Materials Science and Engineering Commons^™

Understanding The Metallic And Oxide Phases In Platinum-Based Bimetallic Heterogeneous Catalysts After High-Temperature Oxidation, Stephen John Porter Jr

Nanoscience and Microsystems ETDs

Platinum (Pt) and palladium (Pd) are critical components in diesel emission control systems, enabling the conversion of harmful pollutants under demanding conditions. However, Pt’s effectiveness is hindered by sintering under high-temperature oxidizing environments. This dissertation investigates how Pt and Pd evolve under oxidizing conditions at 800°C, highlighting their distinct thermodynamic behaviors and interactions. Using TEM, EDS, EELS, XRF, XRD, and EXAFS, we show that Pd suppresses Pt sintering by reducing the volatility of PtO₂, leading to the formation of stable particles. Both Pt and Pd are present in metallic and oxide states, forming biphasic 'Janus' particles with conjoined metal and …

Numerical Simulation Of The Pitting Corrosion Behavior Of Stainless Steel Bellows Influenced By Varying Liquid Film Thicknesses, Lu-Jun Ren, Guo-Min Li, Zhen-Xiao Zhu, Hai-Yan Xiong, Bing Li

Journal of Electrochemistry

To advance the understanding of the corrosion behavior of stainless steel bellows in marine atmospheric environments and enhance the precision of service life predictions, this study employs finite element simulations to investigate the pitting corrosion rates and pit morphologies of bellows peaks and troughs under varying electrolyte film thicknesses. The model incorporates localized electrochemical reactions, oxygen concentration, and homogeneous solution reactions. For improved computational accuracy, the fitted polarization curve data were directly applied as nonlinear boundary conditions on the electrode surface via interpolation functions. Simulation results reveal that the peak regions exhibit faster corrosion rates than the trough regions. With …

Regulating The Amount Of Graphene Oxide For Enhanced Capacitive Energy Storage Of Mof Derived Materials, Yong-Ji Qin, Jing-Quan Yang, Hao Wang, Mei-Ling Lian, Pei-Pei Jia, Jun Luo, Xi-Jun Liu, Jun-Feng Liu

Journal of Electrochemistry

In pursuit of more efficient and stable electrochemical energy storage materials, composite materials consisting of metal oxides and graphene oxide have garnered significant attention due to their unique structures and exceptional properties. Graphene oxide (GO), a two-dimensional material with an extremely high specific surface area and excellent conductivity, offers new possibilities for enhancing the electrochemical performance of metal oxides. In this work, we synthesized metal- organic framework (MOF) and GO composites by regulating the amount of GO, and successfully prepared composites of metal oxides supported by nitrogen-doped carbon frameworks and GO through a simple one-step calcination process. Based on the …

Pd-Based Hydrogen Separation Membranes Synthesized Via A Liquid-Phase Route, Chase W. Thompson

Chemical and Biological Engineering ETDs

Palladium (Pd) membranes have gained significant attention for their ability to selectively separate hydrogen, a critical process for clean energy applications such as fuel cells and hydrogen storage. However, challenges such as grain growth, sintering, hydrogen embrittlement, and film uniformity limit their scalability and long-term stability. This thesis focuses on the controlled synthesis, deposition, and stability of Pd nanoparticles to optimize membrane performance for hydrogen separation. This work investigates solution-phase synthesis of Pd nanoparticles, focusing on temperature, precursor concentration, and solvent composition as key variables influencing particle growth and dispersion. Pd membranes were fabricated using nanoparticle deposition onto porous supports, …

Vacuum Consistent Electrochemistry In Ionic Liquid Combined With Oxide Epitaxy, Yuji Matsumoto

Journal of Electrochemistry

We introduce our state-of-the art of “vacuum consistent electrochemistry” to an investigation of the interfaces between oxides and ionic liquid (IL). Pulsed laser deposition (PLD) has been one of the powerful and sophisticated techniques to realize nanoscale preparation of high-quality epitaxial oxide thin films. On the other hand, electrochemistry is a simple, very sensitive, and non-destructive analysis technique for solid-liquid interfaces. To ensure the reproducibility in experiment of the interfaces of such epitaxial oxide films, as well as bulk oxide single-crystals, with IL, we employ a home-built PLD-electrochemical (EC) system with IL as an electrolyte. The system allows one to …

Pm Irras Studies Of Organized Molecular Films At A Gold Electrode Surface, Zhang-Fei Su, Ai-Cheng Chen, Jacek Lipkowski

Journal of Electrochemistry

This feature article illustrates the potential of polarization modulation infrared reflection absorption spectroscopy (PM IRRAS) to provide molecular-level information about the structure, orientation and conformation of constituents of thin films at electrode surfaces. PM IRRAS relies on the surface selection rules stating that the p-polarized IR beam is enhanced, while the s-polarized beam is attenuated at the metal surface. The difference between p- and s-polarized beams eliminates the background of the solvent and provides IR spectra at a single electrode potential. In contrast, two other popular in situ IR spectroscopic techniques, namely, subtractively normalized interfacial Fourier transform infrared spectroscopy (SNIFTIRS) …

Redox-Active Monolayers On Ito Prepared By Post-Amidation And Direct Esterification And Their Spectroelectrochemical Characterization, Takamasa Sagara, Sae Nakai, Ryusuke Yofu, Shota Kojin

Journal of Electrochemistry

A redox-active monolayer on an optically transparent electrode constitutes a typical platform for spectroelectrochemical sensing. The necessity for its sophistication arises from the availability of multi-dimensional sensing signals. Simultaneous monitoring of the redox current and color change synchronized with the oxidation state change significantly enhances sensitivity and selectivity. This study aimed to elucidate the modification of an indium tin oxide (ITO) electrode with a viologen monolayer with an ordered orientation. Novel methods were developed to immobilize a viologen molecule bearing a carboxyl group to form assembled monolayers through a condensation reaction using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide with N-hydroxy-succinimide (EDC/NHS). In the two methods …

Ambient Co2 Capture And Valorization Enabled By Tandem Electrolysis Using Solid-State Electrolyte Reactor, Yan-Bo Hua, Bao-Xin Ni, Kun Jiang

Journal of Electrochemistry

Electrocatalytic carbon dioxide reduction is a promising technology for addressing global energy and environmental crises. However, its practical application faces two critical challenges: the complex and energy-intensive process of separating mixed reduction products and the economic viability of the carbon sources (reactants) used. To tackle these challenges simultaneously, solid-state electrolyte (SSE) reactors are emerging as a promising solution. In this review, we focus on the feasibility of applying SSE for tandem electrochemical CO₂ capture and conversion. The configurations and fundamental principles of SSE reactors are first discussed, followed by an introduction to its applications in these two specific areas, …

Systematic Review: Recent Developments In Magnetic-Nanoparticle-Based Dna Extraction, Stanley Evander Emeltan Tjoa, Mudasir Mudasir, Edi Suharyadi, Budi Setiadi Daryono

Makara Journal of Science

Deoxyribonucleic acid (DNA) is a research object for various molecular fields of study, and DNA extraction is a basic procedure in molecular biology laboratories. DNA extraction methods are evolving, from several steps using organic solvents to recent technology using magnetic nanoparticles as adsorbents for the purification step. The use of magnetic nanoparticles for DNA extraction is magnetizing because it is simple without heavy machinery, such as centrifugation and organic solvents. The application of this method is extensive and diverse. This systematic review summarizes current development trends for some aspects of this DNA extraction system from the magnetic nanoparticle synthesis method, …

Colloidal Quantum Dots: A Path Toward Making Mid-Wave Infrared Sensing A Ubiquitous Technology, Mohammad Mostafa Al Mahfuz

Dissertations

Reducing the size, weight, power consumption, and cost (SWaP-C) of infrared detectors could make infrared sensing more widely accessible. In the critical mid-wavelength infrared (MWIR) spectral range of 3-5 gm, commercially available detectors are limited by the high costs associated with epitaxial growth and hybridization, as well as the need for cryogenic cooling. These factors restrict their use to defense and space applications.

Colloidal quantum dots present a promising material for overcoming these challenges, with wafer-scale monolithic integration and Auger suppression being the key material capabilities to minimize the sensor's SWaP-C. Infrared sensors based on colloidal quantum dots have been …

Understanding The Morphology And Mass Transport Resistance Of Mesoporous Carbon-Supported Pemfc Based On Modeling Analysis, Hao Deng, Jia Liu, Zhong-Jun Hou

Journal of Electrochemistry

Mesoporous carbon supports mitigate Pt sulfonic poisoning through nanopore-confined Pt deposition, yet their morphological impacts on oxygen transport remain unclear. This study integrates carbon support morphology simulation with an enhanced agglomerate model to establish a mathematical framework elucidating pore evolution, Pt utilization, and oxygen transport in catalyst layers. Results demonstrate dominant local mass transport resistance governed by three factors: (1) active site density dictating oxygen flux; (2) ionomer film thickness defining shortest transport path; (3) ionomer-to-Pt surface area ratio modulating practical pathway length. At low ionomer-to-carbon (I/C) ratios, limited active sites elevate resistance (Factor 1 dominant). Higher I/C ratios improve …

Preparation And Modification Of Mxene Composites For Application In Electrochemical Energy Storage, Zhang-Hai You, Ding-Ze Lu, Kiran Kumar Kondamareddy, Wen-Ju Gu, Peng-Fei Cheng, Jing-Xuan Yang, Rui Zheng, Hong-Mei Wang

Journal of Electrochemistry

With the acceleration of advanced industrialization and urbanization, the environment is deteriorating rapidly, and non-renewable energy resources are depleted. The gradual advent of potential clean energy storage technologies is particularly urgent. Electrochemical energy storage technologies have been widely used in multiple fields, especially supercapacitors and rechargeable batteries, as vital elements of storing renewable energy. In recent years, two-dimensional material MXene has shown great potential in energy and multiple application fields thanks to its excellent electrical properties, large specific surface area, and tunability. Based on the layered materials of MXene, researchers have successfully achieved the dual functions of energy storage and …

Theoretical Insights Into The Atomic And Electronic Structures Of Polyperyleneimide: On The Origin Of Photocatalytic Oxygen Evolution Activity, Yi-Qing Wang, Zhi Lin, Ming-Tao Li, Shao-Hua Shen

Journal of Electrochemistry

Polymeric perylene diimide (PDI) has been evidenced as a good candidate for photocatalytic water oxidation, yet the origin of the photocatalytic oxygen evolution activity remains unclear and needs further exploration. Herein, with crystal and atomic structures of the self-assembled PDI revealed from the X-ray diffraction pattern, the electronic structure is theoretically illustrated by the first-principles density functional theory calculations, suggesting the suitable band structure and the direct electronic transition for efficient photocatalytic oxygen evolution over PDI. It is confirmed that the carbonyl O atoms on the conjugation structure serve as the active sites for oxygen evolution reaction by the crystal …

Three-Dimensional Melamine Carbon Sponge/Nai As Cathode Materials For Sodium-Ion Batteries, Qian-Ying Huang, Yue Liu, Zi-Xin Lin, Shu-Yi Zheng, Ting-Ting Mei, Yu-Ting Tang, Ying-He Zhang, Jun Liu

Journal of Electrochemistry

The sodium-iodine (Na-I) battery exhibits significant potential as an alternative energy storage device to the lithium-ion battery. However, its development is hindered by inadequate electrical and thermal stability, as well as the dissolution and shuttling of polyiodide. In this study, we report a preparation method for melamine carbon sponge (MC) via carbonizing a commercially available kitchen sponge. It was revealed that the as-prepared MC, composed of unique self-growing carbon nanotubes, could provide both physical and chemical adsorption capabilities for intermediate polyiodides to improve the electrochemical performance of NaI. Consequently, the NaI/MC electrode effectively minimized polyiodide dissolution and reduced the electrochemical …

Functional Devices Based On Freestanding 2d Materials, Shijue Xu

McKelvey School of Engineering Graduate Student Theses & Dissertations

Two-dimensional (2D) materials have attracted extensive attention in the field of nanoelectronics due to their atomic-scale thickness, high surface-to-volume ratio, tunable electronic properties, and compatibility with low-temperature processing. These characteristics make them highly suitable for the construction of emerging device architectures, particularly in both ionic and electronic devices.

In this work, we investigate the application of 2D materials in two distinct classes of devices: ionically-driven memristors and electronically-dominated metal–semiconductor contacts. For the memristor study, we fabricate heterostructure-based resistive switching devices using h-BN and WSe₂ as active layers. These 2D material-based memristors exhibit stable power consumption loops and high linearity …

Exploring Metal Additive Manufacturing In Martian Atmospheric Environments, Zane Mebruer

Mechanical Engineering Undergraduate Honors Theses

On-surface manufacturing is key to the success of a planetary colonization, especially that of Mars. However, traditional subtractive manufacturing processes are equipment, energy, and material intensive, meaning novel additive manufacturing (AM) processes must be pursued for this end. Selective laser melting, one of the most effective and versatile AM methods, would be incredibly beneficial to a Martian mission but requires an artificial argon atmosphere to create effective parts. The purpose of this study was to examine if carbon dioxide, the gas that makes up over 95% of Mars’ surface atmosphere, would be a sufficient substitute for argon in SLM fabrication. …

Mechanistic Insights Into Polymer-Assisted Graphene Exfoliation: The Roles Of Velocity, Adhesion, Cohesion, Temperature, Peeling Mode, And Edge Defect Via Coarse-Grained Molecular Dynamics, Linjiale Dai

All Theses

Graphene exfoliation is a critical step in the fabrication of high-quality graphene

layers. However, the underlying fracture mechanisms remain poorly understood. In this

work, I employed coarse-grained (CG) molecular dynamics (MD) simulations to

investigate how factors such as interfacial binding energy, substrate cohesion, temperature,

peeling mode, and edge defects influence the outcome of the exfoliation process. To model

polymer-assisted mechanical exfoliation, I used a finite-size system in which multilayer

graphene (MLG) is sandwiched between two thin polymer films. Leveraging the

spatiotemporal efficiency of the CG model, I performed fifty simulation iterations per

parameter set and analyzed the results from a …

Electrocatalytic Nitric Oxide Reduction To Yield Ammonia Over Fe3C Nanocrystals, Sen Lin, Lang Zhang, Tong Hou, Jun-Yang Ding, Zi-Mo Peng, Yi-Fan Liu, Xi-Jun Liu

Journal of Electrochemistry

Nitric oxide (NO), which generally originates from vehicle exhaust and industrial flue gases, is one of the most serious air pollutants. In this case, the electrochemical NO reduction reaction (NORR) not only removes the atmospheric pollutant NO but also produces valuable NH₃. Hence, through the synthesis and modification of Fe₃C nanocrystal catalysts, the as-obtained optimal sample of Fe₃C/C-900 was adopted as NORR catalyst at ambient conditions. As a result, the Fe₃C/C-900 catalyst showed an NH₃ Faraday efficiency of 76.5% and an NH₃ yield rate of 177.5 μmol·h^–1·cm^{–2 …}

Ordering Degree Regulation Of Pt2Nico Intermetallics For Efficient Oxygen Reduction Reaction, Chen-Hao Zhang, Han-Yu Hua, Jun-Hao Yang, Qian Zhang, Chang Yang, De-Li Wang

Journal of Electrochemistry

Alloying transition metals with Pt is an effective strategy for optimizing Pt-based catalysts toward the oxygen reduction reaction (ORR). Atomic ordered intermetallic compounds (IMC) provide unique electronic and geometrical effects as well as stronger intermetallic interactions due to the ordered arrangement of metal atoms, thus exhibiting superior electrocatalytic activity and durability. However, quantitatively analyzing the ordering degree of IMC and exploring the correlation between the ordering degree and ORR activity remains extremely challenging. Herein, a series of ternary Pt₂NiCo intermetallic catalysts (o-Pt₂NiCo) with different ordering degree were synthesized by annealing temperature modulation. Among them, the o-Pt …

Performance Of Co2/H2O Co-Electrolysis In A Flat-Tube Solid Oxide Electrolysis Cell Stack Under Air-Free Environment, Xiao-Hui Zhong, Fei Wang, An-Qi Wu, Bei-Bei Han, Jian-Xin Wang, Wan-Bing Guan

Journal of Electrochemistry

This work investigates the transient performance and stability of CO₂/H₂O co-electrolysis in an air-free environment using a flat-tube solid oxide electrolysis cell (SOEC) stack. The results show that the transient behavior of the stack with and without blowing gas in the air electrode is almost the same. With a current density of 0.67 A·cm⁻²@750 °C, the stack operated for over 200 h under co-electrolysis conditions with no air blowing, and the voltage drop rate of the stack was approximately 0.203%/100 hours. Microstructure analysis reveals significant loss of Ni particles and formation of an insulating …

Variation Of Membrane Electrode Assembly Catalyst Layer In Unitized Regenerative Fuel Cell, Yollanda Nurcholifah, Dedi Rohendi, Edy Herianto Majlan, Nirwan Syarif, Addy Rachmat, Dwi Hawa Yulianti, Nyimas Febrika S

Journal of Electrochemistry

A unitized regenerative fuel cell (URFC) is a device that may function reversibly as either a fuel cell (FC) or water electrolysis (WE). An important component of this device is the Membrane electrode assembly (MEA). Therefore, this study aimed to compare the performance outcomes of MEA using electrodes with single and three catalyst layers. This study measured Electrochemical Surface Area (ECSA), Electrochemical Impedance Spectroscopy (EIS), X-ray Diffraction analysis (XRD), and X-ray Fluorescence (XRF). Furthermore, the round-trip efficiency (RTE) of the MEA, as well as the performance in FC and WE mode, was measured. In comparison, The ECSA values of Pt-Ru/C …

Josephson Junctions: Fabrication And Applications For The Axion Dark Matter Experiment, Jonah M. Sachs

Senior Honors Papers / Undergraduate Theses

The observation of axions could revolutionize the world of physics. Through microwave frequency cavity readout of the photons associated with these axions, the ADMX project at WashU utilizes multiple different forms of the Josephson junction (JJ), a superconductive circuit element. The physics behind the JJ are essential to understanding its operation for resonant cavity readout in addition to parametric amplification. Parametric amplifiers produced using JJs can approach the signal-to-noise ratio set by quantum mechanics, and prove essential for the amplification chain used by the ADMX experiment for axionic detection. The limits of these amplifiers are set by the noise tuning …

Study On Dopamine Electrochemical Sensing Based On Au@Mos2, Ning An, Ni Su, Xin-Ran Li, Jian-Yu Liu, Qi-Yan Wang

Journal of Electrochemistry

Dopamine (DA) is a vital neurotransmitter, and accurate detection of its concentration is critical for both clinical diagnostics and neuroscience research. Due to its electrochemical activity, DA is commonly detected using electrochemical methods, which are favored for their simplicity, fast response time, and suitability for in vivo analysis. In this work, a highly sensitive DA electrochemical sensor was developed using an Au@MoS₂ composite, created by modifying molybdenum disulfide (MoS₂) nanosheets with gold nanoparticles through HAuCl₄ reduction, and it was aimed at enhancing DA adsorption and improving detection performance. Scanning Electron Microscopy (SEM), transmission electron microscopy (TEM), …

Recent Advances In Non-Enzymatic Electrochemical Sensors For Theophylline Detection, Gustria Ernis, Yulia M T A Putri, Muhammad Iqbal Syauqi, Prastika Krisma Jiwanti, Yeni Wahyuni Hartati, Takeshi Kondo, Qonita Kurnia Anjani, Jarnuzi Gunlazuardi

Journal of Electrochemistry

Detection of target analytes at low concentrations is significant in various fields, including pharmaceuticals, healthcare, and environmental protection. Theophylline (TP), a natural alkaloid used as a bronchodilator to treat respiratory disorders such as asthma, bronchitis, and emphysema, has a narrow therapeutic window with a safe plasma concentration ranging from 55.5–111.0 μmol·L^–1 in adults. Accurate monitoring of TP levels is essential because too low or too high can cause serious side effects. In this regard, non-enzymatic electrochemical sensors offer a practical solution with rapidity, portability, and high sensitivity. This article aims to provide a comprehensive review of the recent developments …

Investigating Spatial Mapping Of Lipid And Protein Alterations Within Cells And Tissues Using Raman Microspectroscopy, Elnaz Sheikh

LSU Doctoral Dissertations

The progression of various diseases is associated with alterations in the microenvironment of cells, consisting of a variety of metabolites like lipids and proteins. It is well known that lipids and proteins are potential biomarkers for indicating alterations within the cell microenvironment induced by disease, and various methods are frequently used for their examination. To understand the chemical composition and spatial distribution of constituents in tissues and cells, confocal Raman spectroscopy and microscopy, as non-destructive tools, have shown potential for monitoring abnormalities at the cellular level with high resolution and can facilitate detection through targeting multiple biomarkers. The application of …

Synthesis, Characterization And Electrical Properties Evaluation Of Zirconium Dioxide Capacitors, Thomas P. Chandy

USF Tampa Graduate Theses and Dissertations

This thesis focuses on the fabrication and comprehensive characterization of thin-film capacitors utilizing zirconium dioxide (ZrO2) as the dielectric material, placed between aluminum electrodes. The research primarily aims to examine the impact of varying ZrO2 film thickness and the effects of post-deposition annealing on the structural, morphological, and electrical properties of the capacitors. A controlled sputtering deposition technique was employed to ensure uniform film growth, maintaining consistency in thickness and material quality across all samples.

A comprehensive set of characterization techniques was employed to analyze the capacitors. Scanning electron microscope (SEM) was used to assess surface roughness, revealing fewer defects …

Synthesis, Characterization And Delamination Studies Of Metallic Thin Films Prepared Using Sputtering And Ebeam Evaporation Methods, Anoop Joseph

USF Tampa Graduate Theses and Dissertations

In many mechanical applications, including the manufacturing, automotive, and cutting tool sectors, metallic thin film coatings are crucial due to their tribological and protective properties. This research focuses on the development of metallic thin films of Aluminum (Al), Chromium (Cr) and Titanium (Ti) using deposition techniques like Sputtering and Electron Beam Evaporation. Metallic thin films were fabricated, with variations in thickness for each material, allowing for an in-depth study of the effects of Sputtering and Ebeam Evaporation deposition method on film characteristics. The thickness of these metallic thin films were evaluated using High-Resolution Scanning Electron Microscopy (HRSEM) and Profilometer while …

Analytical Electrochemistry Of Nickel, Platinum, And Platinum-Nickel Electrodepositions, Kyle James Troche

Nanoscience and Microsystems ETDs

Nickel and platinum electrodeposits have numerous applications in corrosion and wear-resistant coatings, electronic connectors, heat resistance, metal finishings, and catalysts. The addition of additives can vastly change the morphology of the deposition. Electrokinetic parameters can be calculated by conducting rotating disk electrode (RDE) experiments along with Koutecky-Levich analysis. Significant challenges need to be addressed to deposit uniform films of Pt-Ni alloys from a single co-deposition bath. The main challenge is platinum’s catalytic property to reduce the overpotential for the hydrogen generation reaction. An Investigation into methanol and carbon monoxide’s hydrogen generation reaction suppression was conducted. Electrodeposition of nickel, platinum, and …

Enhancing Cycle Life Of Graphite ‖ Lifepo4 Batteries Via Copper Substituted Li2Ni1-XCuXO2 Cathode Prelithiation Additive, Jian-Ming Zheng, Jing-Wen Zhang, Tian-Peng Jiao

Journal of Electrochemistry

Lithium nickel oxide (Li₂NiO₂), as a sacrificial cathode prelithiation additive, has been used to compensate for the lithium loss for improving the lifespan of lithium-ion batteries (LIBs). However, high-cost Li₂NiO₂ suffers from inferior delithiation kinetics during the first cycle. Herein, we investigate the effects of the cost-effective Cu substitution of Li₂Ni_1-xCu_xO₂ (x = 0, 0.2, 0.3, 0.5, 0.7) synthesized by high-temperature solid-phase method on the structure, morphology, electrochemical performance of graphite‖LiFePO₄ battery. The X-ray Diffraction (XRD) refinement result demonstrates that Cu substitution strategy is favorable …

Metal Nitrides As Cathode Hosts For Lithium-Sulfur Batteries, Hai-Ji Xiong, Cheng-Wei Zhu, Ding-Rong Deng, Qi-Hui Wu

Journal of Electrochemistry

Lithium-sulfur batteries are considered as one of the potential solutions as integrating renewable energy systems for large-scale energy storage because of their high theoretical energy density (2600 Wh·kg^–1) and specific capacity (1675 mAh·g^–1). Currently, various strategies have been proposed to overcome the technical barriers, e.g., “shuttle effect”, capacity decay and volumetric change, which impede the successful commercialization of lithium-sulfur batteries. This paper reviews the applications of metal nitrides as the cathode hosts for high-performance lithium-sulfur batteries, summarizes the design strategies of different host materials, and discusses the relationship between the properties of metal nitrides and their …