Deposits of clastic carbonate-dominated (calciclastic) sedimentary slope systems in the rock record have been identified mostly as linearly-consistent carbonate apron deposits, even though most ancient clastic carbonate slope deposits fit the submarine fan systems better. Calciclastic submarine fans are consequently rarely described and are poorly understood. Subsequently, very little is known especially in mud-dominated calciclastic submarine fan systems. Presented in this study are a sedimentological core and petrographic characterisation of samples from eleven boreholes from the Lower Carboniferous of Bowland Basin (Northwest England) that reveals a >250 m thick calciturbidite complex deposited in a calciclastic submarine fan setting. Seven facies are recognised from core and thin section characterisation and are grouped into three carbonate turbidite sequences. They include: 1) Calciturbidites, comprising mostly of highto low-density, wavy-laminated bioclast-rich facies; 2) low-density densite mudstones which are characterised by planar laminated and unlaminated muddominated facies; and 3) Calcidebrites which are muddy or hyper-concentrated debrisflow deposits occurring as poorly-sorted, chaotic, mud-supported floatstones. These

Phd by thesis

The microorganisms in biofilms live in a self-produced matrix of hydrated extracellular polymeric substances (EPS) that form their immediate environment. EPS are mainly polysaccharides, proteins, nucleic acids and lipids; they provide the mechanical stability of biofilms, mediate their adhesion to surfaces and form a cohesive, three-dimensional polymer network that interconnects and transiently immobilizes biofilm cells. In addition, the biofilm matrix acts as an external digestive system by keeping extracellular enzymes close to the cells, enabling them to metabolize dissolved, colloidal and solid biopolymers. Here we describe the functions, properties and constituents of the EPS matrix that make biofilms the most successful forms of life on earth.

The biofilm matrix

Polymer/layered silicate nanocomposites: a review from preparation to processing

Nanocrystals are fundamental to modern science and technology. Mastery over the shape of a nanocrystal enables control of its properties and enhancement of its usefulness for a given application. Our aim is to present a comprehensive review of current research activities that center on the shape-controlled synthesis of metal nanocrystals. We begin with a brief introduction to nucleation and growth within the context of metal nanocrystal synthesis, followed by a discussion of the possible shapes that a metal nanocrystal might take under different conditions. We then focus on a variety of experimental parameters that have been explored to manipulate the nucleation and growth of metal nanocrystals in solution-phase syntheses in an effort to generate specific shapes. We then elaborate on these approaches by selecting examples in which there is already reasonable understanding for the observed shape control or at least the protocols have proven to be reproducible and controllable. Finally, we highlight a number of applications that have been enabled and/or enhanced by the shape-controlled synthesis of metal nanocrystals. We conclude this article with personal perspectives on the directions toward which future research in this field might take.

Shape‐Controlled Synthesis of Metal Nanocrystals: Simple Chemistry Meets Complex Physics?

Recent years have seen a renewed interest in the harvesting and conversion of solar energy. Among various technologies, the direct conversion of solar to chemical energy using photocatalysts has received significant attention. Although heterogeneous photocatalysts are almost exclusively semiconductors, it has been demonstrated recently that plasmonic nanostructures of noble metals (mainly silver and gold) also show significant promise. Here we review recent progress in using plasmonic metallic nanostructures in the field of photocatalysis. We focus on plasmon-enhanced water splitting on composite photocatalysts containing semiconductor and plasmonic-metal building blocks, and recently reported plasmon-mediated photocatalytic reactions on plasmonic nanostructures of noble metals. We also discuss the areas where major advancements are needed to move the field of plasmon-mediated photocatalysis forward.

Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy

A revolution in novel nanoparticles and colloidal building blocks has been enabled by recent breakthroughs in particle synthesis These new particles are poised to become the ‘atoms’ and ‘molecules’ of tomorrow’s materials if they can be successfully assembled into useful structures Here, we discuss the recent progress made in the synthesis of nanocrystals and colloidal particles and draw analogies between these new particulate building blocks and better-studied molecules and supramolecular objects We argue for a conceptual framework for these new building blocks based on anisotropy attributes and discuss the prognosis for future progress in exploiting anisotropy for materials design and assembly

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Anisotropy of building blocks and their assembly into complex structures

The melt-state linear and nonlinear shear rheological properties of hybrid materials of polypropylene and amine-exchanged montmorillonite were studied. The materials were prepared by melt mixing with maleic anhydride functionalized polypropylene as the compatibilizer. The clay interlayer spacing (as determined by wide-angle X-ray scattering) increased upon melt mixing; however, the short-range ordering of the clay layers was preserved. Above inorganic loadings of 2.0 wt % the hybrid materials exhibited apparent low-frequency plateaus in the linear viscoelastic moduli. The hybrid storage modulus was sensitive to the chemistry of the amine exchanged into the clay. The amount of stress overshoot observed in flow reversal experiments was found to be a function of the rest time allowed between the reversal. The transient stress in start-up of steady shear scaled with the applied strain. These observations allow features of the polypropylene/montmorillonite hybrid structure to be deduced. The transient nonlinea...

Rheology of Polypropylene/Clay Hybrid Materials

We review the sequences of structural states that can be induced in colloidal suspensions by the application of flow. Structure formation during flow is strongly affected by the delicate balance among interparticle forces, Brownian motion and hydrodynamic interactions. The resulting non-equilibrium microstructure is in turn a principal determinant of the suspension rheology. Colloidal suspensions with near hard-sphere interactions develop an anisotropic, amorphous structure at low dimensionless shear rates. At high rates, clustering due to strong hydrodynamic forces leads to shear thickening rheology. Application of steady-shear flow to suspensions with repulsive interactions induces a rich sequence of transitions to one-, two-and three-dimensional order. Oscillatory-shear flow generates metastable ordering in suspensions with equilibrium liquid structure. On the other hand, short-range attractive interactions can lead to a fluid-to-gel transition under quiescent suspensions. Application of flow leads to orientation, breakup, densification and spatial reorganization of aggregates. Using a non-Newtonian suspending medium leads to additional possibilities for organization. We examine the extent to which theory and simulation have yielded mechanistic understanding of the microstructural transitions that have been observed.

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Flow-induced structure in colloidal suspensions

Self-assembly is a fundamental mechanism by which structures form in materials. Over the past decades, a primary focus has been to relate materials’ behaviors to the spatial arrangement of their fundamental building blocks. These building blocks may comprise atoms, molecules, macromolecules and colloidal particles. It is well known that the same chemical substance can have vastly different properties depending on the way its building blocks are arranged—that is, on its crystal structure. For example, carbon atoms arranged in the diamond structure make for the hardest material on earth, whereas in the graphite structure of a charcoal drawing pen, layers of carbon are abraded without effort. The difference between both materials lies in the way atoms are stacked and the type of bond that forms between them. Likewise, colloidal particles might be arranged in a diamond structure. On that scale, this structure makes a material useful not for its hardness, but for its optical properties such as a photonic band gap.1 Today, building blocks of exotic shape and functionality are beginning to be engineered at nanometer and micrometer scales. New synthesis and fabrication techniques are being pioneered to make nanoparticles and colloids whose asymmetric shapes and anisotropic interactions provide a spectrum of crystal polymorphs and assembled structures unprecedented in colloid science. Methods now exist for coding instructions for assembly onto individual building blocks, thereby exploiting biomimetic principles of self-organization observed in proteins, for example. These new building blocks will be the “atoms” and “molecules” of tomorrow’s materials, self-assembling into unique structures made possible solely by their design. The urgent question for engineers today is: to what extent may the richness of molecular crystal structures be imparted to suspensions of nanoparticles and colloidal “molecules”? In this Perspective, we compare building blocks being made today at nanometer and micrometer scales and discuss issues important for generating and predicting their self-assembly into novel and useful structures. In the section titled “Effect of Shape and Composition on Assembly”, we discuss issues of building block shape and composition, and the role of these factors in the self-organization of particles into ordered assemblies. The section titled “Scale Dependent Effects on Assembly” discusses issues of Brownian motion, interparticle forces, and vitrification and gelation. In the section “Building Block Design Rules from Computer Simulation”, we describe several simulation methods appropriate for modeling nanoparticle and colloidal self-assembly, and describe examples of computer models of particles “programmed” for assembly by the use of anisotropic interactions. This section is followed by a brief conclusion and outlook.

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Self‐assembly: From nanoscale to microscale colloids

We review the diverse range of materials made up of rod-shaped colloids. A common feature of such suspensions is the strong and efficient contribution of rods to the material's solid-like rheological properties such as elastic modulus and yield stress. Colloidal rod suspensions span from biomaterials such as f-actin and fd virus to inorganic materials such as boehmite and hematite, and to commercial fibers such as cellulose. We argue that, depending on the strength of pair potential interactions, such rod suspensions form microstructures that vary between the two limits of heterogeneous fractal clusters and homogeneous fiber networks. The volume fraction range for transition between these two limiting cases is strongly aspect ratio dependent. The two limiting microstructures can be distinguished by differences in the scattering vector dependence of their structure factors, as long as the range of scattering vector probed is sufficient to span regimes both above and below qL ≈ 1. Here q is the scattering vector and L is the rod length. Theories of the Brownian dynamics of fractal clusters and fiber networks show that the two types of microstructure can lead to the arrested dynamics of gelation and the glass transition, respectively. The volume fraction and aspect ratio dependences of the dynamical slowing down of these two cases differ significantly; we suggest that probing these differences is a convenient way to distinguish between gels and glasses of colloidal rods. This distinction is important to clarify because these microstructures are determinants of rheological properties such as elasticity and yielding. By combining these structural and dynamical ideas about rods, we classify a set of literature measurements on more than fifteen different colloidal materials and thereby distinguish between regimes of gelation and vitrification. We conclude by suggesting directions for future research in the arrested dynamics, the non-linear rheology, and the absolute lower limit of gelation in colloidal rod suspensions.

Michael J. Solomon

Papers

Anisotropy of building blocks and their assembly into complex structures

Rheology of Polypropylene/Clay Hybrid Materials

Flow-induced structure in colloidal suspensions

Self‐assembly: From nanoscale to microscale colloids

Microstructural regimes of colloidal rod suspensions, gels, and glasses