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Andrew Putnis

Publications and source records attributed to Andrew Putnis.

5 recordsLinked to original sources

Nano-cluster composite structure of calcitic sponge spicules--a case study of basic characteristics of biominerals.

Spicules of calcareous sponges are elaborately shaped skeletal elements that nonetheless show characteristics of calcite single-crystals. Our atomic force microscopic and transmission electron microscopic investigation of the triradiate spicules of the sponge Pericharax heteroraphis reveals a nano-cluster structure with mostly well-aligned small crystal domains and pockets with accumulated domain misalignments. Combined high-resolution and energy-filtering transmission electron microscopy revealed carbon enrichments located in between crystal domain boundaries, which strongly suggests an intercalated network-like proteinaceous organic matrix. This matrix is proposed to be involved in the nano-clustered calcite precipitation via a transient phase that may enable a 'brick-by-brick' formation of composite and yet single-crystalline spicules with elaborate morphologies. This composite cluster structure reduces the brittleness of the material by dissipating strain energy and deflecting crack propagation from the calcite cleavage planes, but the lattice symmetry and anisotropic growth properties of calcite still play a major role in the morphogenesis of these unusual calcite single-crystals. Our structural, crystallographic, textural, and chemical analysis of sponge spicules corroborates the view that nano-clustered crystal growth, induced by organic matrices, is a basic characteristic of biomineralisation that enables the production of composite materials with elaborate morphologies.

Animals↗

Off-axis electron holography of magnetic nanowires and chains, rings, and planar arrays of magnetic nanoparticles.

A selection of recent results illustrating the application of off-axis electron holography to the study of magnetic microstructure in closely-spaced nanoparticles and nanowires is reviewed. Examples are taken from the characterization of FeNi nanoparticle chains, Co nanoparticle rings, two-dimensional arrays of naturally occurring magnetite crystals in minerals, and single crystalline Co nanowires. Approaches that can be used to separate the magnetic signal of interest from the mean inner potential contribution to the measured holographic phase shift are described, and the spatial and phase resolution that can be achieved are discussed.

Algorithms↗

Interaction of calcium carbonates with lead in aqueous solutions.

Pure calcium carbonate (calcite and aragonite) solid materials of different particle size (100-200 microm fragments and millimeter-sized single crystals) were interacted with Pb in aqueous solutions at room temperature under atmospheric PCO2. In the case of the micrometer-sized samples, the macroscopic investigation using a batch-type treatment procedure (solutions between 10 and 1000 mg/L Pb) and ICP-AES, SEM-EDS, and powder-XRD showed that the metal is readily removed from the aqueous media by both materials and indicated the sorption processes (mainly surface precipitation leading to overgrowth of cerussite and hydrocerussite crystals) taking place in parallel with surface dissolution processes. The various processes occurring at the calcium carbonate solid-water interface were clearly distinguished and defined in the case of the millimeter-sized samples interacted with 1000 mg/L Pb using a combination of wet-chemical, in-situ (AFM) and ex-situ (AFM, SEM) microscopic, and surface spectroscopic (XPS, 12C-RBS) techniques. The in-situ AFM data revealed the dissolution processes on the surface of the calcium carbonates and the simultaneous heterogeneous nucleation of lead carbonate phases and confirmed the secondary dissolution of lead carbonate crystals grown epitaxially from the initial nuclei. The XPS spectra confirmed that adsorption of Pb occurs simultaneously to dissolution at short interaction times (less than approximately 10 min, prior to precipitation-nucleation/crystal growth) in the case of both CaCO3 polymorphs and that the calcite surface with adsorbed Pb may have an aragonite-type character. The 12C-RBS spectra indicated that absorption (incorporation of Pb2+ ions) also takes place in parallel at the surface layers of the calcium carbonates, resulting in formation of solid solutions.

Absorption↗

Nucleation of solid solutions crystallizing from aqueous solutions.

The study of nucleation and growth mechanisms of salts from aqueous solutions, as a function of supersaturation, is described using both macroscopic and microscopic experiments. In situ observations in a fluid cell in an atomic force microscope (AFM) reveal phenomena not accounted for in standard crystal-growth theories, specifically on the role of the crystal structure of the substrate in controlling spiral growth and two-dimensional nucleation. As a model example, the crystallization of two isostructural salts, BaSO(4) and SrSO(4), is described. The growth of solid-solution crystals is considerably more complex. The supersaturation of a given aqueous solution relative to a solid solution is different with respect to each solid composition, and it leads to the possibility that different compositions can simultaneously grow by different mechanisms on the same crystal face. Oscillatory compositional zoning is another consequence of the interplay between the thermodynamics and the kinetics of nucleation. The factors which control nucleation and growth of the solid solution (Ba,Sr)SO(4) from an aqueous solution are described. The predictions made from the theory are compared with direct observations of crystal growth in an AFM.

Barium Sulfate↗

Direct imaging of nanoscale magnetic interactions in minerals.

The magnetic microstructure of a natural, finely exsolved intergrowth of submicron magnetite blocks in an ulvöspinel matrix is characterized by using off-axis electron holography in the transmission electron microscope. Single-domain and vortex states in individual blocks, as well as magnetostatic interaction fields between them, are imaged at a spatial resolution approaching the nanometer scale. The images reveal an extremely complicated magnetic structure dominated by the shapes of the blocks and magnetostatic interactions. Magnetic superstates, in which clusters of magnetite blocks act collectively to form vortex and multidomain states that have zero net magnetization, are observed directly.

Journal Article↗