Showing papers on "Nucleation published in 2015"

Mechanism and Kinetics of Li2S Precipitation in Lithium–Sulfur Batteries

Abstract: The kinetics of Li2 S electrodeposition onto carbon in lithium-sulfur batteries are characterized. Electrodeposition is found to be dominated by a 2D nucleation and growth process with rate constants that depend strongly on the electrolyte solvent. Nucleation is found to require a greater overpotential than growth, which results in a morphology that is dependent on the discharge rate.

On the lag phase in amyloid fibril formation

Abstract: The formation of nanoscale amyloid fibrils from normally soluble peptides and proteins is a common form of self-assembly phenomenon that has fundamental connections with biological functions and human diseases. The kinetics of this process has been widely studied and exhibits on a macroscopic level three characteristic stages: a lag phase, a growth phase and a final plateau regime. The question of which molecular events take place during each one of these phases has been a central element in the quest for a mechanism of amyloid formation. In this review, we discuss the nature and molecular origin of the lag-phase in amyloid formation by making use of tools and concepts from physical chemistry, in particular from chemical reaction kinetics. We discuss how, in macroscopic samples, it has become apparent that the lag-phase is not a waiting time for nuclei to form. Rather, multiple parallel processes exist and typically millions of primary nuclei form during the lag phase from monomers in solution. Thus, the lag-time represents a time that is required for the nuclei that are formed early on in the reaction to grow and proliferate in order to reach an aggregate concentration that is readily detected in bulk assays. In many cases, this proliferation takes place through secondary nucleation, where fibrils may present a catalytic surface for the formation of new aggregates. Fibrils may also break (fragmentation) and thereby provide new ends for elongation. Thus, at least two – primary nucleation and elongation – and in many systems at least four – primary nucleation, elongation, secondary nucleation and fragmentation – microscopic processes occur during the lag phase. Moreover, these same processes occur during all three phases of the macroscopic aggregation process, albeit at different rates as governed by rate constants and by the concentration of reacting species at each point in time.

A Unified in Vitro Evaluation for Apatite-Forming Ability of Bioactive Glasses and Their Variants

Abstract: The aim of this study was to propose and validate a new unified method for testing dissolution rates of bioactive glasses and their variants, and the formation of calcium phosphate layer formation on their surface, which is an indicator of bioactivity At present, comparison in the literature is difficult as many groups use different testing protocols An ISO standard covers the use of simulated body fluid on standard shape materials but it does not take into account that bioactive glasses can have very different specific surface areas, as for glass powders Validation of the proposed modified test was through round robin testing and comparison to the ISO standard where appropriate The proposed test uses fixed mass per solution volume ratio and agitated solution The round robin study showed differences in hydroxyapatite nucleation on glasses of different composition and between glasses of the same composition but different particle size The results were reproducible between research facilities Researchers should use this method when testing new glasses, or their variants, to enable comparison between the literature in the future

Lipid vesicles trigger α-synuclein aggregation by stimulating primary nucleation

Abstract: α-Synuclein (α-syn) is a 140-residue intrinsically disordered protein that is involved in neuronal and synaptic vesicle plasticity, but its aggregation to form amyloid fibrils is the hallmark of Parkinson's disease (PD). The interaction between α-syn and lipid surfaces is believed to be a key feature for mediation of its normal function, but under other circumstances it is able to modulate amyloid fibril formation. Using a combination of experimental and theoretical approaches, we identify the mechanism through which facile aggregation of α-syn is induced under conditions where it binds a lipid bilayer, and we show that the rate of primary nucleation can be enhanced by three orders of magnitude or more under such conditions. These results reveal the key role that membrane interactions can have in triggering conversion of α-syn from its soluble state to the aggregated state that is associated with neurodegeneration and to its associated disease states.

Mechanisms of antiwear tribofilm growth revealed in situ by single-asperity sliding contacts

Abstract: Zinc dialkyldithiophosphates (ZDDPs) form antiwear tribofilms at sliding interfaces and are widely used as additives in automotive lubricants. The mechanisms governing the tribofilm growth are not well understood, which limits the development of replacements that offer better performance and are less likely to degrade automobile catalytic converters over time. Using atomic force microscopy in ZDDP-containing lubricant base stock at elevated temperatures, we monitored the growth and properties of the tribofilms in situ in well-defined single-asperity sliding nanocontacts. Surface-based nucleation, growth, and thickness saturation of patchy tribofilms were observed. The growth rate increased exponentially with either applied compressive stress or temperature, consistent with a thermally activated, stress-assisted reaction rate model. Although some models rely on the presence of iron to catalyze tribofilm growth, the films grew regardless of the presence of iron on either the tip or substrate, highlighting the critical role of stress and thermal activation.

Mechanism of self-assembly process and seeded supramolecular polymerization of perylene bisimide organogelator.

Abstract: The mechanism of supramolecular polymerization has been elucidated for an archetype organogelator molecule composed of a perylene bisimide aromatic scaffold and two amide substituents. This molecule self-assembles into elongated one-dimensional nanofibers through a cooperative nucleation–growth process. Thermodynamic and kinetic analyses have been applied to discover conditions (temperature, solvent, concentration) where the spontaneous nucleation can be retarded by trapping of the monomers in an inactive conformation, leading to lag times up to more than 1 h. The unique kinetics in the nucleation process was confirmed as a thermal hysteresis in a cycle of assembly and disassembly processes. Under appropriate conditions within the hysteresis loop, addition of preassembled nanofiber seeds leads to seeded polymerization from the termini of the seeds in a living supramolecular polymerization process. These results demonstrate that seeded polymerizations are not limited to special situations where off-pathway...

Calcium carbonate nucleation driven by ion binding in a biomimetic matrix revealed by in situ electron microscopy

Abstract: In situ liquid-phase electron microscopy experiments show that the binding of calcium ions to a biomimetic polymer matrix can direct the nucleation of amorphous calcium carbonate, a main precursor phase in calcium carbonate mineralization.

Synthesis of large single-crystal hexagonal boron nitride grains on Cu-Ni alloy.

Abstract: High nucleation density has thus far limited the quality and grain size of CVD-grown hexagonal boron nitride. Here, by optimizing the Ni ratio in Cu–Ni substrates, the authors successfully reduce nucleation density and report single-crystal hexagonal boron nitride grains up to 7500 μm2.

The heat-up synthesis of colloidal nanocrystals

Abstract: The successful transition of any nanocrystal-based product from the research phase to the commercial arena hinges on the ability to produce the required nanomaterial on large scales. The synthesis of colloidal nanocrystals using a heat-up (non-injection) method is a reliable means to achieve high quality nanomaterials on large scales with little or no batch-to-batch variation. In this class of synthesis precursors are heated within a reaction medium to induce a chemical reaction that yields monomer for nucleation and growth. Use of the heat-up technique circumvents the pitfalls of mixing time and poor heat management inherent to classical “hot-injection” methods. In heat-up syntheses monomer is produced in a more continuous fashion during the heating stage, making it more difficult to separate the nucleation and growth stages of the reaction, a factor that is conventionally considered detrimental toward achieving homogeneous colloidal dispersions. However, through the judicious selection of precursors, st...

Mineralogy, nucleation and growth of dolomite in the laboratory and sedimentary environment: A review

Abstract: Dolomite [CaMg(CO3)2] forms in numerous geological settings, usually as a diagenetic replacement of limestone, and is an important component of petroleum reservoir rocks, rocks hosting base metal deposits and fresh water aquifers. Dolomite is a rhombohedral carbonate with a structure consisting of an ordered arrangement of alternating layers of Ca2+ and Mg2+ cations interspersed with CO32− anion layers normal to the c-axis. Dolomite has R3¯ symmetry, lower than the (CaCO3) R3¯c symmetry of calcite primarily due to Ca–Mg ordering. High-magnesium calcite also has R3¯c symmetry and differs from dolomite in that Ca2+ and Mg2+ ions are not ordered. High-magnesium calcite with near-dolomite stoichiometry (≈50 mol% MgCO3) has been observed both in nature and in laboratory products and is referred to in the literature as protodolomite or very high-magnesium calcite. Many dolomites display some degree of cation disorder (Ca2+ on Mg2+ sites and vice versa), which is detectable using transmission electron microscopy and X-ray diffractometry. Laboratory syntheses at high temperature and pressure, as well as studies of natural dolomites show that factors affecting dolomite ordering, stoichiometry, nucleation and growth include temperature, alkalinity, pH, concentration of Mg and Ca, Mg to Ca ratio, fluid to rock ratio, mineralogy of the carbonate being replaced, and surface area available for nucleation. In spite of numerous attempts, dolomite has not been synthesized in the laboratory under near-surface conditions. Examination of published X-ray diffraction data demonstrates that assertions of dolomite synthesis in the laboratory under near-ambient conditions by microbial mediation are unsubstantiated. These laboratory products show no evidence of cation ordering and appear to be very high-magnesium calcite. Elevated-temperature and elevated-pressure experiments demonstrate that dolomite nucleation and growth always are preceded by very high-magnesium calcite formation. It remains to be demonstrated whether microbial-mediated growth of very high-magnesium calcite in nature provides a precursor to dolomite nucleation and growth analogous to reaction paths in high-temperature experiments.

Two-step nucleation mechanism in solid-solid phase transitions.

Abstract: The microscopic kinetics of ubiquitous solid-solid phase transitions remain poorly understood. Here, by using single-particle-resolution video microscopy of colloidal films of diameter-tunable microspheres, we show that transitions between square and triangular lattices occur via a two-step diffusive nucleation pathway involving liquid nuclei. The nucleation pathway is favoured over the direct one-step nucleation because the energy of the solid/liquid interface is lower than that between solid phases. We also observed that nucleation precursors are particle-swapping loops rather than newly generated structural defects, and that coherent and incoherent facets of the evolving nuclei exhibit different energies and growth rates that can markedly alter the nucleation kinetics. Our findings suggest that an intermediate liquid should exist in the nucleation processes of solid-solid transitions of most metals and alloys, and provide guidance for better control of the kinetics of the transition and for future refinements of solid-solid transition theory.

Soft matter in hard confinement: phase transition thermodynamics, structure, texture, diffusion and flow in nanoporous media

Abstract: Spatial confinement in nanoporous media affects the structure, thermodynamics and mobility of molecular soft matter often markedly. This article reviews thermodynamic equilibrium phenomena, such as physisorption, capillary condensation, crystallisation, self-diffusion, and structural phase transitions as well as selected aspects of the emerging field of spatially confined, non-equilibrium physics, i.e. the rheology of liquids, capillarity-driven flow phenomena, and imbibition front broadening in nanoporous materials. The observations in the nanoscale systems are related to the corresponding bulk phenomenologies. The complexity of the confined molecular species is varied from simple building blocks, like noble gas atoms, normal alkanes and alcohols to liquid crystals, polymers, ionic liquids, proteins and water. Mostly, experiments with mesoporous solids of alumina, gold, carbon, silica, and silicon with pore diameters ranging from a few up to 50 nm are presented. The observed peculiarities of nanopore-confined condensed matter are also discussed with regard to applications. A particular emphasis is put on texture formation upon crystallisation in nanoporous media, a topic both of high fundamental interest and of increasing nanotechnological importance, e.g. for the synthesis of organic/inorganic hybrid materials by melt infiltration, the usage of nanoporous solids in crystal nucleation or in template-assisted electrochemical deposition of nano structures.

Direct calculation of ice homogeneous nucleation rate for a molecular model of water

Abstract: Ice formation is ubiquitous in nature, with important consequences in a variety of environments, including biological cells, soil, aircraft, transportation infrastructure, and atmospheric clouds. However, its intrinsic kinetics and microscopic mechanism are difficult to discern with current experiments. Molecular simulations of ice nucleation are also challenging, and direct rate calculations have only been performed for coarse-grained models of water. For molecular models, only indirect estimates have been obtained, e.g., by assuming the validity of classical nucleation theory. We use a path sampling approach to perform, to our knowledge, the first direct rate calculation of homogeneous nucleation of ice in a molecular model of water. We use TIP4P/Ice, the most accurate among existing molecular models for studying ice polymorphs. By using a novel topological approach to distinguish different polymorphs, we are able to identify a freezing mechanism that involves a competition between cubic and hexagonal ice in the early stages of nucleation. In this competition, the cubic polymorph takes over because the addition of new topological structural motifs consistent with cubic ice leads to the formation of more compact crystallites. This is not true for topological hexagonal motifs, which give rise to elongated crystallites that are not able to grow. This leads to transition states that are rich in cubic ice, and not the thermodynamically stable hexagonal polymorph. This mechanism provides a molecular explanation for the earlier experimental and computational observations of the preference for cubic ice in the literature.

Microstructural evolution of gas hydrates in sedimentary matrices observed with synchrotron X-ray computed tomographic microscopy

Abstract: The formation process of gas hydrates in sedimentary matrices is of crucial importance for the physical and transport properties of the resulting aggregates. This process has never been observed in situ at submicron resolution. Here we report on synchrotron-based microtomographic studies by which the nucleation and growth processes of gas hydrate were observed at 276 K in various sedimentary matrices such as natural quartz (with and without admixtures of montmorillonite type clay) or glass beads with different surface properties, at varying water saturation. Both juvenile water and metastably gas-enriched water obtained from gas hydrate decomposition was used. Xenon gas was employed to enhance the density contrast between gas hydrate and the fluid phases involved. The nucleation sites can be easily identified and the various growth patterns are clearly established. In sediments under-saturated with juvenile water, nucleation starts at the water-gas interface resulting in an initially several micrometer thick gas hydrate film; further growth proceeds to form isometric single crystals of 10–20 µm size. The growth of gas hydrate from gas-enriched water follows a different pattern, via the nucleation in the bulk of liquid producing polyhedral single crystals. A striking feature in both cases is the systematic appearance of a fluid phase film of up to several micron thickness between gas hydrates and the surface of the quartz grains. These microstructural findings are relevant for future efforts of quantitative rock physics modeling of gas hydrates in sedimentary matrices and explain the anomalous attenuation of seismic/sonic waves.

Two-Step Nucleation and Growth of InP Quantum Dots via Magic-Sized Cluster Intermediates

Abstract: We report on the role of magic-sized clusters (MSCs) as key intermediates in the synthesis of indium phosphide quantum dots (InP QDs) from molecular precursors. Heterogeneous growth from the MSCs directly to InP QDs was observed without intermediate sized particles. These observations suggest that previous efforts to control nucleation and growth by tuning precursor reactivity have been undermined by formation of these kinetically persistent MSCs prior to QD formation. The thermal stability of InP MSCs is influenced by the presence of exogenous bases as well as choice of the anionic ligand set. Addition of a primary amine, a common additive in previous InP QD syntheses, to carboxylate-terminated MSCs was found to bypass the formation of MSCs, allowing for homogeneous growth of InP QDs through a continuum of isolable sizes. Substitution of the carboxylate ligand set for a phosphonate ligand set increased the thermal stability of one particular InP MSC to 400 °C. The structure and optical properties of the ...

Structure Determination of [Au18(SR)14]

Abstract: Unravelling the atomic structures of small gold clusters is the key to understanding the origin of metallic bonds and the nucleation of clusters from organometallic precursors. Herein we report the X-ray crystal structure of a charge-neutral [Au18(SC6H11)14] cluster. This structure exhibits an unprecedented bi-octahedral (or hexagonal close packing) Au9 kernel protected by staple-like motifs including one tetramer, one dimer, and three monomers. Until the present, the [Au18(SC6H11)14] cluster is the smallest crystallographically characterized gold cluster protected by thiolates and provides important insight into the structural evolution with size. Theoretical calculations indicate charge transfer from surface to kernel for the HOMO-LUMO transition.

Synthesis of Hexagonal Boron Nitride Monolayer: Control of Nucleation and Crystal Morphology

Abstract: Monolayer hexagonal boron nitride (hBN) attracts significant attention due to the potential to be used as a complementary two-dimensional dielectric in fabrication of functional 2D heterostructures. Here we investigate the growth stages of the hBN single crystals and show that hBN crystals change their shape from triangular to truncated triangular and further to hexagonal depending on copper substrate distance from the precursor. We suggest that the observed hBN crystal shape variation is affected by the ratio of boron to nitrogen active species concentrations on the copper surface inside the CVD reactor. Strong temperature dependence reveals the activation energies for the hBN nucleation process of ∼5 eV and crystal growth of ∼3.5 eV. We also show that the resulting h-BN film morphology is strongly affected by the heating method of borazane precursor and the buffer gas. Elucidation of these details facilitated synthesis of high quality large area monolayer hexagonal boron nitride by atmospheric pressure ...

The Many Faces of Heterogeneous Ice Nucleation: Interplay Between Surface Morphology and Hydrophobicity

Abstract: What makes a material a good ice nucleating agent? Despite the importance of heterogeneous ice nucleation to a variety of fields, from cloud science to microbiology, major gaps in our understanding of this ubiquitous process still prevent us from answering this question. In this work, we have examined the ability of generic crystalline substrates to promote ice nucleation as a function of the hydrophobicity and the morphology of the surface. Nucleation rates have been obtained by brute-force molecular dynamics simulations of coarse-grained water on top of different surfaces of a model fcc crystal, varying the water-surface interaction and the surface lattice parameter. It turns out that the lattice mismatch of the surface with respect to ice, customarily regarded as the most important requirement for a good ice nucleating agent, is at most desirable but not a requirement. On the other hand, the balance between the morphology of the surface and its hydrophobicity can significantly alter the ice nucleation rate and can also lead to the formation of up to three different faces of ice on the same substrate. We have pinpointed three circumstances where heterogeneous ice nucleation can be promoted by the crystalline surface: (i) the formation of a water overlayer that acts as an in-plane template; (ii) the emergence of a contact layer buckled in an ice-like manner; and (iii) nucleation on compact surfaces with very high interaction strength. We hope that this extensive systematic study will foster future experimental work aimed at testing the physiochemical understanding presented herein.

Direct Observation of Graphene Growth and Associated Copper Substrate Dynamics by in Situ Scanning Electron Microscopy

Abstract: This work highlights the importance of in situ experiments for an improved understanding of graphene growth on copper via metal-catalyzed chemical vapor deposition (CVD). Graphene growth inside the chamber of a modified environmental scanning electron microscope under relevant low-pressure CVD conditions allows visualizing structural dynamics of the active catalyst simultaneously with graphene nucleation and growth in an unparalleled way. It enables the observation of a complete CVD process from substrate annealing through graphene nucleation and growth and, finally, substrate cooling in real time and nanometer-scale resolution without the need of sample transfer. A strong dependence of surface dynamics such as sublimation and surface premelting on grain orientation is demonstrated, and the influence of substrate dynamics on graphene nucleation and growth is presented. Insights on the growth mechanism are provided by a simultaneous observation of the growth front propagation and nucleation rate. Furthermo...

Nucleation of metastable aragonite CaCO3 in seawater

Abstract: Predicting the conditions in which a compound adopts a metastable structure when it crystallizes out of solution is an unsolved and fundamental problem in materials synthesis, and one which, if understood and harnessed, could enable the rational design of synthesis pathways toward or away from metastable structures. Crystallization of metastable phases is particularly accessible via low-temperature solution-based routes, such as chimie douce and hydrothermal synthesis, but although the chemistry of the solution plays a crucial role in governing which polymorph forms, how it does so is poorly understood. Here, we demonstrate an ab initio technique to quantify thermodynamic parameters of surfaces and bulks in equilibrium with an aqueous environment, enabling the calculation of nucleation barriers of competing polymorphs as a function of solution chemistry, thereby predicting the solution conditions governing polymorph selection. We apply this approach to resolve the long-standing "calcite-aragonite problem"--the observation that calcium carbonate precipitates as the metastable aragonite polymorph in marine environments, rather than the stable phase calcite--which is of tremendous relevance to biomineralization, carbon sequestration, paleogeochemistry, and the vulnerability of marine life to ocean acidification. We identify a direct relationship between the calcite surface energy and solution Mg:Ca [corrected] ion concentrations, showing that the calcite nucleation barrier surpasses that of metastable aragonite in solutions with Mg:Ca ratios consistent with modern seawater, allowing aragonite to dominate the kinetics of nucleation. Our ability to quantify how solution parameters distinguish between polymorphs marks an important step toward the ab initio prediction of materials synthesis pathways in solution.

A comprehensive laboratory study on the immersion freezing behavior of illite NX particles: a comparison of 17 ice nucleation measurement techniques

Abstract: . Immersion freezing is the most relevant heterogeneous ice nucleation mechanism through which ice crystals are formed in mixed-phase clouds. In recent years, an increasing number of laboratory experiments utilizing a variety of instruments have examined immersion freezing activity of atmospherically relevant ice-nucleating particles. However, an intercomparison of these laboratory results is a difficult task because investigators have used different ice nucleation (IN) measurement methods to produce these results. A remaining challenge is to explore the sensitivity and accuracy of these techniques and to understand how the IN results are potentially influenced or biased by experimental parameters associated with these techniques. Within the framework of INUIT (Ice Nuclei Research Unit), we distributed an illite-rich sample (illite NX) as a representative surrogate for atmospheric mineral dust particles to investigators to perform immersion freezing experiments using different IN measurement methods and to obtain IN data as a function of particle concentration, temperature (T), cooling rate and nucleation time. A total of 17 measurement methods were involved in the data intercomparison. Experiments with seven instruments started with the test sample pre-suspended in water before cooling, while 10 other instruments employed water vapor condensation onto dry-dispersed particles followed by immersion freezing. The resulting comprehensive immersion freezing data set was evaluated using the ice nucleation active surface-site density, ns, to develop a representative ns(T) spectrum that spans a wide temperature range (−37 °C In general, the 17 immersion freezing measurement techniques deviate, within a range of about 8 °C in terms of temperature, by 3 orders of magnitude with respect to ns. In addition, we show evidence that the immersion freezing efficiency expressed in ns of illite NX particles is relatively independent of droplet size, particle mass in suspension, particle size and cooling rate during freezing. A strong temperature dependence and weak time and size dependence of the immersion freezing efficiency of illite-rich clay mineral particles enabled the ns parameterization solely as a function of temperature. We also characterized the ns(T) spectra and identified a section with a steep slope between −20 and −27 °C, where a large fraction of active sites of our test dust may trigger immersion freezing. This slope was followed by a region with a gentler slope at temperatures below −27 °C. While the agreement between different instruments was reasonable below ~ −27 °C, there seemed to be a different trend in the temperature-dependent ice nucleation activity from the suspension and dry-dispersed particle measurements for this mineral dust, in particular at higher temperatures. For instance, the ice nucleation activity expressed in ns was smaller for the average of the wet suspended samples and higher for the average of the dry-dispersed aerosol samples between about −27 and −18 °C. Only instruments making measurements with wet suspended samples were able to measure ice nucleation above −18 °C. A possible explanation for the deviation between −27 and −18 °C is discussed. Multiple exponential distribution fits in both linear and log space for both specific surface area-based ns(T) and geometric surface area-based ns(T) are provided. These new fits, constrained by using identical reference samples, will help to compare IN measurement methods that are not included in the present study and IN data from future IN instruments.

Heterogeneous nucleation and shape transformation of multicomponent metallic nanostructures.

Abstract: To be able to control the functions of engineered multicomponent nanomaterials, a detailed understanding of heterogeneous nucleation at the nanoscale is essential. Here, by using in situ synchrotron X-ray scattering, we show that in the heterogeneous nucleation and growth of Au on Pt or Pt-alloy seeds the heteroepitaxial growth of the Au shell exerts high stress (∼2 GPa) on the seed by forming a core/shell structure in the early stage of the reaction. The development of lattice strain and subsequent strain relaxation, which we show using atomic-resolution transmission electron microscopy to occur through the slip of {111} layers, induces morphological changes from a core/shell to a dumbbell structure, and governs the nucleation and growth kinetics. We also propose a thermodynamic model for the nucleation and growth of dumbbell metallic heteronanostructures.

Palaeomagnetic field intensity variations suggest Mesoproterozoic inner-core nucleation.

Abstract: The Earth's inner core grows by the freezing of liquid iron at its surface. The point in history at which this process initiated marks a step-change in the thermal evolution of the planet. Recent computational and experimental studies have presented radically differing estimates of the thermal conductivity of the Earth's core, resulting in estimates of the timing of inner-core nucleation ranging from less than half a billion to nearly two billion years ago. Recent inner-core nucleation (high thermal conductivity) requires high outer-core temperatures in the early Earth that complicate models of thermal evolution. The nucleation of the core leads to a different convective regime and potentially different magnetic field structures that produce an observable signal in the palaeomagnetic record and allow the date of inner-core nucleation to be estimated directly. Previous studies searching for this signature have been hampered by the paucity of palaeomagnetic intensity measurements, by the lack of an effective means of assessing their reliability, and by shorter-timescale geomagnetic variations. Here we examine results from an expanded Precambrian database of palaeomagnetic intensity measurements selected using a new set of reliability criteria. Our analysis provides intensity-based support for the dominant dipolarity of the time-averaged Precambrian field, a crucial requirement for palaeomagnetic reconstructions of continents. We also present firm evidence for the existence of very long-term variations in geomagnetic strength. The most prominent and robust transition in the record is an increase in both average field strength and variability that is observed to occur between a billion and 1.5 billion years ago. This observation is most readily explained by the nucleation of the inner core occurring during this interval; the timing would tend to favour a modest value of core thermal conductivity and supports a simple thermal evolution model for the Earth.

Vacancy-Induced Formation and Growth of Inversion Domains in Transition-Metal Dichalcogenide Monolayer

Abstract: Sixty degree grain boundaries in semiconducting transition-metal dichalcogenide (TMDC) monolayers have been shown to act as conductive channels that have profound influence on both the transport properties and exciton behavior of the monolayers. Here, we show that annealing TMDC monolayers at high temperature induces the formation of large-scale inversion domains surrounded by such 60° grain boundaries. To study the formation mechanism of such inversion domains, we use the electron beam in a scanning transmission electron microscope to activate the dynamic process within pristine TMDC monolayers. The electron beam acts to generate chalcogen vacancies in TMDC monolayers and provide energy for them to undergo structural evolution. We directly visualize the nucleation and growth of such inversion domains and their 60° grain boundaries atom-by-atom within a MoSe2 monolayer and explore their formation mechanism. Combined with density functional theory, we conclude that the nucleation of the inversion domains a...