arXiv subjects

Terence Musho

Publications and source records attributed to Terence Musho.

11 recordsLinked to original sources

arXiv2026

Microwave-Stimulated Serpentinization of Olivine for Geological Hydrogen Production

Serpentinization of ultramafic rocks is a naturally occurring mineralogical process that can generate molecular hydrogen through the oxidation of ferrous iron during water-rock reaction. Although the resource potential is large, the natural reaction is kinetically limited, and practical hydrogen recovery requires methods that can accelerate conversion without imposing an energy penalty that exceeds the value of the hydrogen produced. This short communication reports a preliminary atmospheric-pressure microwave serpentinization experiment using a water-saturated 2 g crushed olivine sample. Microwave irradiation produced a rapid increase in measured hydrogen concentration compared with conventional hot-plate heating under otherwise similar conditions. The preliminary experiment showed approximately a 12-fold increase in hydrogen concentration and an apparent rate increase from about 2 ppb s$^{-1}$ for conventional heating to about 10 ppb s$^{-1}$ during microwave exposure. These results suggest that electromagnetic stimulation can enhance serpentinization kinetics, likely through rapid volumetric heating, selective coupling to iron-bearing phases, and localized thermal gradients. The result provides an initial experimental basis for evaluating microwave stimulation as a route to accelerated geologic hydrogen production and motivates follow-on measurements using calibrated gas analysis, absorbed-power measurements, dielectric characterization, and elevated-pressure testing.

cond-mat.mtrl-sci↗

arXiv2021

A Machine Learning Model for Predicting Progressive Crack Extension based on DCPD Fatigue Data

Time history data collected from a Direct Current Potential Drop (DCPD) fatigue experiment at a range of temperatures was used to train a Bidirectional Long-Short Term Memory Neural Network (BiLSTM) model. The model was trained on high sampling rate experimental data from crack initiation up through the Paris regime. The BiLSTM model was able to predict the progressive crack extension at intermediate temperatures and stress intensities. The model was able to reproduce crack jumps and overall crack progression. The BiLSTM model demonstrated the potential to be used as a tool for future investigation into fundamental mechanisms such as high-temperature oxidation and new damage models.

physics.app-ph↗

arXiv2021

Experimental Investigation of Crack Jumps during Initiation and Growth in IN718

The following study investigates the statistical nature of crack jumps during fatigue of Inconel 718. In-situ measurement in atmospheric air of the crack length at several loading and temperature conditions was conducted using a direct current potential drop (DCPD) method. Both annealed and heat-treated Inconel 718 samples were investigated. For a single sample, the normalized change of crack length was confirmed to not be a random process. This finding is significant in highlighting the time history features, which could be used in training machine learning models for the fundamental understanding of oxidation and the prediction of crack initiation and growth.

physics.app-ph↗

arXiv2020

Machine Learning Approach for Transforming Scattering Parameters to Complex Permittivity

This study investigates the application of an artificial neural network to predict the complex dielectric properties of granular catalysts commonly used in microwave reaction chemistry. The study utilizes finite element electromagnetic simulations and two-dimensional convolutional neural networks to solve for a large solution space of varying dielectrics. This convolutional neural network was trained using a supervised learning approach and a common backpropagation. The frequency range of interest was between 0.1 to 13.5 GHz with the real part of the dielectric constants ranging from 1 to 100 and the imaginary part ranging from 0.0 to 0.2. The network was double validated using experimental data collected from a coaxial airline. The model was demonstrated to convert either experimental or computational derived scattering parameter to complex permittivities. Moreover, the model eliminates the need for iterative solutions that often have difficulty with the piecewise continuous nature of frequency dependent scattering parameters.

physics.app-ph↗

arXiv2020

Dielectric Measurement of Powdery Materials using a Coaxial Transmission Line

The following study investigates the use of a coaxial transmission line for determining the properties of powdery dielectric materials (1-10GHz). Four powdery materials with dielectric constants ranging from 3.5 to 70 (SiO$_2$, Al$_2$O$_3$, CeO$_2$, and TiO$_2$) were experimentally investigated at varying volume loading fractions. Powder particles were mixed with a paraffin matrix and properties of the powder were analyzed using ten mixing equations to verify their accuracy. These powder-paraffin composites were also modeled at varying volume loadings for comparison with experimental data to gain a better understanding of the interactions between the different phases. The optimal volume loading fraction was determined to be 10% for all powders tested. A metric for selecting the most well-suited mixing equation was proposed that involved taking the ratio of the particle dielectric to that of the matrix. This study ultimately provides guidance for experimentally measuring the dielectric properties of unknown powdery materials that have application for new devices that utilized powder-based dielectric materials.

physics.app-ph↗

arXiv2019

GHz Dielectric Measurement of Powdery TiO

This study experimentally determines the dielectric properties of a powdery titanium (II) oxide (TiO) material within the microwave range (0.1-13.5 GHz). The properties were determined using a coaxial airline method using a TiO/paraffin mixture at several loading fractions. A permittivity of 60 for volume fraction below 30% and 100 for volume fraction above were measured.

physics.app-ph↗

arXiv2018

Density Functional Theory Evaluation of Cation-doped Bismuth Molybdenum Oxide Photocatalysts for Nitrogen Fixation

This study investigates the photocatalytic nitrogen fixation on a cation-doped surface (Bi$_{x}$M$_{y}$)$_2$MoO$_6$ where (M = Fe, La, Yb) in both the orthorhombic and monoclinic configurations using a density functional theory (DFT) approach with experimentally validated model inputs. The proceeding discussion focuses on the Heyrovsky-type reactions for both the associative and dissociative reaction pathway related to nitrogen reduction. Key fundamental insight in the reduction mechanism is discussed that relates the material properties of the substitutional ions to the nitrogen and hydrogen affinities. Physical insight is gathered through interpretation of bound electronic states at the surface. Compositional phases of higher Fe and Yb concentrations resulted in decreased Mo-O binding and increased affinity between Mo and the N and H species on the surface. The modulation of the Mo-O binding is induced by strain as Yb and Fe are implemented, this, in turn, shifts energy levels and modulates the band gap energy by approximately 0.2 eV. This modification of Mo-O bond as substitution occurs is a result of the orbital hybridization of M-O (M = Fe, Yb) that causes a strong orbital interaction that shifts states. The optimal composition was predicted to be an orthorhombic configuration of (Bi$_{0.75}$Fe$_{0.25}$)$_2$MoO$_6$ with a predicted maximum thermodynamic energy barrier of 1.4 eV. This composition demonstrates effective nitrogen and hydrogen affinity that follows the associative or biological nitrogen fixation pathway.

cond-mat.mtrl-sci↗

arXiv2018

Study of Cu2O Particle Morphology on Microwave Field Enhancement

The dielectric enhancement and modulation of a cuprous oxide (Cu2O) microwave-active catalyst material is investigated from an experimental and computational point of view. Experimental synthesis of two particle morphologies that included a cube and spike were carried out using an EDTA hydrothermal synthesis method. The permittivity for the spiked particles at low volume fraction in a paraffin composite exhibited a 20% increase when compared to the cube-shaped particles at the same volume fraction. Using a finite difference time domain (FDTD) simulation, the improvement in permittivity was attributed to the enhanced electric field near the tip of the spike particles and the neighboring interaction at higher volume fractions. The increased electric field at the tips of the particles induces a change in polarizability (dipole density) within the matrix material, which increases the effective dielectric properties of the composite. Furthermore, it was determined that an electrically conductive particle within a high permittivity matrix material is advantageous for generating high localized electric fields that can be utilized for microwave-assisted catalytic reactions.

physics.app-ph↗

arXiv2017

Ab initio Screening of a Sulfur Desorbed MoS$_2$ Photocatalyst for Nitrogen Fixation

The following study investigates the thermodynamic reaction barriers during nitrogen fixation for an inorganic sulfur desorbed photocatalyst Molybdenum disulfide surface. The design space is investigated using an density functional theory (DFT) method within a space bound by MMoS$_2$ M=Mo,Fe,Co. The discussion focuses on Heyrovsky type reactions along both the associative and dissociative pathway. A key insight into the roles of the inorganic and the balance between nitrogen and hydrogen affinity, providing evidence for an optimal material that minimizes the required over-potential. It is found that phases with a higher concentration of Mo face high reaction barrier involving nitrogen, where phases with higher concentrations of Fe and Co face high reaction barriers involving hydrogen species. In the absence of kinetic considerations, the best phase was predicted to be the 1T phase with a Mo$_{0.75}$Fe$_{0.25}$S$_{2}$ composition. This phase proved to have a balance of hydrogen and nitrogen affinity and follows the dissociative pathway, which can be evolved through non-thermal methods.

physics.chem-ph↗

arXiv2017

Transformation of a Metal-organic Framework for Tuned Catalytic Activity

Metal-organic frameworks (MOFs) are an attractive substrate for catalytic reactions due to the high area density of reaction sites and the ability to tailor an array of material attributes. This study focuses on a thermally stable crystalline UiO-66(Zr) MOF structure and the modulation of the electronic structure using two strategies to improve the catalytic conversion and selectivity of benzene alcohol to benzedehyate. Those two strategies include the functionalization of the organic struts with branched ligands and manually creating structural defects with unsaturated organic linkers. A combination of computational and experimental results provide evidence of improved catalytic activity of MOFs via these two approaches. Functional groups attached to the main organic strut modify the electronic environment of the photoactive aromatic carbon and thereby decrease the optical band gap by 1eV. Whereas the introduction of structural defects due to the organic linker desaturation provided a shift in the HUMO as a result of the decrease in strut coordination with the inorganic knots.

physics.chem-ph↗

arXiv2015

Thermodynamics of the Oxygen Evolution Electrocatalysis in Metal-Organic Frameworks

Metal-organic frameworks (MOFs) provide a versatile and tailorable material platform that embody many desirable attributes for photocatalytic water-splitting. The approach taken in this study was to use Density Functional Theory (DFT) to predict the thermodynamic energy barriers of the oxygen evolution reaction (OER) for three MOF functionalizations. A Zr-MIL-125 MOF design was selected for this study that incorporates three linker designs, a 1,4-benzenedicarboxylate (BDC), BDC functionalized with an amino group (BDC+NH2), and BDC functionalized with nitro group (BDC+NO2). The study found several key differences between homogeneous planar catalyst thermodynamics and MOF based thermodynamics, the most significant being the non-unique or heterogeneity of reaction sites. Additionally, the funcationalization of the MOF was found to significantly influence the hydroperoxyl binding energy, which proves to be the largest hurdle for both oxide and MOF based catalyst. Both of these findings provide evidance that many of the limitations precluding planar homogeneous catalysts can be surpassed with a MOF based catalyst. While none of the MOF designs selected for this study out-performed state-of-the-art oxide based catalysts, the BDC+NH2 proved to be the best with a predicted over-potential for spontaneous OER evolution to be 3.03eV.

physics.chem-ph↗