Colorimetric quantification of linking in thermoreversible nanocrystal gel assemblies

Nanocrystal gel networks can be responsive, tunable materials, but deliberately designing their structure and controlling their properties have been challenging. By employing reversibly bonded molecular linkers, gelation can be realized under conditions predicted by thermodynamics. But, simulations have offered the only microscopic insights, with no experimental means to monitor linking leading to gelation. Here, we introduce a metal coordination linkage with a distinct optical signature allowing us to quantify linking in situ and establish the structural and thermodynamic basis for assembly. Due to coupling between linked indium tin oxide nanocrystals, their infrared absorption shifts abruptly at a chemically tunable gelation temperature. We quantify bonding spectroscopically and use molecular dynamics simulations to understand bonding motifs as a function of temperature, revealing that gel formation is governed by reaching a critical number of effective links that extend the nanocrystal network. Microscopic insights from our colorimetric linking chemistry enable switchable gels based on equilibrium thermodynamic principles, opening the door to rational design of programmable nanocrystal net-work assemblies.

A study on deformation-induced degradation of the compressible polymeric pressurized vessel through a non-equilibrium thermodynamic framework

The present paper investigates the degradation of compressible polymers based on the proposed model on strain-induced degradation of incompressible polymers. In a non-equilibrium thermodynamic framework, constitutive equations and evolution laws are derived using the principle of maximum energy dissipation rate and specifying how energy can be stored and dissipated. As a computational model, the governing equations are applied to the pressurized polymeric vessel subjected to the Ogden–Hill compressible hyperelastic material model. To analyze the axisymmetric plane-strain degradable vessel, programming in ANSYS Parametric Design Language (APDL) and the Standard Galerkin Finite Element Method (SGFEM) are applied. The results show that the degradable compressible Ogden–Hill model can also predict the degradation of incompressible polymers subjected to the neo-Hookean model. Results also reveal that the highest dissipation rate and material softening occur at the inner radius of the inflated degradable vessel. Creep-like and stress-relaxation-like responses of the polymeric vessel with time-position-dependent material properties are examined. ANSYS coding indicates good accuracy and efficiency in studying the compressible vessel subjected to inhomogeneous degradation.