566 research outputs found
Crystallographic orientation inhomogeneity and crystal splitting in biogenic calcite
The calcitic prismatic units forming the outer shell of the bivalve Pinctada margaritifera have been analysed using scanning electron microscopyâelectron back-scatter diffraction, transmission electron microscopy and atomic force microscopy. In the initial stages of growth, the individual prismatic units are single crystals. Their crystalline orientation is not consistent but rather changes gradually during growth. The gradients in crystallographic orientation occur mainly in a direction parallel to the long axis of the prism, i.e. perpendicular to the shell surface and do not show preferential tilting along any of the calcite lattice axes. At a certain growth stage, gradients begin to spread and diverge, implying that the prismatic units split into several crystalline domains. In this way, a branched crystal, in which the ends of the branches are independent crystalline domains, is formed. At the nanometre scale, the material is composed of slightly misoriented domains, which are separated by planes approximately perpendicular to the c-axis. Orientational gradients and splitting processes are described in biocrystals for the first time and are undoubtedly related to the high content of intracrystalline organic molecules, although the way in which these act to induce the observed crystalline patterns is a matter of future research
Power-law distributions in empirical data
Power-law distributions occur in many situations of scientific interest and
have significant consequences for our understanding of natural and man-made
phenomena. Unfortunately, the detection and characterization of power laws is
complicated by the large fluctuations that occur in the tail of the
distribution -- the part of the distribution representing large but rare events
-- and by the difficulty of identifying the range over which power-law behavior
holds. Commonly used methods for analyzing power-law data, such as
least-squares fitting, can produce substantially inaccurate estimates of
parameters for power-law distributions, and even in cases where such methods
return accurate answers they are still unsatisfactory because they give no
indication of whether the data obey a power law at all. Here we present a
principled statistical framework for discerning and quantifying power-law
behavior in empirical data. Our approach combines maximum-likelihood fitting
methods with goodness-of-fit tests based on the Kolmogorov-Smirnov statistic
and likelihood ratios. We evaluate the effectiveness of the approach with tests
on synthetic data and give critical comparisons to previous approaches. We also
apply the proposed methods to twenty-four real-world data sets from a range of
different disciplines, each of which has been conjectured to follow a power-law
distribution. In some cases we find these conjectures to be consistent with the
data while in others the power law is ruled out.Comment: 43 pages, 11 figures, 7 tables, 4 appendices; code available at
http://www.santafe.edu/~aaronc/powerlaws
One-step synthesis of a highly homogeneous SBA-NHC hybrid material: En route to single-site NHC-metal heterogeneous catalysts with high loadings
The one-step synthesis of a mesoporous silica of SBA type, functionalized with a 1-(2,6-diisopropylphenyl)-3-propyl-imidazolium (iPr2Ar-NHC-propyl) cation located in the pore channels, is described. This material was obtained by the direct hydrolysis and co-condensation of tetraethylorthosilicate (TEOS) and 1-(2,6-diisopropylphenyl)-3-[3-(triethoxysilyl)propyl]-imidazolium iodide in the presence of Pluronic P123 as a non-ionic structure-directing agent and aqueous HCl (37%) as an acid catalyst. Small-angle X-ray diffraction measurements, scanning and transmission electron microscopies, as well as dinitrogen sorption analyses revealed that the synthesized material is highly mesoporous with a 2D hexagonal arrangement of the porous network. 13C and 29Si CP-MAS NMR spectroscopy confirmed that the material contains intact iPr2Ar-NHC-propyl cations, which are covalently anchored via silicon atoms fused into the silica matrix. Moreover, comparison of the latter data with those of an analogous post-synthetic grafted SBAâNHC material allowed us to establish that, as expected, (i) it is most probably more homogeneous and (ii) it shows a more robust anchoring of the organic units. Finally, elemental mapping by energy dispersive X-ray spectroscopy in the scanning electron microscope demonstrated a very homogeneous distribution of the imidazolium units within the one-pot material, moreover with a high content. This study thus demonstrates that a relatively bulky and hydrophilic imidazolium unit can be directly co-condensed with TEOS in the presence of a structure-directing agent to provide in a single step a highly ordered and homogeneous mesoporous hybrid SBAâNHC material, possessing a significant number of cationic NHC sites
Highly optimized tolerance and power laws in dense and sparse resource regimes
Power law cumulative frequency vs. event size distributions
are frequently cited as evidence for complexity and
serve as a starting point for linking theoretical models and mechanisms with
observed data. Systems exhibiting this behavior present fundamental
mathematical challenges in probability and statistics. The broad span of length
and time scales associated with heavy tailed processes often require special
sensitivity to distinctions between discrete and continuous phenomena. A
discrete Highly Optimized Tolerance (HOT) model, referred to as the
Probability, Loss, Resource (PLR) model, gives the exponent as a
function of the dimension of the underlying substrate in the sparse
resource regime. This agrees well with data for wildfires, web file sizes, and
electric power outages. However, another HOT model, based on a continuous
(dense) distribution of resources, predicts . In this paper we
describe and analyze a third model, the cuts model, which exhibits both
behaviors but in different regimes. We use the cuts model to show all three
models agree in the dense resource limit. In the sparse resource regime, the
continuum model breaks down, but in this case, the cuts and PLR models are
described by the same exponent.Comment: 19 pages, 13 figure
Ordered structure of FeGe<sub>2</sub> formed during solid-phase epitaxy
Fe3Si/Ge(Fe,Si)/Fe3Si thin-film stacks were grown by a combination of molecular beam epitaxy and solid-phase epitaxy (Ge on Fe3Si). The stacks were analyzed using electron microscopy, electron diffraction, and synchrotron x-ray diffraction. The Ge(Fe,Si) films crystallize in the well-oriented, layered tetragonal structure FeGe2 with space group P4mm. This kind of structure does not exist as a bulk material and is stabilized by the solid-phase epitaxy of Ge on Fe3Si. We interpret this as an ordering phenomenon induced by minimization of the elastic energy of the epitaxial film
Tuning the surface structure of supported PtNi<sub>x</sub> bimetallic electrocatalysts for the methanol electro-oxidation reaction
The structures of PtNix nanoalloy particles were modified through thermal annealing in different atmospheres. The evolution of surface structures was uncovered by advanced transmission electron microscopy, and the structureâfunction correlation in methanol electro-oxidation was probed. It provided new insights into the design and synthesis of highly efficient electrocatalysts
Fluctuation-driven capacity distribution in complex networks
Maximizing robustness and minimizing cost are common objectives in the design
of infrastructure networks. However, most infrastructure networks evolve and
operate in a highly decentralized fashion, which may significantly impact the
allocation of resources across the system. Here, we investigate this question
by focusing on the relation between capacity and load in different types of
real-world communication and transportation networks. We find strong empirical
evidence that the actual capacity of the network elements tends to be similar
to the maximum available capacity, if the cost is not strongly constraining. As
more weight is given to the cost, however, the capacity approaches the load
nonlinearly. In particular, all systems analyzed show larger unoccupied
portions of the capacities on network elements subjected to smaller loads,
which is in sharp contrast with the assumptions involved in (linear) models
proposed in previous theoretical studies. We describe the observed behavior of
the capacity-load relation as a function of the relative importance of the cost
by using a model that optimizes capacities to cope with network traffic
fluctuations. These results suggest that infrastructure systems have evolved
under pressure to minimize local failures, but not necessarily global failures
that can be caused by the spread of local damage through cascading processes
A Poissonian explanation for heavy-tails in e-mail communication
Patterns of deliberate human activity and behavior are of utmost importance
in areas as diverse as disease spread, resource allocation, and emergency
response. Because of its widespread availability and use, e-mail correspondence
provides an attractive proxy for studying human activity. Recently, it was
reported that the probability density for the inter-event time between
consecutively sent e-mails decays asymptotically as , with
. The slower than exponential decay of the inter-event time
distribution suggests that deliberate human activity is inherently
non-Poissonian. Here, we demonstrate that the approximate power-law scaling of
the inter-event time distribution is a consequence of circadian and weekly
cycles of human activity. We propose a cascading non-homogeneous Poisson
process which explicitly integrates these periodic patterns in activity with an
individual's tendency to continue participating in an activity. Using standard
statistical techniques, we show that our model is consistent with the empirical
data. Our findings may also provide insight into the origins of heavy-tailed
distributions in other complex systems.Comment: 9 pages, 5 figure
Methane Decomposition and Carbon Growth on Y<sub>2</sub>O<sub>3</sub>, Yttria-Stabilized Zirconia, and ZrO<sub>2</sub>
Carbon deposition following thermal methane decomposition under dry and steam reforming conditions has been studied on yttria-stabilized zirconia (YSZ), Y2O3 and ZrO2 by a range of different chemical, structural and spectroscopic characterization techniques, including aberration-corrected electron microscopy, Raman spectroscopy, electric impedance spectroscopy and volumetric adsorption techniques. Concordantly, all experimental techniques reveal the formation of a conducting layer of disordered nanocrystalline graphite covering the individual grains of the respective pure oxides after treatment in dry methane at temperatures T â„ 1000 K. In addition, treatment under moist methane conditions causes additional formation of carbon-nanotube-like architectures by partial detachment of the graphite layers. All experiments show that during carbon growth, no substantial reduction of any of the oxides takes place. Our results therefore indicate that these pure oxides can act as efficient nonmetallic substrates for methane-induced growth of different carbon species with potentially important implications regarding their use in solid oxide fuel cells. By comparison of the three oxides we could moreover elucidate differences in the methane reactivities of the respective SOFC-relevant purely oxidic surfaces under typical SOFC operation conditions without the presence of metallic constituents
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