arXiv subjects

Natascha Gray

Publications and source records attributed to Natascha Gray.

3 recordsLinked to original sources

arXiv2025

Adaptive hydrogels with spatiotemporal stiffening using pH-modulating enzymes

Biological systems achieve adaptive mechanical responses through reaction-diffusion processes that couple chemical wave propagation to structural transitions. Although synthetic hydrogels with enzymatic reactions offer a platform for replicating such autonomous behavior, the mechanistic principles governing chemomechanical transduction remain poorly understood. Here, we present a glucose oxidase-embedded polyacrylamide-alginate hydrogel with slower transduction kinetics that enable independent resolution of chemical waves and mechanical adaptation. Enzymatic pH waves propagate at 15-44 um/min, triggering calcium-mediated alginate crosslinking through pH-responsive calcium-EDTA dissociation. Independent tracking of chemical and mechanical waves reveals that mechanical wavefronts (12 um/min) lag behind chemical propagation, establishing transduction as the rate-limiting step in this chemomechanical coupling. Remarkably, the enzymatic system must continuously supply chemical energy to both propagate the chemical wave and drive ongoing mechanical transitions, imposing energetic costs on reaction-diffusion beyond kinetic constraints alone. Our adaptive system achieves up to 2.1-fold increase in stiffness and enables autonomous conversion of localized stimuli into system-wide mechanical responses. These mechanistic insights establish design principles for engineering adaptive materials with predictable spatiotemporal control in soft robotics and biomedical applications.

cond-mat.soft↗

arXiv2025

Control of polarization and polar chiral textures in BiFeO$_3$ by epitaxial strain and interfacial chemistry

The balance between interfacial chemistry, electrostatics, and epitaxial strain plays a crucial role in stabilizing polarization in ferroelectric thin films. Here, we bring these contributions into competition in BiFeO$_3$ (BFO) thin films grown on the charged-surface-terminated La$_{0.7}$Sr$_{0.3}$MnO$_3$ (LSMO)-buffered NdGaO$_3$ (001) substrates. The large anisotropic compressive strain from the substrate promotes the formation of ferroelectric domains despite the expected stabilization of a uniform out-of-plane polarization by the (La,Sr)O$^{0.7+}$ termination of the metallic buffer. Piezoresponse force microscopy and scanning transmission electron microscopy reveal that the resulting nanoscale domain architecture is stabilized by the deterministic formation of a fluorite-like Bi$_2$O$_2$ surface layer on regions polarized oppositely to the LSMO-imposed polarization orientation. Leveraging this polarization compensation mechanism, we stabilize a uniform out-of-plane polarization in our highly strained BFO films by inserting a Bi$_2$O$_2$-terminated Aurivillius film as a buffer layer. Additionally, we reveal signatures of homochiral polarization textures in our BFO films on the level of domain configurations using local polarization switching experiments. Our work thus brings new strategies for controlling polarization direction and chiral textures in oxide ferroelectrics, opening pathways for functional domain-wall and domain-based electronics.

cond-mat.mtrl-sci↗

arXiv2022

Defeating depolarizing fields with artificial flux closure in ultrathin ferroelectrics

Material surfaces encompass structural and chemical discontinuities that often lead to the loss of the property of interest in the so-called dead layers. It is notably problematic in nanoscale oxide electronics, where the integration of strongly correlated materials into devices is obstructed by the thickness threshold required for the emergence of their functionality. Here, we report the stabilization of ultrathin out-of-plane ferroelectricity in oxide heterostructures through the design of an artificial flux-closure architecture. Inserting an in-plane polarized ferroelectric epitaxial buffer provides continuity of polarization at the interface, and despite its insulating nature we observe the emergence of polarization in our out-of-plane-polarized model ferroelectric BaTiO$_{3}$ from the very first unit cell. In BiFeO$_{3}$, the flux-closure approach stabilizes a conceptually novel 251$^{\circ}$ domain wall. Its unusual chirality is likely associated with the ferroelectric analog to the Dzyaloshinskii-Moriya interaction. We thus see that in an adaptively engineered geometry, the depolarizing-field-screening properties of an insulator can even surpass those of a metal and be a source of new functionalities. This should be a useful insight on the road towards the next generation of ferroelectric-based oxide electronics.

cond-mat.mtrl-sci↗