Assessing the suitability of fly ash geopolymers for high temperature applications

Geopolymers are an inorganic polymer synthesised from the dissolution and polycondensation of aluminosilicates in alkaline solutions under hydrothermal condition, yielding an amorphous, three-dimensional polymeric framework (Davidovits, 1991). They are a broad class of binding material with applications that range from conventional concrete to high tech, light weight composites for use in aviation. Geopolymers have also shown promise for use in high temperature applications, such as fire proof coatings, structural concrete in fire prone areas and thermal insulation for refractory type applications, due to their intrinsic thermal stability (Barbosa and MacKenzie, 2003a).This thesis reports on an investigation into the thermal performance of geopolymers synthesised from a range of fly ashes in order to assess their suitability for use in high temperature applications. Five fly ashes from Australian power stations with contrasting chemical properties were used in the study. Geopolymers were synthesised from each of the fly ashes using sodium silicate or sodium aluminate solutions in order to achieve a set range of Si:Al compositional ratios. Thermal analysis was conducted up to 1000 °C using a constant heat rate as well as a heating regime that simulated the conditions during a fire.The fly ashes were characterised in terms of elemental composition, phase composition, particle size, density and morphology prior to being used to synthesise geopolymers. It was determined that only a portion of each of the fly ashes was available for geopolymerisation and that the reactive Si:Al ratio (amorphous Si:Al ratio) varied greatly between the fly ashes. Collie and Port Augusta fly ashes had relatively low reactive Si:Al ratios (1.15 and 1.84, respectively) whereas Eraring, Tarong and Bayswater fly ashes had high Si:Al ratios (4.98, 8.84 and 7.49, respectively). All of the fly ashes had a predominantly spherical morphology, characteristic of fly ashes, though only the Collie and Port Augusta fly ashes had a significant portion of sub 5 μm particles.The thermo-physical, mechanical and micro-structural properties of the geopolymers made from each of the fly ashes are presented and the effect of the source fly ash characteristics on the hardened product is discussed. The results varied greatly with fly ash source and the most influential fly ash characteristic was the reactive Si:Al ratio. Fly ashes with a high reactive Si:Al ratio (≥5) were sodium aluminate activated and produced geopolymers with low to moderate as-cured compressive strengths but exhibited excellent dimensional stability during heating and greater compressive strengths after heating. Fly ashes with a low reactive Si:Al ratio (<2) were sodium silicate activated and produced geopolymers with high as-cured compressive strengths but exhibited poor dimensional stability during heating and greatly reduced compressive strengths after heating. All samples exhibited strength improving microstructural changes such as improved inter-particle bonding due to sintering after firing. However, the instability of non geopolymer phases during high temperature exposure led to strength losses in some samples depending on the type and composition of the activating solution.Geopolymers from three of the fly ashes were assessed for their performance upon exposure to a simulated fire. Solid and low density foamed variants (ρ ≈ 0.9 g cm-3, k ≈ 0.3 W m-1K-1) of the mixes were used for fire testing. Fire ratings of between 60 and 90 minutes for a sample thickness of 50 mm were achieved. The solid geopolymers exhibited better fire ratings than the low density geopolymers due to their higher water content (as they contained more of the hydrated geopolymer phase). Microstructural analysis of the fire tested samples indicated that the geopolymers were not significantly damaged by dehydration and the fire exposed side exhibited analogous changes to the samples that were gradually heated to 1000 °C.The results in this thesis indicate that fly ash geopolymers have great potential for utilisation in high temperature applications provided they are synthesised from a source material with suitable physical and compositional characteristics

Magnetic Flux Braiding: Force-Free Equilibria and Current Sheets

We use a numerical nonlinear multigrid magnetic relaxation technique to investigate the generation of current sheets in three-dimensional magnetic flux braiding experiments. We are able to catalogue the relaxed nonlinear force-free equilibria resulting from the application of deformations to an initially undisturbed region of plasma containing a uniform, vertical magnetic field. The deformations are manifested by imposing motions on the bounding planes to which the magnetic field is anchored. Once imposed the new distribution of magnetic footpoints are then taken to be fixed, so that the rest of the plasma must then relax to a new equilibrium configuration. For the class of footpoint motions we have examined, we find that singular and nonsingular equilibria can be generated. By singular we mean that within the limits imposed by numerical resolution we find that there is no convergence to a well-defined equilibrium as the number of grid points in the numerical domain is increased. These singular equilibria contain current "sheets" of ever-increasing current intensity and decreasing width; they occur when the footpoint motions exceed a certain threshold, and must include both twist and shear to be effective. On the basis of these results we contend that flux braiding will indeed result in significant current generation. We discuss the implications of our results for coronal heating.Comment: 13 pages, 12 figure

The homotopy theory of dg-categories and derived Morita theory

The main purpose of this work is the study of the homotopy theory of dg-categories up to quasi-equivalences. Our main result provides a natural description of the mapping spaces between two dg-categories $C$ and $D$ in terms of the nerve of a certain category of $(C,D)$-bimodules. We also prove that the homotopy category $Ho(dg-Cat)$ is cartesian closed (i.e. possesses internal Hom's relative to the tensor product). We use these two results in order to prove a derived version of Morita theory, describing the morphisms between dg-categories of modules over two dg-categories $C$ and $D$ as the dg-category of $(C,D)$-bi-modules. Finally, we give three applications of our results. The first one expresses Hochschild cohomology as endomorphisms of the identity functor, as well as higher homotopy groups of the \emph{classifying space of dg-categories} (i.e. the nerve of the category of dg-categories and quasi-equivalences between them). The second application is the existence of a good theory of localization for dg-categories, defined in terms of a natural universal property. Our last application states that the dg-category of (continuous) morphisms between the dg-categories of quasi-coherent (resp. perfect) complexes on two schemes (resp. smooth and proper schemes) is quasi-equivalent to the dg-category of quasi-coherent complexes (resp. perfect) on their product.Comment: 50 pages. Few mistakes corrected, and some references added. Thm. 8.15 is new. Minor corrections. Final version, to appear in Inventione

Generalizing Optical Geometry

We show that by employing the standard projected curvature as a measure of spatial curvature, we can make a certain generalization of optical geometry (Abramowicz and Lasota 1997, Class. Quantum Grav. 14 (1997) A23). This generalization applies to any spacetime that admits a hypersurface orthogonal shearfree congruence of worldlines. This is a somewhat larger class of spacetimes than the conformally static spacetimes assumed in standard optical geometry. In the generalized optical geometry, which in the generic case is time dependent, photons move with unit speed along spatial geodesics and the sideways force experienced by a particle following a spatially straight line is independent of the velocity. Also gyroscopes moving along spatial geodesics do not precess (relative to the forward direction). Gyroscopes that follow a curved spatial trajectory precess according to a very simple law of three-rotation. We also present an inertial force formalism in coordinate representation for this generalization. Furthermore, we show that by employing a new sense of spatial curvature (Jonsson, Class. Quantum Grav. 23 (2006) 1) closely connected to Fermat's principle, we can make a more extensive generalization of optical geometry that applies to arbitrary spacetimes. In general this optical geometry will be time dependent, but still geodesic photons move with unit speed and follow lines that are spatially straight in the new sense. Also, the sideways experienced (comoving) force on a test particle following a line that is straight in the new sense will be independent of the velocity.Comment: 19 pages, 1 figure. A more general analysis is presented than in the former version. See also the companion papers arXiv:0708.2493, arXiv:0708.2533 and arXiv:0708.253

Passive and catalytic antibodies and drug delivery

Antibodies are one of the most promising components of the biotechnology repertoire for the purpose of drug delivery. On the one hand, they are proven agents for cell-selective delivery of highly toxic agents in a small but expanding number of cases. This technology calls for the covalent attachment of the cytotoxin to a tumor-specific antibody by a linkage that is reversible under appropriate conditions (antibody conjugate therapy, ACT —"passive delivery”). On the other hand, the linker cleavage can be accomplished by a protein catalyst attached to the tumor-specific antibody ("catalytic delivery”). Where the catalyst is an enzyme, this approach is known as antibody-directed enzyme prodrug therapy (ADEPT). Where the transformation is brought about by a catalytic antibody, it has been termed antibody-directed abzyme prodrug therapy (ADAPT). These approaches will be illustrated with emphasis on how their demand for new biotechnology is being realized by structure-based protein engineerin

Inertial forces and the foundations of optical geometry

Assuming a general timelike congruence of worldlines as a reference frame, we derive a covariant general formalism of inertial forces in General Relativity. Inspired by the works of Abramowicz et. al. (see e.g. Abramowicz and Lasota, Class. Quantum Grav. 14 (1997) A23), we also study conformal rescalings of spacetime and investigate how these affect the inertial force formalism. While many ways of describing spatial curvature of a trajectory has been discussed in papers prior to this, one particular prescription (which differs from the standard projected curvature when the reference is shearing) appears novel. For the particular case of a hypersurface-forming congruence, using a suitable rescaling of spacetime, we show that a geodesic photon is always following a line that is spatially straight with respect to the new curvature measure. This fact is intimately connected to Fermat's principle, and allows for a certain generalization of the optical geometry as will be further pursued in a companion paper (Jonsson and Westman, Class. Quantum Grav. 23 (2006) 61). For the particular case when the shear-tensor vanishes, we present the inertial force equation in three-dimensional form (using the bold face vector notation), and note how similar it is to its Newtonian counterpart. From the spatial curvature measures that we introduce, we derive corresponding covariant differentiations of a vector defined along a spacetime trajectory. This allows us to connect the formalism of this paper to that of Jantzen et. al. (see e.g. Bini et. al., Int. J. Mod. Phys. D 6 (1997) 143).Comment: 42 pages, 7 figure

Torsion pairs and simple-minded systems in triangulated categories

Let T be a Hom-finite triangulated Krull-Schmidt category over a field k. Inspired by a definition of Koenig and Liu, we say that a family S of pairwise orthogonal objects in T with trivial endomorphism rings is a simple-minded system if its closure under extensions is all of T. We construct torsion pairs in T associated to any subset X of a simple-minded system S, and use these to define left and right mutations of S relative to X. When T has a Serre functor \nu, and S and X are invariant under \nu[1], we show that these mutations are again simple-minded systems. We are particularly interested in the case where T is the stable module category of a self-injective algebra \Lambda. In this case, our mutation procedure parallels that introduced by Koenig and Yang for simple-minded collections in the derived category of \Lambda. It follows that the mutation of the set of simple \Lambda-modules relative to X yields the images of the simple \Gamma-modules under a stable equivalence between \Gamma\ and \Lambda, where \Gamma\ is the tilting mutation of \Lambda\ relative to X.Comment: Minor corrections. To appear in Applied Categorical Structures. The final publication is available at springerlink.com: http://link.springer.com/article/10.1007%2Fs10485-014-9365-

Nanoparticulate nickel sulfides formed in low temperature aqueous solutions

The nature of the nickel sulfides formed in low temperature aqueous solutions is not well-understood. The material has some intrinsic interest to mineralogy, geochemistry and materials science as well as to biogeochemisty, especially as a possible catalyst involved in the origin and early evolution of life. We synthesized Ni sulfide under anoxic conditions at 25 C: (1) chemically, by the addition of 50 mL of 0.1 M NiSO4Æ7H2O to 100 mL of 0.05M Na2SÆ9H2O; (2) electrochemically, with a Ni foil and H2S gas. At pH 6 5, millerite (b-NiS) was produced electrochemically and NiS mixtures, including heazlewoodite (Ni3S2) and polydymite (Ni3S4), were obtained chemically. At pH >11, a- NiS was obtained from the chemical reaction. At pH 6–9, the product produced only two broad peaks (d = ca. 2.7 and 1.8 ) with conventional and synchrotron XRPD which could be assigned to a number of Ni sulfides. It has previously been referred to as ‘‘amorphous NiS’’ Jeong and Manthiram, 2001. Eight SAED reflections were collected which identified the material as godlevskite, orthorhombic NiS. HRTEM shows that the godlevskite particles are ca. 30 nm in diameter and plate-like. SAXS analyses show that the material is 6–8.5 nm thick. Godlevskite is structurally related to makinawite, tetragonal FeS, and is found naturally in similar parageneses-associated with the monosulfide solid solution products of high temperature nickel ores. Mackinawite is the black FeS precipitate from the reaction between Fe(II) and S(-II) in aqueous solution. It appears that, geochemically, godlevskite is the Ni analogue of mackinawite

Generalised models for torsional spine and fan magnetic reconnection

Three-dimensional null points are present in abundance in the solar corona, and the same is likely to be true in other astrophysical environments. Recent studies suggest that reconnection at such 3D nulls may play an important role in the coronal dynamics. In this paper the properties of the torsional spine and torsional fan modes of magnetic reconnection at 3D nulls are investigated. New analytical models are developed, which for the first time include a current layer that is spatially localised around the null, extending along either the spine or the fan of the null. These are complemented with numerical simulations. The principal aim is to investigate the effect of varying the degree of asymmetry of the null point magnetic field on the resulting reconnection process - where previous studies always considered a non-generic radially symmetric null. The geometry of the current layers within which torsional spine and torsional fan reconnection occur is found to be strongly dependent on the symmetry of the magnetic field. Torsional spine reconnection still occurs in a narrow tube around the spine, but with elliptical cross-section when the fan eigenvalues are different, and with the short axis of the ellipse being along the strong field direction. The spatiotemporal peak current, and the peak reconnection rate attained, are found not to depend strongly on the degree of asymmetry. For torsional fan reconnection, the reconnection occurs in a planar disk in the fan surface, which is again elliptical when the symmetry of the magnetic field is broken. The short axis of the ellipse is along the weak field direction, with the current being peaked in these weak field regions. The peak current and peak reconnection rate in this case are clearly dependent on the asymmetry, with the peak current increasing but the reconnection rate decreasing as the degree of asymmetry is increased

Using Time-Series Privileged Information for Provably Efficient Learning of Prediction Models

We study prediction of future outcomes with supervised models that use privileged information during learning. The privileged information comprises samples of time series observed between the baseline time of prediction and the future outcome; this information is only available at training time which differs from the traditional supervised learning. Our question is when using this privileged data leads to more sample-efficient learning of models that use only baseline data for predictions at test time. We give an algorithm for this setting and prove that when the time series are drawn from a non-stationary Gaussian-linear dynamical system of fixed horizon, learning with privileged information is more efficient than learning without it. On synthetic data, we test the limits of our algorithm and theory, both when our assumptions hold and when they are violated. On three diverse real-world datasets, we show that our approach is generally preferable to classical learning, particularly when data is scarce. Finally, we relate our estimator to a distillation approach both theoretically and empirically