Abstract The impact of microstructure on hardness in phase‐separated calcium aluminosilicate glasses is investigated. Changes in hardness are governed by microstructure deformations that occur during indentation. Phase separation leads to decreased hardness due to the incongruent yielding of the droplet and matrix phases. Moreover, the deformation of microstructures possessing dilute, spherical droplets did not have a significant impact on hardness. Microstructures characterized by concentrated, acicular droplets were found to deform through a process of droplet coalescence. This process absorbs additional energy during yielding and results in glasses that deform through droplet coalescence possessing improved hardness.
more »
« less
Microstructural evolution of droplet phase separation in calcium aluminosilicate glasses
Abstract Glasses with nanoscale phase separation have the potential to possess improved hardness and fracture toughness while maintaining their optical transparency. Here we present the results of isothermal heat treatments of phase‐separated calcium aluminosilicate glasses. Our results indicate that a transition from Lifshitz–Slozof–Wagner (LSW)‐type kinetics to a diffusion‐controlled pseudo‐coalescence mechanism occurs at ~17% droplet volume fraction, which results in the droplets becoming increasingly elongated and interconnected. The activation barrier for both mechanisms suggests that calcium diffusion is the underlying means for the coarsening of the silica‐rich domains. Simple approximations show the transition cannot be explained by Brownian motion or Van der Waals attraction between domains, and instead suggest various osmotic forces may be responsible.
more »
« less
- Award ID(s):
- 1762275
- PAR ID:
- 10367499
- Publisher / Repository:
- Wiley-Blackwell
- Date Published:
- Journal Name:
- Journal of the American Ceramic Society
- Volume:
- 105
- Issue:
- 1
- ISSN:
- 0002-7820
- Page Range / eLocation ID:
- p. 193-206
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract The dissolution of silicate glasses has implications in diverse fields ranging from the immobilization of radioactive waste to the development of sustainable alternatives to Portland cement. Here, we used ab initio molecular dynamics simulations biased with well-tempered metadynamics to study Si-O-T bridge dissociation in calcium aluminosilicate glasses, crucial for understanding their dissolution. In a departure from the conventional Michalske-Freiman model, our findings reveal a nucleophilic substitution reaction mechanism characterized by a short-lived, 5-fold coordinated Si intermediate or transition state, depending on the Si bridge coordination, with a near-trigonal bipyramidal geometry. We find that the reorganization required for reaching this state causes the activation energy barriers to be dependent on the Si bridge coordination, with Si Q3species serving as the rate-limiting step in the dissolution reaction. Our findings not only challenge long-standing theoretical models but also pave the way for more accurate and comprehensive frameworks for understanding the dissolution of silicate glasses in various applications.more » « less
-
null (Ed.)The method of surface grating decay has been used to measure surface diffusion in the glasses of two rod-like molecules posaconazole (POS) and itraconazole (ITZ). Although structurally similar antifungal medicines, ITZ forms liquid-crystalline phases while POS does not. Surface diffusion in these systems is significantly slower than in the glasses of quasi-spherical molecules of similar volume when compared at the glass transition temperature T g . Between the two systems, ITZ has slower surface diffusion. These results are explained on the basis of the near-vertical orientation of the rod-like molecules at the surface and their deep penetration into the bulk where mobility is low. For molecular glasses without extensive hydrogen bonds, we find that the surface diffusion coefficient at T g decreases smoothly with the penetration depth of surface molecules and the trend has the double-exponential form for the surface mobility gradient observed in simulations. This supports the view that these molecular glasses have a similar mobility vs. depth profile and their different surface diffusion rates arise simply from the different depths at which molecules are anchored. Our results also provide support for a previously observed correlation between the rate of surface diffusion and the fragility of the bulk liquid.more » « less
-
Abstract Much attention has been devoted to water’s metastable phase behavior, including polyamorphism (multiple amorphous solid phases), and the hypothesized liquid-liquid transition and associated critical point. However, the possible relationship between these phenomena remains incompletely understood. Using molecular dynamics simulations of the realistic TIP4P/2005 model, we found a striking signature of the liquid-liquid critical point in the structure of water glasses, manifested as a pronounced increase in long-range density fluctuations at pressures proximate to the critical pressure. By contrast, these signatures were absent in glasses of two model systems that lack a critical point. We also characterized the departure from equilibrium upon vitrification via the non-equilibrium index; water-like systems exhibited a strong pressure dependence in this metric, whereas simple liquids did not. These results reflect a surprising relationship between the metastable equilibrium phenomenon of liquid-liquid criticality and the non-equilibrium structure of glassy water, with implications for our understanding of water phase behavior and glass physics. Our calculations suggest a possible experimental route to probing the existence of the liquid-liquid transition in water and other fluids.more » « less
-
Abstract Ferroelastic BiVO4has charged surface domains, even though its crystal structure is non‐polar. These charged domains can be detected by piezo‐force microscopy and lead to spatially selective photochemical reactions. The photochemical reactivity of (Bi0.96Na0.04)(V0.92Mo0.08)O4is studied above and below the ferroelastic transition temperature to better understand the origin of charged ferroelastic domains. The results demonstrate that spatially selective reactivity occurs above the ferroelastic transition temperature, similar to what is observed below the transition temperature. Furthermore, when the sample is cooled after brief excursions above the transition temperature, the domains reform with a microstructure that is indistinguishable from what is observed before the transition. The results are consistent with the idea that inhomogeneous distributions of charged point defects, created by stress in the ferroelastic domains, lead to charged domains that promote spatially selective photochemical reactions. If these inhomogeneous defect distributions are not homogenized above the transition temperature, they can template the re‐creation of the original domain microstructure after the transformation back to the ferroelastic phase.more » « less