Delay time of gases's catalytic heterogeneous ignition on various sizes's catalyst particles

In this work, catalytic ignition delay time of combustible gas's small impurities in air on a spherical metal particle of various diameters is analytically determined by the example of gas-air mixtures's flameless combustion with hydrogen impurities on a platinum particle. It is shown that stable flameless combustion is observed after an induction period for particles of a certain range. It has been established that catalytic ignition time of gases is divided into three stages: 1. inert heating, the duration of which still depends on the combustible gas concentration; 2. the stage of self-acceleration and catalyst temperature rise during the course of the catalytic reaction in the transition region; 3. stage of diffusion inhibition and reaching stable catalytic combustion. The characteristic relaxation time was used in a dimensionless form. To determine the duration of the second stage, a modified Frank-Kamenetsky approach is applied. The duration of diffusion inhibition stage in the dimensionless form is practically independent of catalyst particle's diameter, although the catalytic combustion temperature decreases with an increase in the catalyst diameter. Heat transfer by radiation, the role of which increases with the growth of the catalyst size, is included in the effective heat transfer coefficient, which allows maintaining the classical ideology to solving the problem of the induction period.

Thermodynamic Analysis of Relaxation Model for Non-Equilibrium Phase Behavior of Hydrocarbon Mixtures

Mathematical models of phase behavior are widely used to describe multiphase oil and gas-condensate systems during hydrocarbon recovery from natural petroleum reservoirs. Previously a non-equilibrium phase behavior model was proposed as an extension over generally adopted equilibrium models. It is based on relaxation of component chemical potentials difference between phases and provides accurate calculations in some typical situations when non-instantaneous changing of phase fractions and compositions in response to variations of pressure or total composition is to be considered. In this paper we present a thermodynamic analysis of the relaxation model. General equations of non-equilibrium thermodynamics for multiphase flows in porous media are considered, and reduced entropy balance equation for the relaxation process is obtained. Isotropic relaxation process is simulated for a real multicomponent hydrocarbon system with different values of characteristic relaxation time using the non-equilibrium model implemented in the PVT Designer module of the RFD tNavigator simulation software. The results are processed with a special algorithm implemented in Matlab to calculate graphs of the total entropy time derivative and its constituents in the entropy balance equation. It is shown that the constituents have different signs, and the greatest influence on the entropy is associated with the interphase flow of the major component of the mixture and the change of the total system volume in the isotropic process. The characteristic relaxation time affects the rate at which the entropy is approaching its maximum value.

Fully Bio-Based Elastomer Nanocomposites Comprising Polyfarnesene Reinforced with Plasma-Modified Cellulose Nanocrystals

This article proposes a process to prepare fully bio-based elastomer nanocomposites based on polyfarnesene and cellulose nanocrystals (CNC). To improve the compatibility of cellulose with the hydrophobic matrix of polyfarnesene, the surface of CNC was modified via plasma-induced polymerization, at different powers of the plasma generator, using a trans-β-farnesene monomer in the plasma reactor. The characteristic features of plasma surface-modified CNC have been corroborated by spectroscopic (XPS) and microscopic (AFM) analyses. Moreover, the cellulose nanocrystals modified at 150 W have been selected to reinforce polyfarnesene-based nanocomposites, synthesized via an in-situ coordination polymerization using a neodymium-based catalytic system. The effect of the different loading content of nanocrystals on the polymerization behavior, as well as on the rheological aspects, was evaluated. The increase in the storage modulus with the incorporation of superficially modified nanocrystals was demonstrated by rheological measurements and these materials exhibited better properties than those containing pristine cellulose nanocrystals. Moreover, we elucidate that the viscoelastic moduli of the elastomer nanocomposites are aligned with power–law model systems with characteristic relaxation time scales similar to commercial nanocomposites, also implying tunable mechanical properties. In this foreground, our findings have important implications in the development of fully bio-based nanocomposites in close competition with the commercial stock, thereby producing alternatives in favor of sustainable materials.

Dielectric Relaxation, Local Structure and Lattice Dynamics in Mn-Doped Potassium Tantalate Ceramics

Alkaline niobate and tantalate perovskites have attracted attention as polar dielectrics for electronics and telecommunications. Here, we studied the polar behaviour, lattice dynamics, and local structure in conventionally processed K0.985Mn0.015TaO3±δ ceramics using a combination of variable-temperature dielectric and Raman spectroscopies, and X-ray absorption fine structure (XAFS) measurements, respectively. Mn doping induces a low-frequency dielectric relaxation in KTaO3 (KT), which follows the Arrhenius law with an activation energy U ≈ 105 meV and the characteristic relaxation time τ0 ≈ 4.6 × 10−14 s. Our XAFS results support preferential Mn occupancy of the cuboctahedral sites as Mn2+, with these cations strongly off-centred in the oversized oxygen cages. Such disordered Mn displacements generate electric dipoles, which are proposed as the source of the observed dielectric relaxation. We show that in Mn-doped ceramics, the low-frequency polar TO1 mode softens on cooling and, at low temperatures, exhibits a higher frequency than in undoped KT. This mode displays no detectable splitting, which contrasts with Li-doped KT that also contains off-centred Li+ species on the cuboctahedral sites. Therefore, we conclude that the coupling between the Mn displacements and the lattice is weaker than in the Li case, and Mn-doped KT therefore exhibits a dielectric relaxation but no ferroelectric transition.

Quality Control in Fiore Sardo PDO Cheese: Detection of Heat Treatment Application and Production Chain by MRI Relaxometry and Image Analysis

Fiore Sardo (FS), a traditional Italian cheese, is present in the market as a heterogeneous variety of products. The use of heat-treated (HT) milk is forbidden by the official production protocol, but no official analytical method able to detect heat application is yet available. Here, a combined magnetic resonance imaging (MRI) relaxometry and image analysis approach to recognize FS made from raw milk is presented. Artisanal FS cheeses were produced from raw milk (RC) by five shepherds in accordance with the official protocol. They were compared to HT-milk counterparts (HTC). Additionally, industrially manufactured commercial FS cheeses (I) were also purchased and compared to RC and HTC. Relaxometry data of FS indicated the presence of two water populations; the ratio of characteristic relaxation time constant T2 and area fraction (Score, Ṩ) of the fastest relaxing population was used to compare RC, HTC and I samples. RC from HTC were successfully discriminated, the latter exhibiting lower Ṩ (enhanced protein hydration). I cheeses exhibited the lowest Ṩ values, sometimes comparable to HTC. Since visual appearance of RC and HTC is appreciably different, an image analysis deep learning approach using MRI and photographic pictures was adopted to discriminate the two productions, with promising percentages (>93%).

Experimental evidence of mosaic structure in strongly supercooled molecular liquids

When a liquid is cooled to produce a glass its dynamics, dominated by the structural relaxation, become very slow, and at the glass-transition temperature Tg its characteristic relaxation time is about 100 s. At slightly elevated temperatures (~1.2 Tg) however, a second process known as the Johari-Goldstein relaxation, βJG, decouples from the structural one and remains much faster than it down to Tg. While it is known that the βJG-process is strongly coupled to the structural relaxation, its dedicated role in the glass-transition remains under debate. Here we use an experimental technique that permits us to investigate the spatial and temporal properties of the βJG relaxation, and give evidence that the molecules participating in it are highly mobile and spatially connected in a system-spanning, percolating cluster. This correlation of structural and dynamical properties provides strong experimental support for a picture, drawn from theoretical studies, of an intermittent mosaic structure in the deeply supercooled liquid phase.

Parameter estimation for correlated Ornstein-Uhlenbeck time-series

In this article, we develop a Maximum likelihood (ML) approach to estimate parameters from correlated time traces that originate from coupled Ornstein-Uhlenbeck processes. The most common technique to characterize the correlation between time-series is to calculate the Pearson correlation coefficient. Here we show that for time series with memory (or a characteristic relaxation time), our method gives more reliable results, but also results in coupling coefficients and their uncertainties given the data. We investigate how these uncertainties depend on the number of samples, the relaxation times and sampling time. To validate our analytic results, we performed simulations over a wide range of correlation coefficients both using our maximum likelihood solutions and Markov-Chain Monte-Carlo (MCMC) simulations. We found that both ML and MCMC result in the same parameter estimations. We also found that when analyzing the same data, the ML and MCMC uncertainties are strongly correlated, while ML underestimates the uncertainties by a factor of 1.5 to 3 over a large range of parameters. For large datasets, we can therfore use the less computationally expensive maximum likelihood method to run over the whole dataset, and then we can use MCMC on a few samples to determine the factor by which the ML method underestimates the uncertainties. To illustrate the application of our method, we apply it to time series of brain activation using fMRI measurements of the human default mode network. We show that our method significantly improves the interpretation of multi-subject measurements of correlations between brain regions by providing parameter confidence intervals for individual measurements, which allows for distinguishing between the variance from differences between subjects from variance due to measurement error.

Analysis of stress in the conveyor belt (Maxwell–element model)

longitudinal dynamic stresses and investigate the peculiarities of the propagation of dynamic stresses along the route of material transportation. Methodology. To calculate the value of static and dynamic stresses arising in the conveyor belt, the apparatus of mathematical physics was used. Findings. A wave equation is written that determines the propagation of longitudinal vibrations in a conveyor belt, the material of which corresponds to the Maxwell-element model. An expression is obtained for calculating the speed of propagation of elastic vibrations along the conveyor belt, the frequency of vibrations and their wavelength. The characteristic relaxation time of disturbances is determined. The method of successive approximation was used to solve the wave equation. The estimation of the characteristic time of acceleration of the conveyor belt, at which there is no destruction of the material of the conveyor belt, is given. Originality. PDE-models of conveyor-type transport systems are improved, which are used to design belt speed control systems under restrictions on speed control modes. It is shown that under the modes of acceleration or deceleration of the conveyor belt, the effects associated with the occurrence and propagation of dynamic stresses along the conveyor belt, due to the characteristics of the material corresponding to the Maxwell-element model, are insignificant. Practical value. The results obtained make it possible to determine the limitations on the modes of acceleration or deceleration of the conveyor belt, preventing its damage and increased wear. This opens up prospects for designing effective control systems for the parameters of a conveyor belt, unevenly loaded with material along the transport route.

Diffusion Spectrum of Polymer Melt Measured by Varying Magnetic Field Gradient Pulse Width in PGSE NMR

The translational motion of polymers is a complex process and has a big impact on polymer structure and chemical reactivity. The process can be described by the segment velocity autocorrelation function or its diffusion spectrum, which exhibit several characteristic features depending on the observational time scale—from the Brownian delta function on a large time scale, to complex details in a very short range. Several stepwise, more-complex models of translational dynamics thus exist—from the Rouse regime over reptation motion to a combination of reptation and tube-Rouse motion. Accordingly, different methods of measurement are applicable, from neutron scattering for very short times to optical methods for very long times. In the intermediate regime, nuclear magnetic resonance (NMR) is applicable—for microseconds, relaxometry, and for milliseconds, diffusometry. We used a variation of the established diffusometric method of pulsed gradient spin-echo NMR to measure the diffusion spectrum of a linear polyethylene melt by varying the gradient pulse width. We were able to determine the characteristic relaxation time of the first mode of the tube-Rouse motion. This result is a deviation from a Rouse model of polymer chain displacement at the crossover from a square-root to linear time dependence, indicating a new long-term diffusion regime in which the dynamics of the tube are also described by the Rouse model.