Mathematical and physical aspects of the applicability of the Onsager, Prigogine as well as the Glansdorff and Ziegler thermodynamic extremal principles (TEPs) to non-equilibrium thermodynamics are ...examined for systems at fixed temperature with respect to their ability to provide kinetic equations approved in materials science. TEPs represent an alternative to the classical phenomenological equations approach. As TEPs are, more or less, a pure mathematical tool, they cannot significantly contribute to a deeper physical understanding. However, if a system can be described by discrete characteristic (thermodynamic) parameters, it is demonstrated that application of Onsager’s TEP or Ziegler’s TEP represents a systematic way to derive a set of explicit evolution equations for these parameters. This approach can significantly simplify the treatment of the problem and, thus, can also be applied to rather complex systems, for which the classical approach, involving application of phenomenological equations, fails. The application of TEPs is demonstrated on plasticity with respect to constitutive equations as well as on grain growth and coarsening with respect to evolution equations of discrete parameters. No exploitation of Prigogine’s TEP has been reported for applications in materials science. Contrarily, Prigogine’s TEP can be invalidated if the coefficients of the dissipation function depend on the evolution of state variables with time. This is demonstrated by a further practical example worked out for the solute drag phenomenon. Glansdorff’s and Prigogine’s evolution criterion, however, is always fulfilled near the equilibrium state of convex Gibbs energy. Extensions of TEPs to non-linear non-equilibrium thermodynamics are demonstrated for homogeneous and quasi-homogeneous dissipation functions.
Thermoelectric technology, which possesses potential application in recycling industrial waste heat as energy, calls for novel high-performance materials. The systematic exploration of novel ...thermoelectric materials with excellent electronic transport properties is severely hindered by limited insight into the underlying bonding orbitals of atomic structures. Here we propose a simple yet successful strategy to discover and design high-performance layered thermoelectric materials through minimizing the crystal field splitting energy of orbitals to realize high orbital degeneracy. The approach naturally leads to design maps for optimizing the thermoelectric power factor through forming solid solutions and biaxial strain. Using this approach, we predict a series of potential thermoelectric candidates from layered CaAl2Si2-type Zintl compounds. Several of them contain nontoxic, low-cost and earth-abundant elements. Moreover, the approach can be extended to several other non-cubic materials, thereby substantially accelerating the screening and design of new thermoelectric materials.
Faced with a comparatively limited palette of minerals and organic polymers as building materials, evolution has arrived repeatedly on structural solutions that rely on clever geometric arrangements ...to avoid mechanical trade-offs in stiffness, strength and flexibility. In this tutorial review, we highlight the concept of tessellation, a structural motif that involves periodic soft and hard elements arranged in series and that appears in a vast array of invertebrate and vertebrate animal biomaterials. We start from basic mechanics principles on the effects of material heterogeneities in hypothetical structures, to derive common concepts from a diversity of natural examples of one-, two- and three-dimensional tilings/layerings. We show that the tessellation of a hard, continuous surface - its atomization into discrete elements connected by a softer phase - can theoretically result in maximization of material toughness, with little expense to stiffness or strength. Moreover, the arrangement of soft/flexible and hard/stiff elements into particular geometries can permit surprising functions, such as signal filtering or 'stretch and catch' responses, where the constrained flexibility of systems allows a built-in safety mechanism for ensuring that both compressive and tensile loads are managed well. Our analysis unites examples ranging from exoskeletal materials (fish scales, arthropod cuticle, turtle shell) to endoskeletal materials (bone, shark cartilage, sponge spicules) to attachment devices (mussel byssal threads), from both invertebrate and vertebrate animals, while spotlighting success and potential for bio-inspired manmade applications.
Two- or three-dimensional tiling improves the fracture resistance of natural and bioinspired materials and may even provide additional functionality.
The total synthesis of the Lycopodium alkaloid complanadine A, which is an unsymmetrical dimer of lycodine, was achieved by exploiting a common tetracyclic precursor. Key to the success of the ...synthesis was the development of a late-stage site-selective C−H functionalization of a pyridine moiety to arrive at a key boronic ester intermediate.
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Twisted plywood architectures can be observed in many biological materials with high fracture toughness, such as in arthropod cuticles or in lamellar bone. Main purpose of this paper ...is to analyze the influence of the progressive rotation of the fiber direction on the spatial variation of the crack driving force and, thus, on the fracture toughness of plywood-like structures. The theory of fiber composites is used to describe the stiffness matrix of a twisted plywood structure in a specimen-fixed coordinate system. The driving force acting on a crack propagating orthogonally to the fiber-rotation plane is studied by methods of computational mechanics, coupled with the concept of configurational forces. The analysis unfolds a spatial variation of the crack driving force with minima that are beneficial for the fracture toughness of the material. It is shown that the estimation of the crack driving force can be simplified by replacing the complicated anisotropic twisted plywood structure by an isotropic material with appropriate periodic variations of Young’s modulus, which can be constructed based either on the local stiffness or local strain energy density variations. As practical example, the concepts are discussed for a specimen with a stiffness anisotropy similar to lamellar bone.
Twisted plywood-like structures exist in many natural fiber composites, such as bone or insect carapaces, and are known to be very fracture resistant. The crack driving force in such materials is analyzed quantitatively for the first time, using the concept of configurational forces. This tool, well established in the mechanics of materials, is introduced to the modeling of biological material systems with inhomogeneous and anisotropic material behavior. Based on this analysis, it is shown that the system can be approximated by an appropriately chosen inhomogeneous but isotropic material for the calculation of the crack driving force. The spatial variation of the crack driving force and, especially, its local minima are essential to describe the fracture properties of twisted plywood structures.
Two of the most productive lines of social science inquiry in recent years come from the study of 'values' and that of 'infrastructures.' Not coincidentally, both are capacious terms. Values are ...plastic and dynamic, constantly and creatively deployed and reinterpreted - yet their power is legitimated by a seeming durability, their connection to something transcendent as recognised by social conventions. In turn, infrastructures are characterised by their durability - yet, they are constantly and creatively employed and repurposed in practice. Bringing these two approaches together, the synthesis presented in this collection reveals how infrastructures encode social, political, and cultural (as well as economic) values through social conventions, and how they facilitate and shape capitalist accumulation by connecting heterogeneous value worlds.
The landforms of northern Gale crater on Mars expose thick sequences of sedimentary rocks. Based on images obtained by the Curiosity rover, we interpret these outcrops as evidence for past fluvial, ...deltaic, and lacustrine environments. Degradation of the crater wall and rim probably supplied these sediments, which advanced inward from the wall, infilling both the crater and an internal lake basin to a thickness of at least 75 meters. This intracrater lake system probably existed intermittently for thousands to millions of years, implying a relatively wet climate that supplied moisture to the crater rim and transported sediment via streams into the lake basin. The deposits in Gale crater were then exhumed, probably by wind-driven erosion, creating Aeolis Mons (Mount Sharp).
A new model for the evolution of the precipitate structure derived by means of application of the thermodynamic extremum principle is presented. The model describes the evolution of the radii and of ...the chemical composition of individual precipitates of different phases in the multi-component system. In connection with a proper theory of nucleation, the model is able to describe the evolution of the precipitate structure in the classical stages of nucleation, growth and coarsening as well as interaction of precipitates of different phases, of different chemical composition and of different sizes via diffusion in the matrix.
The coarsening of precipitates in a matrix with a non-zero volume fraction is treated by assuming that the exchange of matter between the precipitates occurs by diffusion in the matrix within finite ...zones surrounding the precipitates. The thermodynamic extremal principle is used for the derivation of evolution equations for the precipitate radii. Accordingly, non-steady-state and steady-state distribution functions are deduced, depending on the system parameter characterizing the finite diffusion zones. The distribution functions tend exactly to the established Lifshitz–Slyozov–Wagner distribution for a zero volume fraction of the precipitates. The steady-state distribution functions are expressed by means of distinct volume-fraction-dependent parameters, which are presented by analytical expressions and in diagrams. To treat non-steady-state systems, ensembles of up to 106 precipitates can easily be handled by standard computational methods.
The process by which visual information is incorporated into the brain's spatial framework to represent landmarks is poorly understood. Studies in humans and rodents suggest that retrosplenial cortex ...(RSC) plays a key role in these computations. We developed an RSC-dependent behavioral task in which head-fixed mice learned the spatial relationship between visual landmark cues and hidden reward locations. Two-photon imaging revealed that these cues served as dominant reference points for most task-active neurons and anchored the spatial code in RSC. This encoding was more robust after task acquisition. Decoupling the virtual environment from mouse behavior degraded spatial representations and provided evidence that supralinear integration of visual and motor inputs contributes to landmark encoding. V1 axons recorded in RSC were less modulated by task engagement but showed surprisingly similar spatial tuning. Our data indicate that landmark representations in RSC are the result of local integration of visual, motor, and spatial information.
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