Chemical Supercritical Fluid Infiltration of Pyrocarbon with Thermal Gradients: Deposition Kinetics and Multiphysics Modeling

The chemical supercritical fluid infiltration process is a recent variation of the chemical vapor infiltration (CVI) process that allows rapid and efficient manufacturing of ceramic-matrix composites (CMCs), albeit still needing optimization. This article proposes a quantitative assessment of the process dynamics through experiments and modeling. The kinetics of carbon deposition were determined through two sets of experiments: CVD on a single filament at pressures between 10 and 50 bar and infiltration at pressures ranging between 50 and 120 bar. The CVI experiments were conducted under important thermal gradients and were interpreted using a model-based reconstitution of these gradients. We found that (i) the kinetic law has to incorporate the potential effect of the reverse reaction (i.e., etching of C by H2); (ii) the activation energy and pre-exponential factor both decrease with pressure up to 50 bar, then remain roughly constant, and (iii) although the apparent activation energy is modest, a favorable situation occurs in which an infiltration front builds up and travels from the hottest to the coldest part of the preform due to the presence of sufficient heat flux. A numerical simulation of the process, based on the solution of momentum, heat, and mass balance equations, fed with appropriate laws for the effective transfer properties of the porous medium and their evolution with infiltration progress, was performed and validated by comparing the simulated and actual infiltration profiles.

Thermal Decomposition of 3-Nitro-1,2,4-Triazole-5-One (NTO) and Nanosize NTO Catalyzed by NiFe2O4

Nanosize Nickel ferrite (NiF) was synthesized by the co-precipitation methods and its effect as a 5 % by mass additive was studied on the thermal decomposition of micrometer and nanometer size NTO. In the presence of 5 % NiF additive, the thermal decomposition peak temperature of NTO was decreased from 276.36 to 260.18 oC and that of nano NTO was decreased from 261.38 to 258.89 oC (β=10 oC min-1). The kinetics parameters confirms the catalytic activity of NiF for the thermal decomposition of NTO, and nNTO as the parameters such as activation energy (NTO=~25.45 % and nNTO=~45.94 % decrement), and pre-exponential factor (NTO=~21.94 % and nNTO=~43.12 % decrement) were decreased when 5 % NiF additive was added to NTO, and nNTO. The rate of the decomposition process was increased in the presence of 5 % NiF catalyst, indicating the faster thermal decomposition of both NTO, and nNTO in the presence of nickel catalyst.

Shape- and size- dependent desorption kinetics and surface acidity on nano-SnO2

The desorption kinetic parameters (the desorption activation energy (Ed) and the desorption pre-exponential factor (A)) and the surface acidity (the strength and number of acid sites) of spherical and octahedral...

A weighted group shuffled decoding for low-density parity-check codes

In this paper, we have developed several concepts such as the tree concept, the short cycle concept and the group shuffling concept of a propagation cycle to decrypt low-density parity-check (LDPC) codes. Thus, we proposed an algorithm based on group shuffling propagation where the probability of occurrence takes exponential form exponential factor appearance probability belief propagation-group shuffled belief propagation (EFAP-GSBP). This algorithm is used for wireless communication applications by providing improved decryption performance with low latency. To demonstrate the effectiveness of our suggested technique EFAP-GSBP, we ran numerous simulations that demonstrated that our algorithm is superior to the traditional BP/GSBP algorithm for decrypting LPDC codes in both regular and non-regular forms

Thermodynamic Parameters of Nonisothermal Degradation of A New Family of Organometallic Dendrimer with Isoconversional Methods

The objective of this work is to obtain the thermodynamic parameters, namely, the changes of enthalpy, Gibbs free energy, and the entropy of two degradation steps observed in three of a new family of organometallic dendrimers. The isoconversional Flynn-Wall-Ozawa (FWO) model was employed to calculate the effective activation energy and pre-exponential factor. The changes of enthalpy and the entropy was consistent with the activation energy, whereas the change of Gibbs free energy remains positive during the entire degradation process, implying that the degradation is non-spontaneous and thus requires external heat supply.

Determination of the Thermodynamic Parameters of the Pyrolysis Process of Post-Consumption Thermoplastics by Non-Isothermal Thermogravimetric Analysis

Currently, the pyrolysis process is an important technology for the final treatment of plastic waste worldwide. For this reason, knowing in detail the chemical process and the thermodynamics that accompany cracking reactions is of utmost importance. The present study aims to determine the thermodynamic parameters of the degradation process of conventional thermoplastics (polystyrene (PS), polyethylene terephthalate (PET), high-density polyethylene (HDPE), polypropylene (PP) and polyvinyl chloride (PVC)) from the study of their chemical kinetics by thermogravimetric analysis (TG). Non-isothermal thermogravimetry was performed at three heating rates from room temperature to 550 °C with an inert nitrogen atmosphere with a flow of 20 mL min−1. Once the TG data is obtained, an analysis is carried out with the isoconversional models of Friedman (FR), Kissinger-Akahira-Sunose (KAS), and Flynn-Wall-Ozawa (FWO) in order to determine the one that best fits the experimental data, and with this, the calculation of the activation energy and the pre-exponential factor is performed. The validation of the model was carried out using the correlation factor, determining that the KAS model is the one that best adjusts for the post-consumer thermoplastic degradation process at the three heating rates. With the use of the kinetic parameters, the variation of the Gibbs free energy is determined in each of the cases, where it is necessary that for structures containing aromatic groups a lower energy is presented, which implies a relative ease of degradation compared to the linear structures.

Pyrolytic Behavior of Polyvinyl Chloride: Kinetics, Mechanisms, Thermodynamics, and Artificial Neural Network Application

Pyrolysis of waste polyvinyl chloride (PVC) is considered a promising and highly efficient treatment method. This work aims to investigate the kinetics, and thermodynamics of the process of PVC pyrolysis. Thermogravimetry of PVC pyrolysis at three heating rates (5, 10, and 20 K/min) showed two reaction stages covering the temperature ranges of 490–675 K, and 675–825 K, respectively. Three integral isoconversional models, namely Flynn-Wall-Qzawa (FWO), Kissinger-Akahira-Sunose (KAS), and Starink, were used to obtain the activation energy (Ea), and pre-exponential factor (A) of the PVC pyrolysis. On the other hand, the Coats-Redfern non-isoconversional model was used to determine the most appropriate solid-state reaction mechanism/s for both stages. Values of Ea, and A, obtained by the isoconversional models, were very close and the average values were, for stage I: Ea = 75 kJ/mol, A = 1.81 × 106 min−1; for stage II: Ea = 140 kJ/mol, A = 4.84 × 109 min−1. In addition, while the recommended mechanism of the first stage reaction was P2, F3 was the most suitable mechanism for the reaction of stage II. The appropriateness of the mechanisms was confirmed by the compensation effect. Thermodynamic study of the process of PVC pyrolysis confirmed that both reactions are endothermic and nonspontaneous with promising production of bioenergy. Furthermore, a highly efficient artificial neural network (ANN) model has been developed to predict the weight left % during the PVC pyrolysis as a function of the temperature and heating rate. The 2-10-10-1 topology with TANSIG-LOGSIG transfer function and feed-forward back-propagation characteristics was used.

Mechanochemistry of phosphate esters confined between sliding iron surfaces

The molecular structure of lubricant additives controls not only their adsorption and dissociation behaviour at the nanoscale, but also their ability to reduce friction and wear at the macroscale. Here, we show using nonequilibrium molecular dynamics simulations with a reactive force field that tri(s-butyl)phosphate dissociates much faster than tri(n-butyl)phosphate when heated and compressed between sliding iron surfaces. For both molecules, dissociative chemisorption proceeds through cleavage of carbon−oxygen bonds. The dissociation rate increases exponentially with temperature and stress. When the rate−temperature−stress data are fitted with the Bell model, both molecules have similar activation energies and activation volumes and the higher reactivity of tri(s-butyl)phosphate is due to a larger pre-exponential factor. These observations are consistent with experiments using the antiwear additive zinc dialkyldithiophosphate. This study represents a crucial step towards the virtual screening of lubricant additives with different substituents to optimise tribological performance.