Thermodynamic insight into stimuli-responsive behaviour of soft porous crystals

Knowledge of the thermodynamic potential in terms of the independent variables allows to characterize the macroscopic state of the system. However, in practice, it is difficult to access this potential experimentally due to irreversible transitions that occur between equilibrium states. A showcase example of sudden transitions between (meta) stable equilibrium states is observed for soft porous crystals possessing a network with long-range structural order, which can transform between various states upon external stimuli such as pressure, temperature and guest adsorption. Such phase transformations are typically characterized by large volume changes and may be followed experimentally by monitoring the volume change in terms of certain external triggers. Herein, we present a generalized thermodynamic approach to construct the underlying Helmholtz free energy as a function of the state variables that governs the observed behaviour based on microscopic simulations. This concept allows a unique identification of the conditions under which a material becomes flexible

Raman spectroscopic determination of the length, strength, compressibility, Debye temperature, elasticity, and force constant of the C-C bond in graphene

From the perspective of bond relaxation and vibration, we have reconciled the Raman shifts of graphene under the stimuli of the number-of-layer, uni-axial-strain, pressure, and temperature in terms of the response of the length and strength of the representative bond of the entire specimen to the applied stimuli. Theoretical unification of the measurements clarifies that: (i) the opposite trends of Raman shifts due to number-of-layer reduction indicate that the G-peak shift is dominated by the vibration of a pair of atoms while the D- and the 2D-peak shifts involves z-neighbor of a specific atom; (ii) the tensile strain-induced phonon softening and phonon-band splitting arise from the asymmetric response of the C3v bond geometry to the C2v uni-axial bond elongation; (iii) the thermal-softening of the phonons originates from bond expansion and weakening; and (iv) the pressure- stiffening of the phonons results from bond compression and work hardening. Reproduction of the measurements has led to quantitative information about the referential frequencies from which the Raman frequencies shift, the length, energy, force constant, Debye temperature, compressibility, elastic modulus of the C-C bond in graphene, which is of instrumental importance to the understanding of the unusual behavior of graphene

Nanomechanics and intermolecular forces of amyloid revealed by four-dimensional electron microscopy

The amyloid state of polypeptides is a stable, highly organized structural form consisting of laterally associated β-sheet protofilaments that may be adopted as an alternative to the functional, native state. Identifying the balance of forces stabilizing amyloid is fundamental to understanding the wide accessibility of this state to peptides and proteins with unrelated primary sequences, various chain lengths, and widely differing native structures. Here, we use four-dimensional electron microscopy to demonstrate that the forces acting to stabilize amyloid at the atomic level are highly anisotropic, that an optimized interbackbone hydrogen-bonding network within β-sheets confers 20 times more rigidity on the structure than sequence-specific sidechain interactions between sheets, and that electrostatic attraction of protofilaments is only slightly stronger than these weak amphiphilic interactions. The potential biological relevance of the deposition of such a highly anisotropic biomaterial in vivo is discussed

Aircraft engine hot section technology: An overview of the HOST Project

NASA sponsored the Turbine Engine Hot Section (HOST) project to address the need for improved durability in advanced aircraft engine combustors and turbines. Analytical and experimental activities aimed at more accurate prediction of the aerothermal environment, the thermomechanical loads, the material behavior and structural responses to loads, and life predictions for cyclic high temperature operation were conducted from 1980 to 1987. The project involved representatives from six engineering disciplines who are spread across three work disciplines - industry, academia, and NASA. The HOST project not only initiated and sponsored 70 major activities, but also was the keystone in joining the multiple disciplines and work sectors to focus on critical research needs. A broad overview of the project is given along with initial indications of the project's impact

Reduced thermal expansion by surface-mounted nanoparticles in a pillared-layered metal-organic framework

Control of thermal expansion (TE) is important to improve material longevity in applications with repeated temperature changes or fluctuations. The TE behavior of metal-organic frameworks (MOFs) is increasingly well understood, while the impact of surface-mounted nanoparticles (NPs) on the TE properties of MOFs remains unexplored despite large promises of NP@MOF composites in catalysis and adsorbate diffusion control. Here we study the influence of surface-mounted platinum nanoparticles on the TE properties of Pt@MOF (Pt@Zn2(DP-bdc)2dabco; DP-bdc2-=2,5-dipropoxy-1,4-benzenedicarboxylate, dabco=1,4-diazabicyclo[2.2.2]octane). We show that TE is largely retained at low platinum loadings, while high loading results in significantly reduced TE at higher temperatures compared to the pure MOF. These findings support the chemical intuition that surface-mounted particles restrict deformation of the MOF support and suggest that composite materials exhibit superior TE properties thereby excluding thermal stress as limiting factor for their potential application in temperature swing processes or catalysis

Deblocking of interacting particle assemblies: from pinning to jamming

A wide variety of interacting particle assemblies driven by an external force are characterized by a transition between a blocked and a moving phase. The origin of this deblocking transition can be traced back to the presence of either external quenched disorder, or of internal constraints. The first case belongs to the realm of the depinning transition, which, for example, is relevant for flux-lines in type II superconductors and other elastic systems moving in a random medium. The second case is usually included within the so-called jamming scenario observed, for instance, in many glassy materials as well as in plastically deforming crystals. Here we review some aspects of the rich phenomenology observed in interacting particle models. In particular, we discuss front depinning, observed when particles are injected inside a random medium from the boundary, elastic and plastic depinning in particle assemblies driven by external forces, and the rheology of systems close to the jamming transition. We emphasize similarities and differences in these phenomena.Comment: 20 pages, 8 figures, submitted for a special issue of the Brazilian Journal of Physics entitled: Statistical Mechanics of Irreversible Stochastic Models - I

Nanoscale metamaterials: Meta-MOFs and framework materials with anomalous behavior

International audienceAs the number of framework materials known and characterized in the literature grows, it becomes apparent that they can carry properties rarely encountered in more conventional, dense inorganic materials. Among these materials with unusual physical or chemical properties are the ubiquitous metal-organic frameworks, covalent organic frameworks, dense coordination polymers, and molecular frameworks. Many can respond to stimulation by displaying structural responses and changes in properties that range from counter-intuitive to thermodynamically forbidden. In that, they share large similarities with metamaterials, which are engineered to generate properties not found in “normal” materials. We review here the surprising behavior of these meta-MOFs and other framework materials that display properties “beyond” (μετά) the boundaries of common crystalline materials