MD) simulations with ReaxFF potentials to study the mechanochemical wear of sodium silicate glass rubbed with amorphous silica in the absence and presence of interfacial water molecules. The effect of water molecules on the shear‐induced chemical reaction at the sliding interface was investigated. The dependence of wear on the number of interfacial water molecules in ReaxFF‐MD simulations was in reasonable agreement with the experimental data. Confirming this, the ReaxFF‐MD simulation was used to find further details of atomistic reaction dynamics that cannot be obtained from experimental investigations only. The simulation showed that the severe wear in the dry condition is due to the formation of interfacial Sisubstrate–O–Sicounter_surfacebond that convey the interfacial shear stress to the subsurface and the presence of interfacial water reduces the interfacial bridging bond formation. The leachable sodium ions facilitate surface reactions with water‐producing hydroxyl groups and their key role in the hydrolysis reaction is discussed.
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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.
