Data-Driven Approaches to Learn HyChem Models

The HyChem (Hybrid Chemistry) approach has recently been proposed for modeling high-temperature combustion of real, multi-component fuels. The approach combines lumped reaction steps for fuel thermal and oxidative pyrolysis with detailed chemistry for the oxidation of the resulting pyrolysis products. Determining the pyrolysis submodel requires extensive experimentation on speciation measurements. Recent work has been directed to learn HyChem from an existing HyChem model for a similar fuel, which requires less data. However, the approach usually shows substantial discrepancies with experimental data within the Negative Temperature Coefficient (NTC) regime, as the low-temperature chemistry is more fuel-specific than high-temperature chemistry. This paper proposes a machine learning approach to learn the HyChem models that can cover both high-temperature and low-temperature regimes. Specifically, we develop a HyChem model using the experimental datasets of ignition delay times covering a wide range of temperatures and equivalence ratios. The chemical kinetic model is treated as a neural network model, and we then employ stochastic gradient descent (SGD), a technique that was developed for deep learning, for the training. We demonstrate the approach in learning the HyChem model for F-24, which is a Jet-A derived fuel, and compare the results with previous work employing genetic algorithms. The results show that the SGD approach can achieve comparable model performance with genetic algorithms but the computational cost is reduced by 1000 times. In addition, with regularization in SGD, the SGD approach changes the kinetic parameters from their original values much less than genetic algorithm and is thus more likely to retrain mechanistic meanings. Finally, our approach is built upon open-source packages and can be applied to the development and optimization of chemical kinetic models for internal combustion engine simulations.

Nucleosome Assembly and Disassembly in vitro Are Governed by Chemical Kinetic Principles

As the elementary unit of eukaryotic chromatin, nucleosomes in vivo are highly dynamic in many biological processes, such as DNA replication, repair, recombination, or transcription, to allow the necessary factors to gain access to their substrate. The dynamic mechanism of nucleosome assembly and disassembly has not been well described thus far. We proposed a chemical kinetic model of nucleosome assembly and disassembly in vitro. In the model, the efficiency of nucleosome assembly was positively correlated with the total concentration of histone octamer, reaction rate constant and reaction time. All the corollaries of the model were well verified for the Widom 601 sequence and the six artificially synthesized DNA sequences, named CS1–CS6, by using the salt dialysis method in vitro. The reaction rate constant in the model may be used as a new parameter to evaluate the nucleosome reconstitution ability with DNAs. Nucleosome disassembly experiments for the Widom 601 sequence detected by Förster resonance energy transfer (FRET) and fluorescence thermal shift (FTS) assays demonstrated that nucleosome disassembly is the inverse process of assembly and can be described as three distinct stages: opening phase of the (H2A–H2B) dimer/(H3–H4)2 tetramer interface, release phase of the H2A–H2B dimers from (H3–H4)2 tetramer/DNA and removal phase of the (H3–H4)2 tetramer from DNA. Our kinetic model of nucleosome assembly and disassembly allows to confirm that nucleosome assembly and disassembly in vitro are governed by chemical kinetic principles.

The Effect of Porosity Change in Bentonite Caused by Decay Heat on Radionuclide Transport through Buffer Material

Bentonite is used as a buffer material in most high-level radioactive waste (HLW) repository designs. Smectite clay is the main mineral component of bentonite and plays a key role in controlling the buffer’s physical and chemical behaviors. Moreover, the long-term functions of buffer clay could be lost through smectite dehydration under the prevailing temperature stemming from the heat of waste decay. Therefore, the influence of waste decay temperatures on bentonite performance needs to be studied. However, seldom addressed is the influence of the thermo-hydro-chemical (T-H-C) processes on buffer material degradation in the engineered barrier system (EBS) of HLW disposal repositories as related to smectite clay dehydration. Therefore, we adopted the chemical kinetic model of smectite dehydration to calculate the amount of water expelled from smectite clay minerals caused by the higher temperatures of waste decay heat. We determined that the temperature peak of about 91.3 °C occurred at the junction of the canister and buffer material in the sixth year. After approximately 20,000 years, the thermal caused by the release of the canister had dispersed and the temperature had reduced close to the geothermal background level. The modified porosity of bentonite due to the temperature evolution in the buffer zone between 0 and 0.01 m near the canister was 0.321 (1–2 years), 0.435 (3–10 years), and 0.321 (11–20,000 years). In the buffer zone of 0.01–0.35 m, the porosity was 0.321 (1–20,000 years). In the simulation results of near-field radionuclide transport, we determined that the concentration of radionuclides released from the buffer material for the porosity of 0.321 was higher than that for the unmodified porosity of 0.435. It occurs after 1, 1671, 63, and 172 years for the I-129, Ni-59, Sr-90, and Cs137 radionuclides, respectively. The porosity correction model proposed herein can afford a more conservative concentration and approach to the real release concentration of radionuclides, which can be used for the safety assessment of the repository. Smectite clay could cause volume shrinkage because of the interlayer water loss in smectite and cause bentonite buffer compression. Investigation of the expansion pressure of smectite and the confining stress of the surrounding host rock can further elucidate the compression and volume expansion of bentonite. Within 10,000 years, the proportion of smectite transformed to illite is less than 0.05%. The decay heat temperature in the buffer material should be lower than 100 °C, which is a very important EBS design condition for radioactive waste disposal. The results of this study may be used in advanced research on the evolution of bentonite degradation for both performance assessments and safety analyses of final HLW disposal.

Mathematical Modelling of Turbulent Combustion of Two-Phase Mixtures of Gas and Solid Particles with a Eulerian–Eulerian Approach: The Case of Hydrogen Combustion in the Presence of Graphite Particles

The numerical modelling of turbulent combustion of H2–air mixtures with solid graphite particles is a challenging and key issue in many industrial problems including nuclear safety. This study presents a Eulerian–Eulerian model based on the resolution of the Navier–Stokes equations via large eddy simulation (LES) coupled with a system of ordinary differential equations (ODEs) of the detailed chemical kinetics to simulate the combustion of mixtures of gases and particles. The model was applied to predict the transient evolution of turbulent combustion sequences of mixtures of hydrogen, air and graphite particles under low concentration conditions. When applied to simulate lab-scale combustion experiments, the results showed a good agreement between experimental and numerical data using a detailed chemical kinetic model. Moreover, the model was able to predict some key experimental tendencies and revealed that the presence of a low concentration of graphite particles (~96 g/m3) in the scenario influenced the hydrogen combustion dynamics for mixtures of 20% (in volume) of hydrogen in air. Under these conditions, pressure levels reached at the walls of the sphere were increased and the combustion time was shortened. The results also showed the viability of using this kind of a model for obtaining global combustion parameters such as wall pressure evolution with time.

Study on the Mechanism of the Effect of Temperature on the Decomposition Reaction of SFn (n=1-6) under Discharge Conditions

The study on the mechanism of the effect of temperature on the decomposition reaction of SFn (n = 1–6) under discharge conditions is very important in studying the potential fault of SF6 high voltage switch equipment and perfecting the chemical kinetic model of SFn discharge. In this paper, structural optimizations, vibrational frequency calculations, and zero-point energy calculations for the reactants and products were performed at the B3LYP/6-311 + + G(d,p) theory level. The single-point energies of all species were collected at the CCSD(T)/aug-cc-PVTZ level. The electric and thermal decomposition mechanism of SFn under discharge conditions of 298K–10000K were studied, respectively. The conclusion drawn was that in the temperature range of 298–10000K, the thermal decomposition homopolytic reaction △G began to decline from 200 kJ/mol, while the △G of the other two heterogenous reactions began to decrease from 1000 kJ/mol and 2000 kJ/mol, showing a downward trend of an almost similar slope. The electrolysis of SFn is related to the electron energy. When the electron energy is low, SFn + e→SFn− series reactions occur, and △G of R12, R20, R28, R36, R44 increases with temperature rise, while △G of R4 decreases with temperature. When the electron energy is high, one of SFn−→SFn−1− + F、SFn−→SFn−1 + F− and SFn−→SFn−1 + F + e will occur, and the reactions that occur at various temperature ranges as the temperature rises vary. When the second electron hits the SFn−, the SFn− + e→SFn−1− + F reaction will occur. The △G of this reaction slowly decreases with an increase in temperature. This study in clearer terms explains the decomposition process and mechanism of SFn at different temperatures.