Controlling Nonlinear Dynamics of Milling Bodies in Mechanochemical Devices Driven by Pendular Forcing.

Understanding the dynamics of milling bodies is key to optimize the mixing and the transfer of mechanical energy in mechanochemical processing. In this work, we present a comparative study of mechanochemical reactors driven by harmonic pendular forcing and characterized by different geometries of the lateral borders. We show that the shape of the reactor bases, either flat or curved, along with the size of the milling body and the elasticity of the collisions, represents relevant parameters that govern the dynamical regimes within the system and can control the transition from periodic to chaotic behaviors. We single out possible criteria to preserve target dynamical scenarios when the size of the milling body is changed, by adapting the relative extent of the spatial domain. This allows us to modulate the average energy of the collisions while maintaining the same dynamics and paves the way for a unifying framework to control the dynamical response in different experimental conditions. We finally explore the dynamical and energetic impact of an increasingly asymmetric mechanical force.

Integration of absolute multi-omics reveals dynamic protein-to-RNA ratios and metabolic interplay within mixed-domain microbiomes.

While the field of microbiology has adapted to the study of complex microbiomes via modern meta-omics techniques, we have not updated our basic knowledge regarding the quantitative levels of DNA, RNA and protein molecules within a microbial cell, which ultimately control cellular function. Here we report the temporal measurements of absolute RNA and protein levels per gene within a mixed bacterial-archaeal consortium. Our analysis of this data reveals an absolute protein-to-RNA ratio of 102-104 for bacterial populations and 103-105 for an archaeon, which is more comparable to Eukaryotic representatives' humans and yeast. Furthermore, we use the linearity between the metaproteome and metatranscriptome over time to identify core functional guilds, hence using a fundamental biological feature (i.e., RNA/protein levels) to highlight phenotypical complementarity. Our findings show that upgrading multi-omic toolkits with traditional absolute measurements unlocks the scaling of core biological questions to dynamic and complex microbiomes, creating a deeper insight into inter-organismal relationships that drive the greater community function.

High throughput mechanochemistry: application to parallel synthesis of benzoxazines.

We describe herein an unprecedented mechanochemical "parallel synthesis" of 3,4-dihydro-2H-benzo[e][1,3]oxazine derivatives via a one pot three component reaction. The new milling system uses a multiposition jar (variable sizes are possible), allowing for the processing of up to 12 samples simultaneously, leading to the formation of a fungicide and a building block for polymer preparation with higher throughput compared to standard milling devices.

Multifractal properties of ball milling dynamics.

This work focuses on the dynamics of a ball inside the reactor of a ball mill. We show that the distribution of collisions at the reactor walls exhibits multifractal properties in a wide region of the parameter space defining the geometrical characteristics of the reactor and the collision elasticity. This feature points to the presence of restricted self-organized zones of the reactor walls where the ball preferentially collides and the mechanical energy is mainly dissipated.

Thermodynamic stability of nanometre-sized Cu3Au systems.

Classical molecular dynamics simulations have been used to investigate the order-to-disorder transition in bulk and nanometre-sized Cu3Au systems. The Helmholtz free energy difference between ordered and disordered phases was evaluated at different temperatures through the Bennett's method. The change of free energy differences with temperature was employed to identify the transition temperatures. The obtained information was used to study the dynamics of a nanometre-sized Cu3Au particle in a He gas thermostat at the transition temperature. It is shown that the system underwent rapid fluctuation in the chemical order degree related to the formation of vacancies and of atoms with defective coordination. Additional information on surface energies was also gained through a thermodynamic description of the transition process.

The reversibility of phase transitions in Ti/Co core/shell nanometre-sized particles.

Molecular dynamics simulations have been employed to investigate the thermal response of unsupported Ti/Co core/shell particles with sizes between 2 and 10 nm. Co shells undergo a martensitic hcp-to-fcc phase transformation at temperatures dependent on the particle radius. Ti cores with radii of 2 nm or smaller also undergo the hcp-to-fcc transition. In the presence of Ti cores with radius larger than 2 nm, Co shells 2-4 nm thick exhibit hysteretic effects in the phase transformation. In particular, the transition temperatures under heating and cooling conditions are different. This determines the stabilization of the metastable fcc Co phase, related to the accumulation of lattice defects in the shell as a consequence of local atomic strains at the Ti/Co interface.

Room-temperature self-assembly of equilateral triangular clusters via Friedel oscillations.

We report on the formation of equilateral triangular clusters hollow inside with 5-6 atoms per side, self-assembled on Ni adislands grown on Rh(111). The observation of standing wave patterns on the Ni adislands and the Rh(111) indicates that the self-assembly is mediated by Friedel oscillations. In this context, we propose a model based on the energy of interaction between adsorbates, which explains the formation of the clusters as a result of the assembly of rows of 5-6 adatoms.

Growth of Ag nanometre-sized particles in solution: molecular dynamics simulations.

This work focuses on the growth of nanometre-sized Ag clusters in solution. Molecular dynamics simulations have been employed to gain the necessary detail on the dynamics of solute species and to study the mechanistic features of the processes governing the association of solute atoms in aggregates. Supersaturated liquid solutions of Ag in tetrachloromethane have been considered. A systematic variation of the concentration of Ag atoms in solution permitted us to show the different mechanistic scenarios responsible for the growth processes of solid Ag clusters. It is shown that such processes are limited by the thermal diffusion of solute in the solution bulk at relatively low supersaturation degrees, whereas the growth is limited by interfacial effects at relatively high supersaturation degrees.

A numerical study of the growth process of Au nanometre-sized particles in liquid phases.

Molecular dynamics simulations have been employed to study the growth of faceted and spherical gold (Au) nanometre-sized particles in undercooled Au melts and supersaturated Kr-, Xe- and Rn-based liquid solutions at different degrees of undercooling and supersaturation. Different mechanisms have been observed depending on the chemical environment and temperature. At relatively high temperatures, surface adsorption is shown to critically depend on the dynamics of surface species with low coordination number. At low temperatures, adsorption occurs instead with no selective feature. Dendritic structures are formed at the particle surface at high adsorption rates.

Mechanically induced self-propagating reactions: analysis of reactive substrates and degradation of aromatic sulfonic pollutants.

Mechanochemical reactions have been identified as a valuable alternative to conventional methodologies for the degradation of toxic pollutants as well as for their abatement in contaminated matrices. This paper discusses the application of the mechanochemical technique to the degradation of sulfonic acids in a contaminated matrix. The degradation of the pollutant compound was carried out by taking advantage of combustive reactions on a suitable reactive system ignited under mechanical treatment conditions. Two systems have been investigated as possible reactive substrates. The first one was a Mg-SiO2 powder mixture while the second system was a Ca-SiO2 powder mixture. Milling trials performed under different mechanical processing conditions allowed one to characterise the reactivity of these chemical systems, which basically undergo a reduction/oxidation reaction involving the formation of MgO and Si phases when the Mg-SiO2 system is considered and CaO and Si phases when the Ca-SiO2 system is employed, respectively. The systematic change of the stoichiometric ratios Mg:SiO2 and Ca:SiO2 permitted to identify the minimum Mg or Ca content necessary for the ignition of the combustive reactions. The experimental runs performed with such systems have shown a greater effectiveness of the Mg-SiO2 because of less energy inputs required to ignite a combustion. For this reason the Mg-SiO2 has been considered as a reactive substrate in the following trials. Since the SiO2 amount in stoichiometric excess may be regarded as inert phase, it was substituted with a different phase consisting of the matrix contaminated by sulfonic acids. This aspect permitted to ignite a combustive reaction with the minimum possible content of Mg-SiO2 reacting mixture. The chemical analyses performed after the combustive reaction proved the complete removal of the sulfonic acid from the contaminated matrix.

Onset of chaotic dynamics in a ball mill: Attractors merging and crisis induced intermittency.

In mechanical treatment carried out by ball milling, powder particles are subjected to repeated high-energy mechanical loads which induce heavy plastic deformations together with fracturing and cold-welding events. Owing to the continuous defect accumulation and interface renewal, both structural and chemical transformations occur. The nature and the rate of such transformations have been shown to depend on variables, such as impact velocity and collision frequency that depend, in turn, on the whole dynamics of the system. The characterization of the ball dynamics under different impact conditions is then to be considered a necessary step in order to gain a satisfactory control of the experimental set up. In this paper we investigate the motion of a ball in a milling device. Since the ball motion is governed by impulsive forces acting during each collision, no analytical expression for the complete ball trajectory can be obtained. In addition, mechanical systems exhibiting impacts are strongly nonlinear due to sudden changes of velocities at the instant of impact. Many different types of periodic and chaotic impact motions exist indeed even for simple systems with external periodic excitation forces. We present results of the analysis on the ball trajectory, obtained from a suitable numerical model, under growing degree of impact elasticity. A route to high dimensional chaos is obtained. Crisis and attractors merging are also found. (c) 2002 American Institute of Physics.

Hyperchaotic qualities of the ball motion in a ball milling device.

Ball collisions in milling devices are governed by complex dynamics ruled by impredictable impulsive forces. In this paper, nonlinear dynamics techniques are employed to analyze the time series describing the trajectory of a milling ball in an empty container obtained from a numerical model. The attractor underlying the system dynamics was reconstructed by the time delay method. In order to characterize the system dynamics the calculation of the spectrum of Lyapunov exponents was performed. Six Lyapunov exponents, divided into two terns with opposite sign, were obtained. The detection of the positive tern demonstrates the occurrence of the hyperchaotic qualities of the ball motion. A fractal Lyapunov dimension, equal to 5.62, was also obtained confirming the strange features of the attractor. (c) 1999 American Institute of Physics.