An official website of the United States government
Introducing molecular nanolayers (MNLs) is attractive for enhancing the stability of, and inducing unusual properties at, inorganic thin film interfaces. Although organic molecules anchored to inorganic surfaces have been studied extensively, property enhancement mechanisms underpinned by molecular assemblies at inorganic thin film interfaces are yet to be revealed and understood. Here, ab initio molecular dynamics simulations of tensile strain of Au/MNL/Au thin film nanosandwich models provide insights into molecularly induced strain hardening and toughening. Au/MNL/Au nanosandwiches support up to ≈30% higher stresses and exhibit up to ≈140% higher toughness than pure Au slab models. Both hardening and toughening are governed by molecular length and terminal chemistry in the MNL. Strong Au/MNL interface bonding and greater molecular length promote defect creation in Au, which results in strain hardening. Accommodation of increasing post-hardening strains in the MNL mitigates the stress increase in the Au slabs, delays interface fracture, and contributes to toughening. Remarkably, toughening correlates with equilibrium interface strain, which could be used as a proxy for efficiently identifying promising inorganic/MNL combinations that provide toughening. Our findings are important for the discovery and design of inorganic–organic interfaces, nanomaterials, and composites.
more »
« less
This content will become publicly available on December 24, 2025
Enhancing Toughness and Microstructural Memory by Coupling Crystallinity, Elasticity, and Plasticity in Layered Materials Composed of Liquid Crystalline Oligomers
Molecular dynamics simulations are used to show that triblock oligomers which are first preassembled into a lamellar phase and then crosslinked, exhibit high extensibility and toughness in response to uniaxial tensile deformation parallel to the layer stacking. A coarse-grained model is adopted based on a coil-rod-coil oligomer capped with crosslinkable units. Upon uniaxial strain, a buckling instability ensues in the uncrosslinked systems, which eventually leads to defective lamellar ‘islands’ as the stress drops off. In contrast, a toughening behavior, manifested as a ‘saw-tooth’ stress-strain profile, is observed in the crosslinked systems, which is associated with ‘recrystallization’ of the rod domains mediated by the inter-layer bonds formed upon crosslinking. It is also shown that this toughening mechanism can be encoded in longer multilayer-spanning oligomer designs that forsake the crosslinking step. These structures, which integrate rigidity, elasticity, and plasticity, could be leveraged to experimentally realize novel materials with shape-memory and self-healing properties.
more »
« less
- Award ID(s):
- 2414548
- PAR ID:
- 10592195
- Publisher / Repository:
- American Chemical Society Publications
- Date Published:
- Journal Name:
- Macromolecules
- Volume:
- 57
- Issue:
- 24
- ISSN:
- 0024-9297
- Page Range / eLocation ID:
- 11550 to 11564
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract Dynamic hydrogel crosslinking captures network reorganization and self‐healing of natural materials, yet is often accompanied by reduced mechanical properties compared to covalent analogs. Toughening is possible in certain materials with processing by directional freeze‐casting and salting‐out, producing hierarchically organized networks with directionally enhanced mechanical properties. The implications of including dynamic supramolecular crosslinking alongside such processes are unclear. Here, a supramolecular hydrogel prepared from homoternary crosslinking by pendant guests with a free macrocycle is subsequently processed by directional freeze‐casting and salting‐out. The resulting hydrogels tolerate multiple cycles of compression. Excitingly, supramolecular affinity dictates the mechanical properties of the bulk hydrogels, with higher affinity interactions producing materials with higher Young's modulus and enhanced toughness under compression. The importance of supramolecular crosslinking is emphasized with a supramolecular complex that is converted in situ into a covalent crosslink. While supramolecular hydrogels do not fracture and spontaneously self‐heal when cut, their covalent analogs fracture under moderate strain and do not self‐heal. This work shows a molecular‐scale origin of bulk hydrogel toughening attributed to affinity and dynamics of supramolecular crosslinking, offering synergy in combination with bulk post‐processing techniques to yield materials with enhanced mechanical properties tunable at the molecular scale for the needs of specific applications.more » « less
-
TBF 1180 steel was plastically deformed under different strain paths in order to study both the ductility and RA transformation rates. Specimens were prepared from a 1 mm thick sheet and then tested incrementally under uniaxial tension, plane-strain tension, and biaxial tension. The retained austenite (RA) levels were measured, as a function of the plastic strain, using electron backscatter diffraction (EBSD). The plane-strain tension specimens had the fastest rate of RA transformation as a function of strain, followed by uniaxial tension, and then biaxial tension. The forming limits were measured for each strain path, yielding major limit strains of 0.12 under uniaxial tension, 0.09 under plane-strain tension, and 0.16 under biaxial tension. These results were compared to prior work on a 1.2 mm Q&P 1180 steel sheet, which had a similar yield and ultimate tensile strength, but exhibited slightly greater forming limits than the TBF material. The visual inspection of the micrographs appeared to show an equiaxed RA morphology in the Q&P 1180 steel and a mixture of equiaxed and lamellar RA grains in the TBF 1180 steel. However, the statistics generated by EBSD revealed that both alloys had RA grains with essentially the same aspect ratios. The average RA grain size in the Q&P alloy was found to be about three times larger than that of the TBF alloy. As such, the small but consistent formability advantage exhibited by the Q&P 1180 alloy along all three strain paths can be attributed to its larger average RA grain size, where larger RA grain sizes correlated with a more gradual transformation rate.more » « less
-
Abstract Most elastomers undergo strain‐induced crystallization (SIC) under tension; as individual chains are held rigidly in a fixed position by an applied strain, their alignment along the strain field results in a shift from strain‐hardening (SH) to SIC. A similar degree of stretching is associated with the tension necessary to accelerate mechanically coupled, covalent chemical responses of mechanophores in overstretched chains, raising the possibility of an interplay between the macroscopic response of SIC and the molecular response of mechanophore activation. Here, thiol‐yne‐derived stereoelastomers doped covalently with a dipropiolate‐derivatized spiropyran (SP) mechanophore (0.25–0.38 mol%) are reported. The material properties of SP‐containing films are consistent with undoped controls, indicating that the SP is a reporter of the mechanical state of the polymer. Uniaxial tensile tests reveal correlations between mechanochromism and SIC, which are strain‐rate‐dependent. When mechanochromic films are stretched slowly to the point of mechanophore activation, the covalently tethered mechanophore remains trapped in a force‐activated state, even after the applied stress is removed. Mechanophore reversion kinetics correlate with the applied strain rate, resulting in highly tunable decoloration rates. Because these polymers are not covalently crosslinked, they are recyclable by melt‐pressing into new films, increasing their potential range of strain‐sensing, morphology‐sensing, and shape‐memory applications.more » « less
-
Photocrosslinkable precursors (small molecules or polymers) undergo rapid crosslinking upon photoirradiation, forming covalently crosslinked hydrogels. The spatiotemporally controlled crosslinking, which can be achieved in situ , encourages the utility of photocrosslinked hydrogels in biomedicine as bioadhesives, bioprinting inks, and extracellular matrix mimics. However, the low viscosity of the precursor solutions results in unwanted flows and dilution, leading to handling difficulties and compromised strength of the photocrosslinked hydrogels. Here, we introduce oppositely charged triblock polyelectrolytes as additives for precursor solutions that transform them into self-assembled polyelectrolyte complex (PEC) hydrogels with enhanced shear strength and viscosity, providing interim protection against precursor dilution and mitigating secondary flows. The PEC network also augments the properties of the photocrosslinked hydrogels. Crosslinking of the precursors upon photoirradiation results in the formation of interpenetrating polymer network hydrogels with PEC and covalently-linked networks that exhibit shear moduli exceeding the linear combination of the moduli of the constituent networks and overcome the tensile strength–extensibility tradeoff that restricts the performance of covalently-linked hydrogels. The reinforcement approach is shown to be compatible with four types of photocrosslinkable precursors, does not require any modification of the precursors, and introduces minimal processing steps, paving the way for a broader translation of photocrosslinkable materials for biomedical applications.more » « less
