Chapter 5.4 - Process Modeling

Chemical reaction kinetics is concerned with the determination of rate laws and time laws for a reaction, for example, the oxidation of a metal sheet. Rate laws describe the reaction rate as a function of process parameters: $$v = \frac{{dm}}{{dt}} = v(p{o_2},T,l, \ldots ).$$ ((2.1)) The mass gain per time unit of the sheet can depend on the oxygen pressure, the temperature, the oxide scale thickness l and other parameters. The time law is the integration of the rate law over the reaction time and gives in our example the weight gain as a function of the time and the other parameters mentioned, $$\Delta m\int_{{t_0}}^t {vdt} = \Delta m({p_{{O_2}}},T,l, \ldots t).$$ ((2.2)) If we try to understand the reaction mechanism hidden behind the expiremental data on an atomistic scale, we have to develop a reaction model from first principles which is able to formulate theoritical rate and time laws and to compare them with the curves measured. Metal-gas interactions are complex heterogeneous chemical reactions composed of several individual partial reactions. These partial steps can precede parallel or one behind the other and they are linked together by the concentrations of intermediate reaction products. As long as only one of these steps is the bottle neck of the whole process and, therefore, rate determining the rate and time law can be determined easily. We need only the equilibrium constants of preceding and succeding patial steps and the rate law of the rate determining partial reation.KeywordsPartial ReactionChemisorption EnergyPartial StepIntermediate Reaction ProductChemisorption SpeciesThese keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

There is a definite inconsistency between the classical ZND theory of detonation and contemporary experimental observations and attempts to model real detonation waves. Nevertheless, the classical onedimensional model of detonation is still extensively used in interpreting measurements because of its simplicity and physical clarity. This naturally raises the questions, what does actually the classical model represent and how one can relate the real multidimensional wave structure to an effective onedimensional detonation? The answer to these questions is extremely important from the practical point of view, because it defines how simple the solution of the criticality problems in detonation could be (i.e. whether one has to solve the very cumbersome three-dimensional nonsteady gasdynamic problem with detailed kinetics of the chemical reaction comprising a few hundreds of elementary steps to predict such parameters as critical initiation energy, critical distances, and concentrations, or the solution of a simplified onedimensional gasdynamic problem with global chemical kinetic equations would suffice?). The present communication discusses the following topics with the aim of answering partly the above questions. (1) An analysis of the detailed kinetic calculations of the heat evolution rate in some fuel-air mixtures and comparison of these results with experiments reveals that (a) in the majority of detonable mixtures heat release can be described by global equations with an accuracy quite sufficient for assessing the critical detonation parameters, (b) chemical kinetics shows no so-called recombination zones with an appreciable heat evolution that follow the main reaction zone, (c) the ratio between the induction and the explosion (within which the major fraction of the stored energy is evolved) times exceeds unity under the conditions corresponding to detonation waves in fuel-air mixtures, which contradicts the shock tube measurements. All these results can be reasonably explained by the fact that the chemical reaction in detonation waves (in shock waves as well) proceeds in a gas with a highly inhomogeneous distribution of the parameters (temperatures, pressures, and particle velocity) which gives rise to the so-called hot-spot mechanism of chemical reactions in gaseous and two-phase media. It is shown that the hot spot ignition is the main reason of instability of detonation waves. Nonsynchronous mixture ignition at different points produces the effect of extended heat evolution zone and reduces the effective induction zone. Results of measurements of averaged and local parameters behind detonation waves in gases support the idea that the effective heat evolution rate in the onedimensional representation of the wave is much more complicated than that inherent in the chemical reaction alone, because it contains also a significant contribution of the kinetic and thermodynamic energy redistribution within the major reaction zone and downstream of it, which makes the onedimensional structure of detonation waves deviate significantly from the classical pattern leading to nonmonotonic heat release behind the shock front (the possibility of appearance of two or more effective sonic planes and heat rlease maxima). However, a onedimensional analysis of marginal detonation waves has demonstrated that critical parameters can be estimated quite accurately within simplified models, which is attributable to the fact that the criticality is associated with local termination of the reaction within narrow stream tubes where the flow pattern resembles closely the ZND non-CJ detonation wave structure. Unlike the chemical reaction zone in detonations far away from the limit, which is shorter than the detonation cell size, the reaction zone in marginal detonations is comparable with the cell size. The results of onedimensional calculations of critical diameters and minimal energies of direct initiation of detonation are compared with experim

Assessing the concentration, speciation, and toxicity of dissolved metals during mixing of acid-mine drainage and ambient river water downstream of the Elizabeth Copper Mine, Vermont, USA

Predicting particle orientation: Is an accurate flow field more important than the actual orientation model?

Non-dimensional process maps for normalized dilution limits in laser direct metal deposition

The structure of freely propagating rich CH4/air flames was studied numerically using detailed thermal and transport properties and the GRI-Mech 3.0 mechanism. Different fresh mixture temperatures and ambient pressures were considered in the simulation to investigate the effects of preheat and pressure on the super-adiabatic flame temperature (SAFT) phenomenon. The occurrence of SAFT in rich CH4/air flames is chemical kinetics in nature and is associated with the overproduction of CH2CO and H2O in the reaction zone followed by their endothermic dissociations in the post-flame region. Preheat lowers the degree of H2O concentration overshoot and results in faster depletion of CH2CO concentration in the post-flame region. Preheat accelerates a rich CH4/air flame to approach equilibrium and suppresses the occurrence of SAFT. Increased pressure reduces the H radical concentration in the reaction zone and increases the overshoot of H2O concentration and the peak concentration of CH2CO. Although pressure also accelerates the approach of a rich CH4/air flame to equilibrium, it actually enhances the degree of SAFT.

Hydrothermal liquefaction (HTL) technology has garnered immense research interest due to its potential to convert wet biomass into petroleum-like biocrude. Understanding the reaction mechanism and kinetics of HTL is crucial for understanding the process better, estimating the yields, and scaling up. On the other hand, reaction mechanisms and kinetics largely depend upon the feedstock composition and reaction parameters of HTL. However, the literature lacks an in-depth analysis of the reaction mechanism and kinetics concerning biocrude yield and product distribution for a single to multi-feedstock scenario. This review focuses on the reaction mechanisms of various biomolecular components of lignocellulosic biomass, proteins, and lipids in the HTL process under sub- and supercritical conditions. Furthermore, the HTL reaction kinetics, effect of reaction conditions on reaction mechanisms, and product distribution are explored. The findings agree that reaction temperature and retention time follow inverse relations for high biocrude yield. A high heating rate is recommended for higher biocrude yield to avoid cracking and recombination processes. A high solvent/feedstock ratio, depending on feedstock composition, was favored for optimum biocrude yield. In addition, catalysts and reaction solvents, especially organic solvents, effectively contribute towards high biocrude yield, even up to 70%. Heterogeneous catalysts are favored due to reusability and improved biocrude quality. Also, hydrothermal co-liquefaction (multi-feedstock) use for improving biocrude yield was debated. A detailed discussion on the reaction kinetics of various biomolecular components in the HTL process revealed that reactions in HTL normally follow the first-order rate law. Finally, the authors outline the pointers for future research in HTL for industrial upscaling.

A comprehensive understanding of the melt pool behavior during directed energy deposition (DED) has become essential in identifying process anomalies and controlling the process quality. Previous studies focused on predicting the melt pool characteristics by solely using the process parameters, in this study we use real-time melt pool images to predict the melt pool characteristics. A CMOS camera is used to capture coaxial images of the melt pool during the deposition of single-track prints to improve the prediction model. Multiple regression models are trained and compared to estimate the melt pool profile (width, depth, and height) as a function of process parameters (namely, the laser power, the powder feed rate, and the scanning speed) and features from the ellipse fitting of the real-time melt pool images. A novel image processing algorithm is proposed to extract the major axis, minor axis, and tilt. The sensitivity analysis demonstrated that combining process parameters and coaxial images can improve the prediction performance. The Gaussian Process regression showed the best performance among all the employed regression models.

In the semiconductor manufacturing industry, optimization of advanced equipment and process designs must include both manufacturing metrics (such as cycle time, consumables cost, and product quality) and environmental consequences (such as reactant utilization and by-product emission). We have investigated the optimization of rapid thermal chemical vapor deposition (RTCVD) of polysilicon from SiH/sub 4/ as a function of process parameters using a physically-based dynamic simulation approach. The simulator captures essential time-dependent behaviors of gas flow, heat transfer, reaction chemistry, and sensor and control systems, and is validated by our experimental data. Significant improvements in SiH/sub 4/ utilization (up to 7/spl times/) and process cycle time (up to 3/spl times/) can be achieved by changes in 1) timing for initiating wafer heating relative to starting process gas flow; 2) process temperature (650-750/spl deg/C); and 3) gas flow rate (100-1000 seem). Enhanced gas utilization efficiency and reduced process cycle time provide benefits for both environmental considerations and manufacturing productivity (throughput). Dynamic simulation proves to be a versatile and powerful technique for identifying optimal process parameters and for assessing tradeoffs between various manufacturing and environmental metrics.

The possibility of electromembrane softening treatment of network water at a thermal power station is shown. Technology for the manufacturing of an inert anode free from noble metals or their compounds is proposed. Performed resource tests have demonstrated that such an anode can be in operation in chloride–sulfate solutions for several years almost without wear. A mathematical model describing the electrical current utilization efficiency as a function of process parameters and electrolysis regimes in the electromembrane softening of water has been developed. The results of calculating the current utilization efficiency coefficient by this model are in satisfactory agreement with experimental results. The current utilization coefficient in the formation of NaOH does not depend on the anolyte composition but appreciably decreases with increasing catholyte concentration and slightly grows with increasing current density at a constant catholyte concentration. Experiments have not disclosed any essential dependence between the specific water and CO 3 2- ion transports and the process parameters. Experiments on estimating the depth of the electromembrane softening of initial water for the heat supply networks of Kharkiv have demonstrated that the electromembrane method provides the residual hardness of 0.3–0.4 mg-equiv/dm3, which is almost four times lower than for water subjected to soda–lime treatment. The experiments performed on a test bench setup have confirmed that the application of heterogeneous cation-exchange membranes (both MK-40 (OAO Shchekinoazot) and CMI 9000 (Membrane International)) provides the possibility to attain a high current utilization ratio above 88%. The carbonate index of water after electromembrane softening corresponds to the normative requirements to water for heat supply networks with a heat transfer agent temperature below 150°C (no higher than 0.4 (mg-equiv/dm3)2]. This provides the possibility to use the treated water immediately in heat supply networks without further ion-exchange softening. Some technical and economic parameters of the softening process and the technical parameters of an industrial electromembrane softener are given, and the possibilities of the utilization of wastes and byproducts are considered.

The recent development of the Enriched Analytical Solution Method (EASM) for evaluating the spatio-temporal distribution of the temperature fields generated during the Laser Powder Bed Fusion (LPBF) Additive Manufacturing (AM) processes is provides an opportunity to study the sensitivity of the morphological parameters characterizing the associated melt-pools as a function of process parameters. The present work exercises the EASM for the case of a single-path trace over a 316L base plate under LPBF heat deposition conditions. To assist in the evaluation of solidification parameters, the spatial derivatives of the EASM are also derived. A process parameter subspace spanned by the scan velocity and the laser power is considered and the EASM is utilized for deriving a number of geometrical morphological characteristics of the melt pool as well as the quantities controlling the evolution of the solidification front. Finally, comparisons with initial experimental results obtained by in-situ high speed synchrotron X-ray imaging, capturing the spatio-temporal evolution of the melt pool profile are also presented.

Friction Stir Processing (FSP) is becoming an acceptable technique for modifying the grain structure of sheet metals. One of the most important issues that hinder the widespread use of FSP is the lack of accurate models that can predict the resulting microstructure in terms of process parameters. Most of the work that has been done in the FSP field is experimental, and limited modeling activities have been conducted. In this work, an analytical model is presented that can predict the strain rate distribution and the deformation zone in the friction stir processed zone as a function of process parameters. In the model, the velocity fields within the processed zone are determined by incorporating the effects of both the shoulder and the pin of the tool on the material flow. This is achieved by introducing state variables and weight functions. The model also accounts for different interfacial conditions between the tool and the material. The effects of different process parameters and conditions on the velocity fields and strain rate distributions are discussed. The results clearly show that the model can successfully predict the shape of the deformation zone and that the predicted strain rate values are in good agreement with results reported in the literature.

A surface roughness predictive model in deterministic polishing of ground glass moulds

Hydrothermal gasification (HTG) is applicable to high moisture content biomass feedstock such as wet microalgae. The key interests of this thermochemical processing are its ability to use whole algae instead of simply lipid extracts and to use a wide range of algal feedstocks. It employs water in the form of a reaction medium to disintegrate biomass into hydrogen gas. The products' composition and yields are a function of process parameters, namely feed concentration, pressure, and temperature. There is very limited literature available on model development to understand the impacts of various input parameters on the products of HTG. This study presents development of a detailed process model for HTG and the illustration of process parameters on the gas product yields. The approach includes developing the system model, identifying the key process parameters in the reactor setup that affect syngas yield, and understanding the overall process in terms of final product yield. A simulation of hydrothermal gasification based on thermodynamic equilibrium is studied. Based on the developed process model about 52.1 t/day of hydrogen can be produced from 500 t/day of wet algal biomass. This shows the potential of large‐scale hydrogen production through this process for hydrogen economy. The results from this study could be used by the gas processing industry and policymakers to determine the most feasible means of converting biomass‐based resources into gaseous fuels.

Prediction of regenerative chatter by modelling and analysis of high-speed milling