Measurement Of Hydrogen Concentration Research Articles

Perspective on the Development and Integration of Hydrogen Sensors for Fuel Cell Control

The measurement of hydrogen concentration in fuel cell systems is an important prerequisite for the development of a control strategy to enhance system performance, reduce purge losses and minimize fuel cell aging effects. In this perspective paper, the working principles of hydrogen sensors are analyzed and their requirements for hydrogen control in fuel cell systems are critically discussed. The wide measurement range, absence of oxygen, high humidity and limited space turn out to be most limiting. A perspective on the development of hydrogen sensors based on palladium as a gas-sensitive metal and based on the organic magnetic field effect in organic light-emitting devices is presented. The design of a test chamber, where the sensor response can easily be analyzed under fuel cell-like conditions is proposed. This allows the generation of practical knowledge for further sensor development. The presented sensors could be integrated into the end plate to measure the hydrogen concentration at the anode in- and outlet. Further miniaturization is necessary to integrate them into the flow field of the fuel cell to avoid fuel starvation in each single cell. Compressed sensing methods are used for more efficient data analysis. By using a dynamical sensor model, control algorithms are applied with high frequency to control the hydrogen concentration, the purge process, and the recirculation pump.

Premature Damage in Bearing Steel in Relation with Residual Stresses and Hydrogen Trapping

In this study, premature damage in cylindrical roller bearings made of 100Cr6 (SAE 52100) was investigated. For this purpose, full bearing tests were carried out using two different lubricant formulations with similar viscosities. Published research has pointed out the occurrence of tribo-chemical reactions that cause lubricant degradation and the release of hydrogen in tribo-contact. Hydrogen content measurements were conducted on tested samples, and these measurements showed dependence on the lubricant formulations. Hydrogen diffusion and trapping were identified as significant factors influencing premature damage. The measurement of trapping energies was conducted by thermal desorption spectroscopy, whereas residual stresses, which influence hydrogen diffusion and accumulation, were measured using X-ray diffraction. The measured trapping energies indicated that rolling contact caused the creation and release of hydrogen traps. Over-rolling resulted in changes in residual stress profiles in the materials, demonstrated by changes in stress gradients. These can be directly linked to subsurface hydrogen accumulation. Hence, it was possible to determine that the location of the microstructural damage (WEC) was correlated with the residual stress profiles and the subsurface von Mises stress peaks.

Production and New Green Activation of Conductive 3D-Printed Cu/PLA Electrode: Its Performance in Hydrogen Evolution Reactions in Alkaline Media

In this study, Cu-polylactic acid (PLA) composite filaments were produced with an extruder and three-dimensional (3D) Cu/PLA electrodes were 3D printed with Fused Deposition Modelling (FDM) method. To improve the electrochemical performance of the 3D-Cu/PLA electrode, a novel electrochemical activation method, which differentiates from complex activation methods in the literature, was applied in 1 M KOH solution without using any solvent. Field emission scanning electron microscopy (FE-SEM), Energy-Dispersive X-ray Spectroscopy (EDX), Fourier Transform Infrared Spectroscopy (FT-IR), and RAMAN techniques were used to characterize the 3D-Cu/PLA electrode before and after activation. The results showed that Cu particles were released after the degradation of PLA after activation. In addition, the thermal stability of the 3D electrode was demonstrated by the TGA technique. The performance of the 3D Cu/PLA electrode before and after activation in the hydrogen evolution reaction (HER) in 1M solution was measured using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and cathodic polarization curves methods. The EIS results showed that the charge transfers resistance values of the 3D-Cu/PLA electrode in 1 M KOH decreased significantly after activation. Post-activation hydrogen content measurements of the 3D-Cu/PLA electrode after electrolysis at different potentials and energy efficiency tests at different current densities were also carried out. The results indicate that the electrocatalytic properties of 3D-Cu electrodes were improved for HER through the activation process.

A Review on hydrogen embrittlement behavior of steel structures and measurement methods

Hydrogen can be found within metals under a variety of industrial and environmental conditions. Hydrogen-metal interactions can take place through hydrogen embrittlement, hydrogen sulfide corrosion, or hydrogen absorption. Steel and other metals that are exposed to hydrogen may experience a difficulty known as hydrogen embrittlement that affects their mechanical properties. The material's ductility and toughness may be reduced as a result of this phenomena, it also increasing the risk of brittle fracture. In steel, atomic hydrogen mainly diffuses into the microstructure of the steel, causing hydrogen embrittlement. Localized weakening of the bonds between the metal atoms might result from hydrogen atoms occupying interstitial positions in the metal lattice. Especially when under stress, this may lead to a more susceptible to fracture and cracking. Concerns with hydrogen embrittlement arise in sectors like aerospace and oil and gas that use high-strength steels. If not appropriately handled, it may result in catastrophic failures. Use of hydrogen-resistant alloys, appropriate heat treatments, and protection from conditions that promote hydrogen uptake are examples of preventive measures. This literature review paper covers the definition of hydrogen embrittlement (HE), mechanisms causing HE, measurement of hydrogen concentration and preventive measures that restrict hydrogen diffusion to the steel.

Electrochemical hydrogen permeation measurement during cyclic stress testing of a ferritic chromium steel

AbstractIn the present work, the hydrogen diffusion during cyclic stress testing in the ferritic chromium steel 1.4521 (X2CrMoTi18‐2) is investigated. Therefore, electrochemical hydrogen permeation measurements are carried out on a hollow cylinder geometry. Simultaneously an alternating stress is applied using a stress ratio of R=‐1. At low stress amplitudes, no influence on the diffusion behaviour of hydrogen is found. At a higher stress amplitude, close to the macroscopic yield strength, a delayed hydrogen permeation by a factor of two is observed. It is postulated that this observation is a result of the nucleation of new hydrogen traps during the measurement. Hydrogen content measurements using carrier gas hot extraction support this hypothesis.

Solid Electrochemical Method of Measuring Hydrogen Concentration with O2-/H+ Hetero-Ionic Junction

Solid Electrochemical Method of Measuring Hydrogen Concentration with O2-/H+ Hetero-Ionic Junction

Simultaneous measurement of hydrogen and methane concentrations with temperature self-calibration based on a SPR sensor with an anchor-shaped photonic crystal fiber

Hydrogen and methane are flammable and explosive gases, and their simultaneous measurement holds significant importance in applications of industrial safety and energy transmission. A high-sensitivity multi-parameter sensor based on the surface plasmon resonance (SPR) within an anchor-shaped photonic crystal fiber (AS-PCF) have been proposed and analyzed in detail, which can simultaneously measure hydrogen and methane concentrations while providing temperature self-compensation. To achieve simultaneous detection of hydrogen and methane, an open ring channel is introduced in both the x and y directions of the PCF. Each of these channels is coated with a layer of gold film and gas-sensitive films for hydrogen and methane, respectively. The designed AS-PCF structure is optimized to increase the reactive surface area between the gas and the gas-sensitive films, simultaneously enhancing the energy leakage of core modes to improve sensor performance. In addition, temperature sensitivity is augmented by filling PCF air holes with ethanol and enhancing the asymmetry of the fiber structure. The changes of gas concentration and environmental temperature are derived by demodulating the peak wavelength shifts in the loss and interference spectra. Simulation analysis demonstrates that the sensor can achieve average sensitivities of −0.23 nm/% for hydrogen and −4.84 nm/% for methane within the gas concentration range of 0.5 % to 3 %. Meanwhile, the temperature sensitivity can reach 0.58 nm/°C within the temperature range of 10 °C to 30 °C. This sensor demonstrates excellent linearity and high sensitivity, making it a promising tool for multi-gas measurements in various applications.

High pressure-sensitive and stable fiber Fabry-Perot interferometer with nano-diaphragm assembled by H-O catalysis bonding.

Herein, a high pressure-sensitive and stable fiber Fabry-Perot (FP) interferometer with nano-diaphragm assembled by H-O catalysis bonding is proposed and demonstrated. In order to assemble a nano-diaphragm-based fiber FP interferometer by H-O catalysis bonding technique, a SiO2 film, introduced as a bridging layer on the nano-diaphragm, can be regarded as a solid adhesive to bridge hollow-core fiber end-face and nano-diaphragm. As thus, by depositing bonded layers on different diaphragm materials, this H-O catalysis bonding technology can be used to for assembling FP interferometer with different materials nano-diaphragms. Experimentally, Si nano-diaphragm is transferred to hollow-core fiber end-face to build a stable fiber FP interferometer without polymeric adhesive. Experimental results reveal that this Si nano-diaphragm-based fiber FP interferometer has a high (79.6 pm/kPa) pressure sensitivity and a low (17.3 pm/°C) temperature sensitivity. Besides that, different materials nano-diaphragm also can be assembled by using this H-O catalysis bonding technique, and the functional FP interferometer can be realized by using functional nano-diaphragm material. Thus, a Pd nano-diaphragm is successfully assembled to build a FP interferometer with a hydrogen concentration measurement capacity. Further investigation will focus on exploitation of multi-material nano-film patterning transfer and different nano-film integration by using this H-O catalysis bonding transfer.

High-performance hydrogen gas sensor system based on transparent coaxial cylinder capacitive electrodes and a volumetric analysis technique

A high-performance H2 gas sensor system based on capacitive electrodes and a volumetric analysis technique were developed. Coaxial capacitive electrodes were fabricated by placing a thin copper rod in the center and by adhering a transparent conductive film on the exterior surface of a graduated cylinder. Thus, H2 from a polymer specimen lowered the water level in the cylinder between the two electrodes, producing measurable changes in capacitance that allowed for the measurement of the H2 concentration emitted from the specimen enriched by H2 under high-pressure conditions. The sensing system detected diffused/permeated hydrogen gas from a specimen and hydrogen gas leaks caused by imperfect sealing. The hydrogen gas sensor responded almost instantly at 1 s and measured hydrogen concentrations ranging from 0.15 to 1500 ppm with controllable sensitivity and a measurable range. In addition, performance tests with polymer specimens used in hydrogen infrastructure verified that the sensor system was reliable; additionally, it had a broad measurement range to four decimal places. The sensor system developed in this study could be applied to detect and characterize pure gases (He, N2, O2 and Ar) by real time measurement.

In situ measurement of hydrogen concentration in steel using laser-induced breakdown spectroscopy (LIBS)

AbstractThe ISO 3690 standard “Determination of hydrogen content in arc weld metal” requires a thermal activation of the diffusible hydrogen in a piece of weld metal for the subsequent ex situ concentration measurement by carrier gas hot extraction CGHE or thermal desorption spectroscopy (TCD). Laser-induced breakdown spectroscopy (LIBS) offers a time and spatially resolved, almost non-destructive, in situ measurement of hydrogen at surfaces without sample preparation. We measured hydrogen in steels, which were charged either electrochemically or by high-pressure hydrogen gas, and compared the results. Further, the feasibility of quantitative hydrogen line scan measurements with LIBS was demonstrated by measuring hydrogen at water jet cut surfaces. The hydrogen concentrations measured with the help of LIBS were compared with CGHE measurements. It was observed that hydrogen can be reliably measured with LIBS for concentrations larger than 2 wt.-ppm. The maximum hydrogen concentration achieved using electrochemical charging was 85.1 ppm. The results show that LIBS is a promising technique for time- and spatially resolved measurements of hydrogen in steels.

Accurate measurement of hydrogen concentration in transition metal hydrides utilizing electronic excitations by MeV ions

This study focuses on enhancing the accuracy of hydrogen content verification in hydrogen-rich ultrathin materials relevant for sustainable energy applications. Ion beams are used for distinctive real-space detection leveraging elastic and inelastic interactions with hydrogen atoms. However, the lack of experimental reference data on electronic interactions poses a challenge to the accuracy of analytical techniques. We investigate the effect of absorbed hydrogen on the electronic energy deposition of 15N-ions in amorphous transition metal compounds, specifically V and Zr, covering concentrations >1H/M. Employing resonant nuclear reactions and Rutherford backscattering, the energy loss is found to increase considerably with hydrogen content, in line with Bragg's additivity. The electronic energy loss cross section for 15N-ions at 6.5 MeV measured (64.55±3.38) eV cm2/1015 atoms. Results are compared to semi-empirical and theoretical models. The findings improve hydrogen profiling accuracy using 15N-nuclear reaction analysis and enable unprecedented methods for hydrogen quantification by other, commonly available ion beams.

Fast repeatable measurement of hydrogen concentration based on a reflective fiber hybrid interferometer probe with vernier effect

A hydrogen (H2) sensor based on hybrid Fabry-Perot interference (FPI) and Michelson interference (MI) with Vernier effect is demonstrated. The optical probe is manufactured by fusing a multimode fiber (MMF) and a double-side hole fiber (DSHF) between a single-mode fiber (SMF) and a hollow core fiber (HCF) filled with polydimethylsiloxane (PDMS) at the end to form a cascaded FP and MI, which can generate a vernier envelope. by fusing a multimode fiber (MMF) and a double-side hole fiber (DSHF) between a single-mode fiber (SMF) and a hollow core fiber (HCF) filled with PDMS at the end. To accomplish H2 sensing, palladium-tungstic oxide (Pd-WO3) powder is attached to the exterior surface of PDMS, which will cause an exothermic redox reaction with H2. The released heat will lead to the volume expansion of PDMS with remarkable thermal response characteristics, and finally cause the movement of the vernier-like spectral envelope with the variation of H2 concentration. The sensitivity of the proposed sensor is 2.2 nm/% in the range of 0 %–1% through the H2 measurement experiment. For H2 with a concentration of 1 %, it has the response time of 28 s and shows good reversibility in the cyclic experiment. In addition, the sensitivity of temperature and relative humidity (RH) is 0.21 nm/°C and 0.0014 nm/%RH, respectively. The proposed sensor adopts a reflective probe, which is compact in structure and small in volume, and shows fast response and excellent repeatability. It has great advantages in H2 measurement in narrow spaces and long distances.

Hydrogen concentration measurements using spark induced breakdown spectroscopy in a real engine

This study develops spark induced breakdown spectroscopy (SIBS) for measurements of direct injected hydrogen concentration in a multi-cylinder engine operated at real conditions. To this end, calibration is performed in the air excess ratio (λ) range of 2.1 ∼ 2.9 and simultaneously, high-speed schlieren imaging of laminar hydrogen flame propagation is performed in an optical high-pressure constant volume combustion chamber (CVCC). To achieve real engine applications, the SIBS is further developed using a modified conventional spark plug for sapphire window insertion onto the positive electrode and guided arc formation via a newly designed nipple type ground electrode. Specifically, the peak spectra intensity ratio of Hα (656 nm) to O (777 nm) is used for calibration, which shows a linear correlation with λ. For the first time, the calibrated SIBS is applied to a real engine operated at 46.2 ∼ 63.9 Nm load and 2000 rpm with 3.5 MPa hydrogen direct injection. The results show lower local λ than the global λ despite early injection timing of 165 crank angles before top dead centre, indicating a significant influence of in-cylinder flow motion on the spatial distribution of hydrogen-air mixtures.

Experimental Study on Distribution Characteristics and Leakage Detection of Hydrogen Release from Hydrogen Supply System of Fuel Cell Truck

The hydrogen supply system of a fuel cell truck is in a semi-enclosed space where hydrogen is easy to accumulate if a hydrogen leak occurs. The acquisition of hydrogen dispersion behavior data is essential to support the detection of hydrogen release. The purpose of this article is to present the characteristics of hydrogen concentration distribution and delay time of hydrogen leakage detection under different leakage parameters. The experiments have been performed in a hydrogen storage cabin with six hydrogen sensors arranged on the roof to measure hydrogen concentration. During the tests, hydrogen was released into the test cabin through standard leaks. Two different release rates (80 NL/min and 450 NL/min), three different release positions, and six release directions are investigated to analyze the effects on the distribution of hydrogen concentration and leakage detection delay time. This article presents both the experimental facility and results. The experimental results can help optimize the placement of hydrogen sensors and the design of a hydrogen leakage detection system.

Stability and reproducibility of solid electrolyte amperometry sensors at the analysis of hydrogen in nitrogen-containing gas mixtures

This paper illustrates the results of long-term tests on the stability of the output signal of the solid electrolyte amperometry sensor when measuring the hydrogen concentration in the H2 + N2 gaseous mixture. The obtained experimental data verify the stability and reproducibility of the sensor output signal for hydrogen concentration measurements in the nitrogen-containing gaseous mixture during > 8000 h of operation. The output signal drift, i.e., the limiting current value, was insignificant, less than ± 5 %. The sensor operation was performed at 3 temperature shifts with different time intervals; these changes did not have any impact either on the sensor integrity or on its operation. The structure of the solid electrolyte sensor, intermediate solid electrolyte / electrode layer and electrodes did not undergo any significant changes during operation. The dynamic characteristics of the sensor, the response time in particular, remained stable during the operation.

Investigation of an alternative method for hydrogen content measurement during laser beam welding under water

Hydrogen-induced cold cracks are among the most dangerous types of damage in welding technology, as they do not occur immediately after welding. Cold cracking behaviour plays a special role in the development of underwater welding processes, as the supply of hydrogen is particularly high due to dissociation of water. As part of the investigations in this paper, weld seams are performed using laser beam welding under water with a Yb:YAG laser and a power of up to 4 kW on 10 mm S235JR-steel samples. To measure the hydrogen content, an alternative approach to carrier gas hot extractions and mercury displacement methods is used. Here, the samples are stored directly after welding in a collecting device filled with paraffin oil. By displacing the paraffin oil with diffused hydrogen and subsequent imaging analysis, the hydrogen content can be calculated directly via the volume without expensive analysers.

Minimum Detection Concentration of Hydrogen in Air Depending on Substrate Type and Design of the 3ω Sensor.

Hydrogen has emerged as a promising carbon-neutral fuel source, spurring research and development efforts to facilitate its widespread adoption. However, the safe handling of hydrogen requires precise leak detection sensors due to its low activation energy and explosive potential. Various detection methods exist, with thermal conductivity measurement being a prominent technique for quantifying hydrogen concentrations. However, challenges remain in achieving high measurement sensitivity at low hydrogen concentrations below 1% for thermal-conductivity-based hydrogen sensors. Recent research explores the 3ω method's application for measuring hydrogen concentrations in ambient air, offering high spatial and temporal resolutions. This study aims to enhance hydrogen leak detection sensitivity using the 3ω method by conducting thermal analyses on sensor design variables. Factors including substrate material, type, and sensor geometry significantly impact the measurement sensitivity. Comparative evaluations consider the minimum detectable hydrogen concentration while accounting for the uncertainty of the 3ω signal. The proposed suspended-type 3ω sensor is capable of detecting hydrogen leaks in ambient air and provides real-time measurements that are ideal for monitoring hydrogen diffusion. This research serves to bridge the gap between precision and real-time monitoring of hydrogen leak detection, promising significant advancements in the related safety applications.

Evaluation of hydrogen recombination characteristics of a PAR using SPARC PAR experimental results

Passive auto-catalytic recombiners (PARs) are widely used to mitigate a hydrogen hazard. The first step to evaluate the hydrogen safety by PARs is to obtain qualified test data of the PARs for validation of their analytical model. SPARC PAR tests SP8 and SP9 were conducted to evaluate the hydrogen recombination characteristics of a honeycomb-shaped catalyst PAR. To obtain the hydrogen recombination rate from the PAR test data, two methods, Method-1 and Method-2, introduced by the THAI project, were applied. Since a large gradient of hydrogen concentration developed during hydrogen injection can cause a large error in the hydrogen mass obtained by integrating the measured hydrogen concentrations, a gate was installed at the PAR inlet to homogenize hydrogen in the test vessel before the PAR operation in the tests. A computational fluid dynamics (CFD) code with a PAR model was also applied to evaluate the characteristics of the PAR recombination according to the PAR inlet conditions, and the results were compared with those from Method-1 and Method-2. It was confirmed that the recombination rates from Method-1 require a correction factor to be compatible with results from Method-2 and the CFD simulation in the case of the SPARC-PAR tests.

Inhibitory effect of La3+ on hydrogen damage of 27CrMo44S/1 steel in H2S-containing acidic solution

The effect of La3+ on the hydrogen permeation behavior of 27CrMo44S/1 steel in acidic environments containing H2S is investigated through the measurement of steady-state permeation current density (i∞), hydrogen diffusivity (D), and subsurface hydrogen concentration (C0). Results indicate that the addition of La3+ can remarkably reduce i∞. The corrosion products with La3+ involved in the film formation process in the H2S-free environment have a good hydrogen barrier effect, but the addition of La3+ hardly influence the D value of 27CrMo44S/1 steel in the H2S-containing environment. However, the presence of La3+ substantially reduces the C0 on metal surface regardless of the presence of H2S in the solution. Static immersion and tensile experiments illustrate that the addition of La3+ can improve the corrosion resistence and plasticity loss of the material in the H2S environment.

Development of a 2D digital proton–proton scattering technique for hydrogen depth profiling

Measuring hydrogen concentration and determining its depth profile in different substrates has always been a major challenge for material science. Proton–proton scattering is a nondestructive technique for hydrogen analysis in thin samples. In this paper, the development of a 2D coincidence proton–proton spectroscopy was performed using a 3 MeV Van de Graaff accelerator. In the presented technique, the coincidence recording of the proton–proton scattering events by a waveform digitizer provides the sum‐difference energy spectrum of the correlated events. By determining the proton energy loss in the sample, the hydrogen depth profile was extracted. To correct the error in the counting efficiency due to the multiple scattering, the Monte Carlo simulation was performed using the Corteo code. The performance of the technique was tested by measuring the concentration of hydrogen on both sides of a thin layer of aluminum. The results confirmed that the established technique is sensitive enough to separate the hydrogen peaks of these two thin layers.