All-Around Electromagnetic Wave Absorber Based on Ni-Zn Ferrite.

Exploring a convenient, scalable, yet effective broadband electromagnetic wave absorber (EMA) in the gigahertz (GHz) region is of high interest today to quench its expanding demand. Ni-Zn ferrite is considered as a potential EMA; however, their performance study as a scalable effective millimeter-length absorber is still limited. Herein, we investigated EM wave attenuation properties of Ni0.5Zn0.5Fe2O4 (NZF) samples substituting Mn ion in place of Fe3+ as well as Zn2+ within a widely used frequency range of 0.1-9 GHz. Through composition optimization, Ni0.5Zn0.4Mn0.1Fe2O4 (NZM0.1F) EMA demonstrates excellent microwave absorption performance accompanied by simultaneous maximum reflection loss (RL) of -50.2 dB and wide BW of 6.8 GHz (with RL < -10 dB, i.e., attenuation >90%) at an optimum thickness of 6 mm. Moreover, the attenuation constant significantly increases from ∼217 to 301 Np/m with Mn doping. The key contribution arises from magnetic-dielectric properties synergy along with enhanced dielectric and magnetic losses owing to cation chemistry and site occupation in spinel NZF. In addition, porosity is induced in the system by a controlled two-step heat treatment process that promotes total loss with multiple internal reflections of the EM wave. Furthermore, RL is simulated by varying incident EM wave angles for the NZM0.1F sample displaying its angle insensitivity up to 50°. Our results reveal NZM0.1F as a futuristic environment-friendly microwave absorber material that is suitable for practical high-frequency applications.

Sorption-Induced Fiber Optic Plasmonic Gas Sensing via Small Grazing Angle of Incidence.

Sensing technologies based on plasmonic nanomaterials are of interest for various chemical, biological, environmental, and medical applications. In this work, an incorporation strategy of colloidal plasmonic nanoparticles (pNPs) in microporous polymer for realizing distinct sorption-induced plasmonic sensing is reported. This approach is demonstrated by introducing tin-doped indium oxide pNPs into a polymer of intrinsic microporosity (PIM-1). The composite film (pNPs-polymer) provides distinct and tunable optical features on the fiber optic (FO) platform that can be used as a signal transducer for gas sensing (e.g., CO2 ) under atmospheric conditions. The resulting pNPs-polymer composite demonstrates high sensitivity response on FO in the evanescent field configuration, provided by the dramatic response of modes above the total-internal-reflection angle. Furthermore, by varying the pNPs content in the polymer matrix, the optical behavior of the pNPs-polymer composite film can be tuned to affect the operational wavelength by over several hundred nanometers and the sensitivity of the sensor in the near-infrared range. It is also shown that the pNPs-polymer composite film exhibits remarkable stability over a period of more than 10 months by mitigating the physical aging issue of the polymer.

Quasi-Distributed Fiber Sensor-Based Approach for Pipeline Health Monitoring: Generating and Analyzing Physics-Based Simulation Datasets for Classification.

This study presents a framework for detecting mechanical damage in pipelines, focusing on generating simulated data and sampling to emulate distributed acoustic sensing (DAS) system responses. The workflow transforms simulated ultrasonic guided wave (UGW) responses into DAS or quasi-DAS system responses to create a physically robust dataset for pipeline event classification, including welds, clips, and corrosion defects. This investigation examines the effects of sensing systems and noise on classification performance, emphasizing the importance of selecting the appropriate sensing system for a specific application. The framework shows the robustness of different sensor number deployments to experimentally relevant noise levels, demonstrating its applicability in real-world scenarios where noise is present. Overall, this study contributes to the development of a more reliable and effective method for detecting mechanical damage to pipelines by emphasizing the generation and utilization of simulated DAS system responses for pipeline classification efforts. The results on the effects of sensing systems and noise on classification performance further enhance the robustness and reliability of the framework.

Investigation of Goubau Wave Propagation on Large Pipes for Sensing Applications.

We examine the application of guided waves on a single conductor (Goubau waves) for sensing. In particular, the use of such waves to remotely interrogate surface acoustic wave (SAW) sensors mounted on large-radius conductors (pipes) is considered. Experimental results using a small-radius (0.0032 m) conductor at 435 MHz are reported. The applicability of published theory to conductors of large radius is examined. Finite element simulations are then used to study the propagation and launching of Goubau waves on steel conductors up to 0.254 m in radius. Simulations show that waves can be launched and received, although energy loss into radiating waves is a problem with current launcher designs.

A machine learning based computational approach for prediction of cation distribution in spinel crystal.

In this study, a machine learning based computational approach has been developed to investigate the cation distribution in spinel crystals. The computational approach integrates the construction of datasets consisting of the energies calculated from density functional theory, the training of machine learning models to derive the relationship between system energy and structural features, and atomistic Monte Carlo simulations to sample the thermodynamic equilibrium structures of spinel crystals. It is found that the support vector machine model yields excellent performance in energy predictions based on spinel crystal structures. Furthermore, the developed computational approach has been applied to predict the cation distribution in single spinel MgAl2O4 and MgFe2O4 and double spinel MgAl2-aFeaO4. Agreeing with the available experimental data, the computational approach correctly predicts that the equilibrium degree of inversion of MgAl2O4 increases with temperature, whereas the degree of inversion of MgFe2O4 decreases with temperature. Additionally, it is predicted that the equilibrium occupancy of Mg cations at the tetrahedral and octahedral sites in MgAl2-aFeaO4 could be tuned as a function of chemical composition. Therefore, this study presents a reliable computational approach that can be extended to study the variation of cation distribution with processing temperature and chemical composition in a wide range of complex multi-cation spinel oxides with numerous applications.

Synthesis of High-Quality Mg-MOF-74 Thin Films via Vapor-Assisted Crystallization.

The unique features of metal-organic frameworks (MOFs), such as their large surface areas and diversity of structures, make them suitable for a broad range of applications including storage, separation, and sensing of gases. Among all the MOFs, Mg-MOF-74 with the highest CO2 uptake at 1 bar and 25 °C would be particularly beneficial for CO2-related applications. One of the most critical enabling technologies for implementing Mg-MOF-74 is the preparation of dense and continuous films that would maximize the sorption behaviors. However, Mg-MOF-74 thin films present significant challenges in demonstrating large-scale coatings. Herein, we demonstrate for the first time high-quality Mg-MOF-74 films synthesized via a vapor-assisted crystallization (VAC) process. The VAC process described herein provides dense and highly crystalline layers of the Mg-MOF-74 thin film with a low coefficient of variation of film thickness below 7%. By minimizing the solvent use, the VAC process is also more environmentally friendly than conventional techniques. In this work, we first optimized a precursor solution for the VAC process and then investigated the effects of synthesis temperature, time, and droplet volume on the growth, crystallinity, and thickness of VAC Mg-MOF-74 films. The porosity of the MOF film was assessed by measuring the CO2 uptake at room temperature and 1 bar. The obtained VAC Mg-MOF-74 films possess a well-defined microporosity, as deduced from CO2 adsorption studies via quartz crystal microbalance (QCM) and comparison with bulk Mg-MOF-74 reference data. Furthermore, CO2 cyclic adsorption-desorption experiments on the VAC Mg-MOF-74 films showed scaled uptakes to a wide range of CO2 concentration without showing significant variations in the baseline. We specifically demonstrate how the film's quality of the MOF affects adsorption behavior of CO2 on VAC Mg-MOF-74 and drop-cast Mg-MOF-74 films.

Fiber Coupled Near-Field Thermoplasmonic Emission from Gold Nanorods at 1100 K.

Nanostructured gold has attracted significant interest from materials science, chemistry, optics and photonics, and biology due to their extraordinary potential for manipulating visible and near-infrared light through the excitation of plasmon resonances. However, gold nanostructures are rarely measured experimentally in their plasmonic properties and hardly used for high-temperature applications because of the inherent instability in mass and shape due to the high surface energy at elevated temperatures. In this work, the first direct observation of thermally excited surface plasmons in gold nanorods at 1100 K is demonstrated. By coupling with an optical fiber in the near-field, the thermally excited surface plasmons from gold nanorods can be converted into the propagating modes in the optical fiber and experimentally characterized in a remote manner. This fiber-coupled technique can effectively characterize the near-field thermoplasmonic emission from gold nanorods. A direct simulation scheme is also developed to quantitively understand the thermal emission from the array of gold nanorods. The experimental work in conjunction with the direct simulation results paves the way of using gold nanostructures as high-temperature plasmonic nanomaterials, which has important implications in thermal energy conversion, thermal emission control, and chemical sensing.

Fiber Optic Sensing Technologies for Battery Management Systems and Energy Storage Applications.

Applications of fiber optic sensors to battery monitoring have been increasing due to the growing need of enhanced battery management systems with accurate state estimations. The goal of this review is to discuss the advancements enabling the practical implementation of battery internal parameter measurements including local temperature, strain, pressure, and refractive index for general operation, as well as the external measurements such as temperature gradients and vent gas sensing for thermal runaway imminent detection. A reasonable matching is discussed between fiber optic sensors of different range capabilities with battery systems of three levels of scales, namely electric vehicle and heavy-duty electric truck battery packs, and grid-scale battery systems. The advantages of fiber optic sensors over electrical sensors are discussed, while electrochemical stability issues of fiber-implanted batteries are critically assessed. This review also includes the estimated sensing system costs for typical fiber optic sensors and identifies the high interrogation cost as one of the limitations in their practical deployment into batteries. Finally, future perspectives are considered in the implementation of fiber optics into high-value battery applications such as grid-scale energy storage fault detection and prediction systems.

Influence of the Anionic Zinc-Adeninate Metal-Organic Framework Structure on the Luminescent Detection of Rare Earth Ions in Aqueous Streams.

Rare earth elements (REEs) are critical to numerous technologies; however, a combination of increasing demand, environmental concerns, and monopolistic marketplace conditions has spurred interest in boosting the domestic REE production from sources such as coal utilization byproducts. The economic viability of this approach requires rapid, inexpensive, and sensitive analytical techniques capable of characterizing the REE content during resource exploration and downstream REE processing (e.g., analyzing REE separation, concentration, and purification production steps). Luminescence-based sensors are attractive because many REEs may be sensitized to produce element-specific emission. Hence, a single material may simultaneously detect and distinguish multiple REEs. Metal-organic frameworks (MOFs) can sensitize multiple REEs, but their viability has been hindered by sensitivity and selectivity challenges. Understanding how the MOF structure impacts the REE sensing efficacy is critical to the rational design of new sensors. Here, we evaluate the sensing performance of seven different anionic zinc-adeninate MOFs with different organic linkers and/or structures for the visible-emitting REEs Tb, Dy, Sm, and Eu. The choice of a linker determines which REEs are sensitized and significantly influences their sensitivity and selectivity against competing species (here, Fe(II) and HCl). For a given linker, structural changes to the MOF can further fine-tune the performance. The MOFs produce some of the lowest detection limits (sub-10 ppb for Tb) reported for the aqueous sensitization-based REE detection. Importantly, the most selective MOFs demonstrated the ability to sensitize the REE signal at sub-ppm levels in a REE-spiked acid mine drainage matrix, highlighting their potential for use in real-world sensing applications.

Centimeter-Scale Pillared-Layer Metal-Organic Framework Thin Films Mediated by Hydroxy Double Salt Intermediates for CO2 Sensor Applications.

Fabrication of metal-organic framework (MOF) thin films over macroscopic surface areas is a subject of great interest for gas sensor application platforms such as optics and microelectronics. However, a direct synthesis of MOF films at ambient conditions, in particular pillared-layer MOF films due to their anisotropic structures, remains a significant challenge. Herein, we demonstrate for the first time a facile construction of dense and continuous pillared-layer MOF thin films on a centimeter scale via an aluminum-doped zinc oxide template and hydroxy double salt (HDS) intermediates at room temperature. A series of Cu(II)-based pillared MOFs with different 1,4-benzenedicarboxylic acid (bdc) ligands were explored for optimizing MOF film formation for CO2 sensor applications. Nonpolar ligands with lower water solubility preferentially formed crystalline pillared MOF structures from HDS intermediates. A Cu2(ndc)2(dabco) (ndc = 1,4-naphthalene-bdc; dabco = 1,4-diazabicyclo[2.2.2]octane) MOF demonstrated the most dense and uniform film growth with micrometer thickness over one square centimeter area. This synthetic approach for growing Cu2(ndc)2(dabco) MOF thin films was successfully translated toward two sensing platforms: a quartz crystal microbalance and an optical fiber sensor. These Cu2(ndc)2(dabco) MOF-coated sensors displayed sensitivity toward CO2 and response/recovery time on the scale of seconds, even at moderate humidity levels. This work provides a road map for producing continuous and anisotropic crystalline MOF thin films over a centimeter scale area on various substrates, which will greatly facilitate their utilization in MOF-based sensor devices, among other applications.

Multiplexable high-temperature stable and low-loss intrinsic Fabry-Perot in-fiber sensors through nanograting engineering.

This paper presents a method of using femtosecond laser inscribed nanograting as low-loss- and high-temperature-stable in-fiber reflectors. By introducing a pair of nanograting inside the core of a single-mode optical fiber, an intrinsic Fabry-Perot interferometer can be created for high-temperature sensing applications. The morphology of the nanograting inscribed in fiber cores was engineered by tuning the fabrication conditions to achieve a high fringe visibility of 0.49 and low insertion loss of 0.002 dB per sensor. Using a white light interferometry demodulation algorithm, we demonstrate the temperature sensitivity, cross-talk, and spatial multiplexability of sensor arrays. Both the sensor performance and stability were studied from room temperature to 1000°C with cyclic heating and cooling. Our results demonstrate a femtosecond direct laser writing technique capable of producing highly multiplexable in-fiber intrinsic Fabry-Perot interferometer sensor devices with high fringe contrast, high sensitivity, and low-loss for application in harsh environmental conditions.

Combined plasmonic Au-nanoparticle and conducting metal oxide high-temperature optical sensing with LSTO.

Fiber optic sensor technology offers several advantages for harsh-environment applications. However, the development of optical gas sensing layers that are stable under harsh environmental conditions is an ongoing research challenge. In this work, electronically conducting metal oxide lanthanum-doped strontium titanate (LSTO) films embedded with gold nanoparticles are examined as a sensing layer for application in reducing gas flows at high temperature (600-800 °C). A strong localized surface plasmon resonance (LSPR) based response to hydrogen is demonstrated in the visible region of the spectrum, while a Drude free electron-based response is observed in the near-IR. Characteristics of these responses are studied both on planar glass substrates and on silica fibers. Charge transfer between the oxide film and the gold nanoparticles is explored as a possible mechanism governing the Au LSPR response and is considered in terms of the corresponding properties of the conducting metal oxide-based matrix phase. Principal component analysis is applied to the combined plasmonic and free-carrier based response over a range of temperatures and hydrogen concentrations. It is demonstrated that the combined visible and near-IR response of these films provides improved versatility for multiwavelength interrogation, as well as improved discrimination of important process parameters (concentration and temperature) through application of multivariate analysis techniques.

Nanostructured sapphire optical fiber embedded with Au nanorods for high-temperature plasmonics in harsh environments.

Sensors for harsh environments must exhibit robust sensing response and considerable thermal and chemical stability. We report the exploration of a novel all-alumina nanostructured sapphire optical fiber (NSOF) embedded with Au nanorods (Au NRs) for plasmonics-based sensing at high temperatures. Temperature dependence of the localized surface plasmon resonance (LSPR) of Au NRs was studied in conjunction with numerical calculations using the Drude model. It was found that LSPR of Au NRs changes markedly with temperature, red shifting and increasing in transmission amplitude as the temperature increases. Furthermore, this variation is highly localized through tunneling by overlapping the near-field of thin cladding and sapphire optical fiber. The NSOF embedded with Au NRs has the potential for sensing in advanced energy generation systems.

Corrosion Sensors for Structural Health Monitoring of Oil and Natural Gas Infrastructure: A Review.

Corrosion has been a great concern in the oil and natural gas industry costing billions of dollars annually in the U.S. The ability to monitor corrosion online before structural integrity is compromised can have a significant impact on preventing catastrophic events resulting from corrosion. This article critically reviews conventional corrosion sensors and emerging sensor technologies in terms of sensing principles, sensor designs, advantages, and limitations. Conventional corrosion sensors encompass corrosion coupons, electrical resistance probes, electrochemical sensors, ultrasonic testing sensors, magnetic flux leakage sensors, electromagnetic sensors, and in-line inspection tools. Emerging sensor technologies highlight optical fiber sensors (point, quasi-distributed, distributed) and passive wireless sensors such as passive radio-frequency identification sensors and surface acoustic wave sensors. Emerging sensors show great potential in continuous real-time in-situ monitoring of oil and natural gas infrastructure. Distributed chemical sensing is emphasized based on recent studies as a promising method to detect early corrosion onset and monitor corrosive environments for corrosion mitigation management. Additionally, challenges are discussed including durability and stability in extreme and harsh conditions such as high temperature high pressure in subsurface wellbores.

Alkylamine-Integrated Metal-Organic Framework-Based Waveguide Sensors for Efficient Detection of Carbon Dioxide from Humid Gas Streams.

Metal-organic framework (MOF)-based chemical sensors have recently been demonstrated to be highly selective, sensitive, and reversible for CO2 sensing across a range of platforms including optical fiber and surface acoustic wave-based sensors. However, interference of water molecules is a primary issue in CO2 sensing systems based upon MOF layers due to cross-sensitivity, stability of MOF-based materials in humid conditions, and associated baseline drift over the lifetime of sensors. Herein, we develop a simple approach of alleviating the negative effect of water vapor to the optical fiber sensor by using alkylamine (i.e., oleylamine) to form a protective hydrophobic layer on the surface of MOFs for improving water stability. Alkylamine-modification of a MOF-coated optical fiber sensor provides a reversible and stable sensing response to a wide range of CO2 concentrations while also enhancing the CO2 sensitivity of the sensor under wet conditions. The FT-IR and breakthrough studies on the oleylamine-modified MOF confirm that the water vapor does not adversely impact the intrinsic CO2 sorption capacities. Thus, this simple stratrgy for enhancing the CO2/H2O selectivity in the MOF sorbent could also be useful for improving CO2 capture/separation performance in flue gas stream.

Zinc-Adeninate Metal-Organic Framework: A Versatile Photoluminescent Sensor for Rare Earth Elements in Aqueous Systems.

Rare earth elements (REEs) are strategically important for national security and advanced technologies. Consequently, significant effort has been devoted towards increasing REE domestic production, including the extraction of REEs from coal, coal combustion byproducts, and their associated waste streams such as acid mine drainage. Analytical techniques for rapid quantification of REE content in aqueous phases can facilitate REE recovery through rapid identification of high-value waste streams. In this work, we show that BioMOF-100 can be used as a fluorescent-based sensitizer for emissive REE ion detection in water, providing rapid (<10 min) analysis times and sensitive detection (parts-per-billion detection limits) for terbium, dysprosium, samarium, europium, ytterbium, and neodymium, even in the presence of acids or secondary metals.

Plasmonic Au nanorods stabilized within anodic aluminum oxide pore channels against high-temperature treatment.

Au nanorods (Au NRs) are promising candidates for sensing applications due to their tunable localized surface plasmon resonance wavelength. At temperatures above 250 °C, however, these structures are morphologically unstable and tend to evaporate. We herein report a novel refractory plasmonic nanocomposite system comprising Au NRs entrapped in anodized aluminum oxide (AAO) scaffolds that are stable up to 800 °C. Au NRs were synthesized in the cylindrical pores of sapphire-supported AAO via in situ electroless deposition on catalytic Au nanoparticles (Au NPs) anchored on the pore walls. The morphological characteristics and surface-enhanced Raman scattering (SERS) functionality of Au NRs before and after heat treatment were evaluated using SEM, XRD and Raman spectroscopy. Compared to unconfined Au NRs that evolved into spherical particles at temperatures below 250 °C and subsequently evaporated from the substrate surface, the morphology of Au NRs in AAO was preserved upon heat treatment at temperatures up to 800 °C. Furthermore, by tuning the AAO scaffolds thickness and pore diameter, the aspect ratio (AR) of the entrapped Au NRs was varied from 2.4 to 7.8. The SERS sensitivity of Au NRs in AAO was found to increase with decreasing AR when the incident light was parallel to the rod longitudinal axis, in close agreement with the calculated fourth power of the local electromagnetic field using the finite-difference time domain method.

Plasmonic Conducting Metal Oxide-Based Optical Fiber Sensors for Chemical and Intermediate Temperature-Sensing Applications.

The demand for real-time sensors in harsh environments at elevated temperature is significant and increasing. In this manuscript, the chemical and temperature sensing using the optical response through the practical fiber platform is demonstrated, and principle component analysis is coupled with targeted experimental film characterization to understand the fundamental sensing layer properties, which dominate measured gas sensing responses in complex gas mixtures. More specifically, tin-doped indium oxide-decorated sensors fabricated with the sol-gel method show stable and stepwise transmission responses varying over a wide range of H2 concentration (5-100%) at 250-350 °C as well as responses to CH4 and CO to a lesser extent. Measured responses are attributed to modifications to the surface plasmon resonance absorption in the near-infrared range and are dominated by the highest concentrations of the most-reducing analyte based upon systematic mixed gas stream experiments. Principal component analysis is utilized for this type of sensor to improve the quantitative and qualitative understanding of responses, clearly identifying that the dominant principle component (PC #1) accounts for ∼78% of total data variance. Correlations between PC #1 and the experimentally derived free carrier concentration confirm that this material property plays the strongest role on the ITO gas sensing mechanism, while correlations between the free carrier mobility and the second most important principle component (PC #2) suggest that this quantity may play a significant but secondary role. As such, the results presented here clarify the relationship between generalized principle components and fundamental sensing materials properties thereby suggesting the pathway toward improved multicomponent gas speciation through sensor layer engineering. The work presented represents a significant step toward the ultimate objective of optical waveguide sensors integrated with multivariate data analytics for multiparameter monitoring with a single sensor element.

Zeolitic imidazolate framework-coated acoustic sensors for room temperature detection of carbon dioxide and methane.

The integration of nanoporous materials such as metal organic frameworks (MOFs) with sensitive transducers can result in robust sensing platforms for monitoring gases and chemical vapors for a range of applications. Here, we report on an integration of the zeolitic imidazolate framework - 8 (ZIF-8) MOF with surface acoustic wave (SAW) and thickness shear mode quartz crystal microbalance (QCM) devices to monitor carbon dioxide (CO2) and methane (CH4) under ambient conditions. The MOF was directly coated on the Y-Z LiNbO3 SAW delay lines (operating frequency, f0 = 436 MHz) and AT-cut quartz TSM resonators (resonant frequency, f0 = 9 MHz) and the devices were tested for various gases in N2 under ambient conditions. The devices were able to detect the changes in CO2 or CH4 concentrations with relatively higher sensitivity to CO2, which was due to its higher adsorption potential and heavier molecular weight. The sensors showed full reversibility and repeatability which were attributed to the physisorption of the gases into the MOF and high stability of the devices. Both types of sensors showed linear responses relative to changes in the binary gas compositions thereby allowing to construct calibration curves which correlated well with the expected mass changes in the sorbent layer based on mixed-gas gravimetric adsorption isotherms measured on bulk samples. For 200 nm thick films, the SAW sensitivities to CO2 and CH4 were 1.44 × 10-6/vol% and 8 × 10-8/vol%, respectively, against the QCM sensitivities 0.24 × 10-6/vol% and 1 × 10-8/vol%, respectively, which were evaluated as the fractional change in the signal. The SAW sensors were also evaluated for 100 nm-300 nm thick films, the sensitivities of which were found to increase with the thickness due to the increased number of pores for the adsorption of a larger amount of gases. In addition, the MOF-coated SAW delay lines had a good response in wireless mode, demonstrating their potential to operate remotely for the detection of the gases at emission sites across the energy infrastructure.

Metal-Organic Framework Thin Film Coated Optical Fiber Sensors: A Novel Waveguide-Based Chemical Sensing Platform.

Integration of optical fiber with sensitive thin films offers great potential for the realization of novel chemical sensing platforms. In this study, we present a simple design strategy and high performance of nanoporous metal-organic framework (MOF) based optical gas sensors, which enables detection of a wide range of concentrations of small molecules based upon extremely small differences in refractive indices as a function of analyte adsorption within the MOF framework. Thin and compact MOF films can be uniformly formed and tightly bound on the surface of etched optical fiber through a simple solution method which is critical for manufacturability of MOF-based sensor devices. The resulting sensors show high sensitivity/selectivity to CO2 gas relative to other small gases (H2, N2, O2, and CO) with rapid (