Outlier Detection and Data Cleaning in Multivariate Non-Normal Samples: The PAELLA Algorithm

A new method of outlier detection and data cleaning for both normal and non-normal multivariate data sets is proposed. It is based on an iterated local fit without a priori metric assumptions. We propose a new approach supported by finite mixture clustering which provides good results with large data sets. A multi-step structure, consisting of three phases, is developed. The importance of outlier detection in industrial modeling for open-loop control prediction is also described. The described algorithm gives good results both in simulations runs with artificial data sets and with experimental data sets recorded in a rubber factory. Finally, some discussion about this methodology is exposed.     

Efficient Estimation of Qualitative Topological Relations based on the Weighted Walkthroughs Model

Weighted walkthroughs are a quantitative model for representing the spatial relation between two raster features in image databases. In this paper, we establish a correspondence between the weighted walkthroughs and qualitative models for spatial reasoning. We provide rules for estimating qualitative geometric properties and topological relations from the quantitative data that are computed for each pair of pixel sets. The approach has been tested through experiments with raster regions.     

An experimental and kinetic modeling study of cyclopentadiene pyrolysis: First growth of polycyclic aromatic hydrocarbons

The importance of 1,3-cyclopentadiene (CPD) and cyclopentadienyl (CPDyl) moieties in the growth of polycyclic aromatic hydrocarbons (PAHs) was studied using new experimental data and ab initio calculations. The experimental investigation was performed in a tubular continuous flow pyrolysis reactor under both high (24molN₂/molCPD)$(24{\text{mol}}_{{\text{N}}_2}/{\text{mol}}_{\text{CPD}})$ and low (5molN₂/molCPD)$(5{\text{mol}}_{{\text{N}}_2}/{\text{mol}}_{\text{CPD}})$ nitrogen dilutions, covering a temperature range of 873–1123 K, at a fixed pressure of 1.7 bara. At the most severe conditions up to 84% of CPD is converted, and the amount of PAHs is more than 65 wt%. Major products observed during CPD pyrolysis were benzene, indene, methyl-indenes and naphthalene, in line with previous studies. On-line GC × GC-FID/(TOF-MS) also allowed to quantify minor species (methane, toluene, styrene, phenanthrene, anthracene, etc.), never reported before at this level of accuracy. The new experimental data have been used to further analyze the role of the successive interactions of CPD, indene, and naphthalene as well as the recombination and addition reactions of their resonantly stabilized radicals and refine their kinetics. The results of the modeling study are in good agreement with existing and new experimental observations.     

A wide range kinetic modeling study of the pyrolysis and combustion of naphthenes

The aim of this paper is to analyze and discuss the kinetics of the pyrolysis and combustion of naphthenes. The primary propagation reactions of cyclohexane and methylcyclohexane are presented to extend the validity of a semi-detailed kinetic model for the pyrolysis and oxidation of hydrocarbons. Naphthenes are relevant species as reference components in liquid fuels and surrogate blends. A lumped approach is used to reduce the complexity of the overall scheme in terms of species and reactions. Particular attention is devoted to the role of the isomerization or internal abstraction of H atoms in competition with β−decomposition ones. Primary oxidation and decomposition reactions of the cyclohexyl radical are discussed to explain and justify this lumping procedure. The modeling predictions are compared with different sets of measurements. The validation of the low temperature oxidation mechanism of cyclohexane is based on the ignition delay times obtained both in the rapid compression machine at Lille and in closed vessels. Jet-stirred reactors at different pressures and stoichiometric ratios also confirm the reliability of the overall mechanism of oxidation. The comparisons between the model’s predictions and the measurements relating to the pyrolysis and oxidation of methylcyclohexane in the Princeton turbulent flow reactor further support this extension of the kinetic scheme to naphthenes. Finally, the agreement with the oxidation experiments using mixtures of toluene + methylcyclohexane is a primary and simple example of the model’s ability to deal with the combustion of real fuels or surrogate blends.     

Prandtl–Tomlinson-Type Models for Coupled Molecular Sliding Friction: Chain-Length Dependence of Friction of Self-assembled Monolayers

Tribology Letters - Most asteroids with a diameter larger than $$\sim 300 \ {\mathrm{m}}$$ are rubble piles, i.e., consisting of more than one solid object. All asteroids are rotating but almost...     

An Unprecedented Stimuli‐Controlled Single‐Crystal Reversible Phase Transition of a Metal–Organic Framework and Its Application to a Novel Method of Guest Encapsulation

The flexibility and unexpected dynamic behavior of a third‐generation metal–organic framework are described for the first time. The synthetic strategy is based on the flexibility and spherical shape of dipyridyl‐based carborane linkers that act as pillars between rigid Co/BTB (BTB: 1,3,5‐benzenetricarboxylate) layers, providing a 3D porous structure ( 1 ). A phase transition of the solid can be induced to generate a new, nonporous 2D structure ( 2 ) without any loss of the carborane linkers. The structural transformation is visualized by snapshots of the multistep single‐crystal‐to‐single‐crystal transformation by single‐crystal and powder X‐ray diffraction. Poor hydrogen bond acceptors such as MeOH, CHCl₃ or supercritical CO₂ induce such a 3D to 2D transformation. Remarkably, the transformation is reversible and the 2D phase 2 is further converted back into 1 by heating in dimethylformamide. The energy requirements involved in such processes are investigated using periodic density functional theory calculations. As a proof of concept for potential applications, encapsulation of C₆₀ is achieved by trapping this molecule during the reversible 2D to 3D phase transition, whereas no adsorption is observed by straight solvent diffusion into the pores of the 3D phase.