Poland
Investigation of Hydrogen Embrittlement Susceptibility and Fracture Toughness Drop after in situ Hydrogen Cathodic Charging for an X65 Pipeline Steel
Apr 2020
Publication
The present research focuses on the investigation of an in situ hydrogen charging effect during Crack Tip Opening Displacement testing (CTOD) on the fracture toughness properties of X65 pipeline steel. This grade of steel belongs to the broader category of High Strength Low Alloy Steels (HSLA) and its microstructure consists of equiaxed ferritic and bainitic grains with a low volume fraction of degenerated pearlite islands. The studied X65 steel specimens were extracted from pipes with 19.15 mm wall thickness. The fracture toughness parameters were determined after imposing the fatigue pre-cracked specimens on air on a specific electrolytic cell under a slow strain rate bending loading (according to ASTM G147-98 BS7448 and ISO12135 standards). Concerning the results of this study in the first phase the hydrogen cations’ penetration depth the diffusion coefficient of molecular and atomic hydrogen and the surficial density of blisters were determined. Next the characteristic parameters related to fracture toughness (such as J KQ CTODel CTODpl) were calculated by the aid of the Force-Crack Mouth Open Displacement curves and the relevant analytical equations.
The Influence of Refractory Metals on the Hydrogen Storage Characteristics of FeTi-based Alloys Prepared by Suspended Droplet Alloying
Jun 2020
Publication
The influence of the addition of refractory metals (molybdenum and tantalum) on the hydrogenation properties of FeTi intermetallic phase-based alloys was investigated. The suspended droplet alloying technique was applied to fabricate FeTiTa-based and FeTiMo-based alloys. The phase composition and hydrogen storage properties of the samples were investigated. The samples modified with the refractory metals exhibited lower plateau pressures and lower hydrogen storage capacities than those of the FeTi reference sample due to solid solution formation. It was observed that the equilibrium pressures decreased with the amount of molybdenum which is in good agreement with the increase in the cell parameters of the TiFe phase. Suspended droplet alloying was found to be a practical method to fabricate alloys with refractory metal additions; however it is appropriate for screening samples with desired chemical and phase compositions rather than for manufacturing purposes.
Hydrogen Explosion Hazards Limitation in Battery Rooms with Different Ventilation Systems
Sep 2019
Publication
When charging most types of industrial lead-acid batteries hydrogen gas is emitted. A large number of batteries especially in relatively small areas/enclosures and in the absence of an adequate ventilation system may create an explosion hazard. This paper describes full scale tests in confined space which demonstrate conditions that can occur in a battery room in the event of a ventilation system breakdown. Over the course of the tests full scale hydrogen emission experiments were performed to study emission time and flammable cloud formation according to the assumed emission velocity. On this basis the characteristics of dispersion of hydrogen in the battery room were obtained. The CFD model Fire Dynamic Simulator (NIST) was used for confirmation that the lack of ventilation in a battery room can be the cause of an explosive atmosphere developing and leading to a potential huge explosive hazard. It was demonstrated that different ventilation systems provide battery rooms with varying efficiencies of hydrogen removal. The most effective type appeared to be natural ventilation which proved more effective than mechanical means.
People’s Attitude to Energy from Hydrogen—From the Point of View of Modern Energy Technologies and Social Responsibility
Dec 2020
Publication
Energy from hydrogen is an appropriate technological choice in the context of sustainable development. The opportunities offered by the use of energy from hydrogen also represent a significant challenge for mobile technologies and daily life. Nevertheless despite a significant amount of research and information regarding the benefits of hydrogen energy it creates considerable controversy in many countries. Globally there is a lack of understanding about the production process of hydrogen energy and the benefits it provides which leads to concerns regarding the consistency of its use. In this study an original questionnaire was used as a research tool to determine the opinions of inhabitants of countries in which hydrogen energy is underutilized and where the infrastructure for hydrogen energy is underdeveloped. Respondents presented their attitude to ecology and indicated their knowledge regarding the operation of hydrogen energy and the use of hydrogen fuel. The results indicate that society is not convinced that the safety levels for energy derived from hydrogen are adequate. It can be concluded that knowledge about hydrogen as an energy source and the production safety and storage methods of hydrogen is very low. Negative attitudes to hydrogen energy can be an important barrier in the development of this energy in many countries.
A Review of Recent Advances on the Effects of Microstructural Refinement and Nano-Catalytic Additives on the Hydrogen Storage Properties of Metal and Complex Hydrides
Dec 2010
Publication
The recent advances on the effects of microstructural refinement and various nano-catalytic additives on the hydrogen storage properties of metal and complex hydrides obtained in the last few years in the allied laboratories at the University of Waterloo (Canada) and Military University of Technology (Warsaw Poland) are critically reviewed in this paper. The research results indicate that microstructural refinement (particle and grain size) induced by ball milling influences quite modestly the hydrogen storage properties of simple metal and complex metal hydrides. On the other hand the addition of nanometric elemental metals acting as potent catalysts and/or metal halide catalytic precursors brings about profound improvements in the hydrogen absorption/desorption kinetics for simple metal and complex metal hydrides alike. In general catalytic precursors react with the hydride matrix forming a metal salt and free nanometric or amorphous elemental metals/intermetallics which in turn act catalytically. However these catalysts change only kinetic properties i.e. the hydrogen absorption/desorption rate but they do not change thermodynamics (e.g. enthalpy change of hydrogen sorption reactions). It is shown that a complex metal hydride LiAlH4 after high energy ball milling with a nanometric Ni metal catalyst and/or MnCl2 catalytic precursor is able to desorb relatively large quantities of hydrogen at RT 40 and 80 °C. This kind of behavior is very encouraging for the future development of solid state hydrogen systems.
Residual Performance of Composite Pressure Vessels Submitted to Mechanical Impacts
Sep 2017
Publication
Type IV pressure vessels are commonly used for hydrogen on-board stationary or bulk storages. During their lifetime they can be submitted to mechanical impacts creating damage within the composite structure not necessarily correlated to what is visible from the outside. When an impact is suspected or when a cylinder is periodically inspected it is necessary to determine whether it can safely stay in service or not. The FCH JU project Hypactor aims at creating a large database of impacts characterized by various non destructive testing (NDT) methods in order to provide reliable pass-fail criteria for damaged cylinders. This paper presents some of the tests results investigating short term burst) and long term (cycling) performance of impacted cylinders and the recommendations that can be made for impact testing and NDT criteria calibration.
Investigation of Praseodymium and Samarium Co-doped Ceria as an Anode Catalyst for DIR-SOFC Fueled by Biogas
Aug 2020
Publication
The Pr and Sm co-doped ceria (with up to 20 mol.% of dopants) compounds were examined as catalytic layers on the surface of SOFC anode directly fed by biogas to increase a lifetime and the efficiency of commercially available DIR-SOFC without the usage of an external reformer.
The XRD SEM and EDX methods were used to investigate the structural properties and the composition of fabricated materials. Furthermore the electrical properties of SOFCs with catalytic layers deposited on the Ni-YSZ anode were examined by a current density-time and current density-voltage dependence measurements in hydrogen (24 h) and biogas (90 h). Composition of the outlet gasses was in situ analysed by the FTIR-based unit.
It has been found out that Ce0.9Sm0.1O2-δ and Ce0.8Pr0.05Sm0.15O2-δ catalytic layers show the highest stability over time and thus are the most attractive candidates as catalytic materials in comparison with other investigated lanthanide-doped ceria enhancing direct internal reforming of biogas in SOFCs.
The XRD SEM and EDX methods were used to investigate the structural properties and the composition of fabricated materials. Furthermore the electrical properties of SOFCs with catalytic layers deposited on the Ni-YSZ anode were examined by a current density-time and current density-voltage dependence measurements in hydrogen (24 h) and biogas (90 h). Composition of the outlet gasses was in situ analysed by the FTIR-based unit.
It has been found out that Ce0.9Sm0.1O2-δ and Ce0.8Pr0.05Sm0.15O2-δ catalytic layers show the highest stability over time and thus are the most attractive candidates as catalytic materials in comparison with other investigated lanthanide-doped ceria enhancing direct internal reforming of biogas in SOFCs.
Prospects for the Use of Hydrogen in the Armed Forces
Oct 2021
Publication
The energy security landscape that we envisage in 2050 will be different from that of today. Meeting the future energy needs of the armed forces will be a key challenge not least for military security. The World Energy Council’s World Energy Scenarios forecast that the world’s population will rise to 10 billion by 2050 which will also necessitate an increase in the size of the armed forces. In this context energy extraction distribution and storage become essential to stabilizing the imbalance between production and demand. Among the available solutions Power to Hydrogen (P2H) is one of the most appealing options. However despite the potential many obstacles currently hinder the development of the P2H market. This article aims to identify and analyse existing barriers to the introduction of P2H technologies that use hydrogen. The holistic approach used which was based on a literature survey identified obstacles and possible strategies for overcoming them. The research conducted presents an original research contribution at the level of hydrogen strategies considered in leading countries around the world. The research findings identified unresolved regulatory issues and sources of uncertainty in the armed forces. There is a lack of knowledge in the armed forces of some countries about the process of producing hydrogen energy and its benefits which raises concerns about the consistency of its exploitation. Negative attitudes towards hydrogen fuel energy can be a significant barrier to its deployment in the armed forces. Possible approaches and solutions have also been proposed to eliminate obstacles and to support decision makers in defining and implementing a strategy for hydrogen as a clean energy carrier. There are decisive and unresolved obstacles to its deployment not only in the armed forces
Studies of the Impact of Hydrogen on the Stability of Gaseous Mixtures of THT
Dec 2020
Publication
One of the most important requirements concerning the quality of natural gases guaranteeing their safe use involves providing the proper level of their odorization. This allows for the detection of uncontrolled leakages of gases from gas networks installations and devices. The concentration of an odorant should be adjusted in such a manner that the gas odor in a mixture with air would be noticeable by users (gas receivers). A permanent odor of gas is guaranteed by the stability of the odorant molecule and its resistance to changes in the composition of odorized gases. The article presents the results of experimental research on the impact of a hydrogen additive on the stability of tetrahydrothiophene (THT) mixtures in methane and in natural gas with a hydrogen additive. The objective of the work was to determine the readiness of measurement infrastructures routinely used in monitoring the process of odorizing natural gas for potential changes in its composition. One of the elements of this infrastructure includes the reference mixtures of THT used to verify the correctness of the readings of measurement devices. The performed experimental tests address possible changes in the composition of gases supplied via a distribution network resulting from the introduction of hydrogen. The lack of interaction between hydrogen and THT has been verified indirectly by assessing the stability of its mixtures with methane and natural gas containing hydrogen. The results of the presented tests permitted the identification of potential hazards for the safe use of gas from a distribution network resulting from changes in its composition caused by the addition of hydrogen.
Evaluation of Corrosion, Mechanical Properties and Hydrogen Embrittlement of Casing Pipe Steels with Different Microstructure
Dec 2021
Publication
In the research the corrosion and mechanical properties as well as susceptibility to hydrogen embrittlement of two casing pipe steels were investigated in order to assess their serviceability in corrosive and hydrogenating environments under operation in oil and gas wells. Two carbon steels with different microstructures were tested: the medium carbon steel (MCS) with bainitic microstructure and the medium-high carbon steel (MHCS) with ferrite–pearlite microstructure. The results showed that the corrosion resistance of the MHCS in CO2-containing acid chloride solution simulating formation water was significantly lower than that of the MCS which was associated with microstructure features. The higher strength MCS with the dispersed microstructure was less susceptible to hydrogen embrittlement under preliminary electrolytic hydrogenation than the lower strength MHCS with the coarse-grained microstructure. To estimate the embrittlement of steels the method of the FEM load simulation of the specimens with cracks was used. The constitutive relations of the true stress–strain of the tested steels were defined. The stress and strain dependences in the crack tip were calculated. It was found that the MHCS was characterized by the lower plasticity on the stage of the neck formation of the specimen and the lower fracture toughness than the other one. The obtained results demonstrating the limitations of the usage of casing pipes made of the MHCS with the coarse-grained ferrite/pearlite microstructure in corrosive and hydrogenating environments were discussed.
Varying Load Distribution Impacts on the Operation of a Hydrogen Generator Plant
Oct 2021
Publication
This study advances several methods to evaluate the operation of a hydrogen generator plant. The model developed helps customize plants that contain multiple generators of varying powers using a decision module which determines the most efficient plant load distribution. Evaluation indices to assess individual devices within the plant are proposed and system flexibility maximizes the amount of renewable energy stored. Three case studies examined the variable load distribution of an electrolysis system connected to a 40 MW wind farm for energy storage purposes and incorporated a “night-valley” operational strategy. These methods facilitate the selection of the proper plant configuration and provide estimates for individual device effectiveness within the system.
Hydrogen Embrittlement and Oxide Layer Effect in the Cathodically Charged Zircaloy-2
Apr 2020
Publication
Poland The present paper is aimed at determining the less investigated effects of hydrogen uptake on the microstructure and the mechanical behavior of the oxidized Zircaloy-2 alloy. The specimens were oxidized and charged with hydrogen. The different oxidation temperatures and cathodic current densities were applied. The scanning electron microscopy X-ray electron diffraction spectroscopy hydrogen absorption assessment tensile and nanoindentation tests were performed. At low oxidation temperatures an appearance of numerous hydrides and cracks and a slight change of mechanical properties were noticed. At high-temperature oxidation the oxide layer prevented the hydrogen deterioration of the alloy. For nonoxidized samples charged at different current density nanoindentation tests showed that both hardness and Young’s modulus revealed the minims at specific current value and the stepwise decrease in hardness during hydrogen desorption. The obtained results are explained by the barrier effect of the oxide layer against hydrogen uptake softening due to the interaction of hydrogen and dislocations nucleated by indentation test and hardening caused by the decomposition of hydrides. The last phenomena may appear together and result in hydrogen embrittlement in forms of simultaneous hydrogen-enhanced localized plasticity and delayed hydride cracking.
Assessment of Operational Degradation of Pipeline Steels
Jun 2021
Publication
This paper summarizes a series of the authors’ research in the field of assessing the operational degradation of oil and gas transit pipeline steels. Both mechanical and electrochemical properties of steels are deteriorated after operation as is their resistance to environmentally-assisted cracking. The characteristics of resistance to brittle fracture and stress corrosion cracking decrease most intensively which is associated with a development of in-bulk dissipated microdamages of the material. The most sensitive indicators of changes in the material’s state caused by degradation are impact toughness and fracture toughness by the J-integral method. The degradation degree of pipeline steels can also be evaluated nondestructively based on in-service changes in their polarization resistance and potential of the fracture surface. Attention is drawn to hydrogenation of a pipe wall from inside as a result of the electrochemical interaction of pipe metal with condensed moisture which facilitates operational degradation of steel due to the combined action of operating stresses and hydrogen. The development of microdamages along steel texture was evidenced metallographically as a trend to the selective etching of boundaries between adjacent bands of ferrite and pearlite and fractographically by revealing brittle fracture elements on the fracture surfaces namely delamination and cleavage indicating the sites of cohesion weakening between ferrite and pearlite bands. The state of the X52 steel in its initial state and after use for 30 years was assessed based on the numerical simulation method.
Effect of Hydrogen Addition on the Energetic and Ecologic Parameters of an SI Engine Fueled by Biogas
Jan 2021
Publication
The global policy solution seeks to reduce the usage of fossil fuels and greenhouse gas (GHG) emissions and biogas (BG) represents a solutions to these problems. The use of biogas could help cope with increased amounts of waste and reduce usage of fossil fuels. Biogas could be used in compressed natural gas (CNG) engines but the engine electronic control unit (ECU) needs to be modified. In this research a spark ignition (SI) engine was tested for mixtures of biogas and hydrogen (volumetric hydrogen concentration of 0 14 24 33 and 43%). In all experiments two cases of spark timing (ST) were used: the first for an optimal mixture and the second for CNG. The results show that hydrogen increases combustion quality and reduces incomplete combustion products. Because of BG’s lower burning speed the advanced ST increased brake thermal efficiency (BTE) by 4.3% when the engine was running on biogas. Adding 14 vol% of hydrogen (H2 ) increases the burning speed of the mixture and enhances BTE by 2.6% at spark timing optimal for CNG (CNG ST) and 0.6% at the optimal mixture ST (mixture ST). Analyses of the rate of heat release (ROHR) temperature and pressure increase in the cylinder were carried out using utility BURN in AVL BOOST software.
Validation of Selected Optical Methods for Assessing Polyethylene (PE) Liners Used in High Pressure Vessels for Hydrogen Storage
Jun 2021
Publication
A polyethylene (PE) liner is the basic element in high-pressure type 4 composite vessels designed for hydrogen or compressed natural gas (CNG) storage systems. Liner defects may result in the elimination of the whole vessel from use which is very expensive both at the manufacturing and exploitation stage. The goal is therefore the development of efficient non-destructive testing (NDT) methods to test a liner immediately after its manufacturing before applying a composite reinforcement. It should be noted that the current regulations codes and standards (RC&S) do not specify liner testing methods after manufacturing. It was considered especially important to find a way of locating and assessing the size of air bubbles and inclusions and the field of deformations in liner walls. It was also expected that these methods would be easily applicable to mass-produced liners. The paper proposes the use of three optical methods namely visual inspection digital image correlation (DIC) and optical fiber sensing based on Bragg gratings (FBG). Deformation measurements are validated with finite element analysis (FEA). The tested object was a prototype of a hydrogen liner for high-pressure storage (700 bar). The mentioned optical methods were used to identify defects and measure deformations.
A Hybrid Energy Storage System Using Compressed Air and Hydrogen as the Energy Carrier
Feb 2020
Publication
In this paper an innovative concept of an energy storage system that combines the idea of energy storage through the use of compressed air and the idea of energy storage through the use of hydrogen (with its further conversion to synthetic natural gas) has been proposed. The thermal integration of two sub-systems allows for efficient storage of large amounts of energy based on the use of pressure tanks with limited volumes. A thermodynamic assessment of the integrated hybrid system was carried out. For the assumed operation parameters an energy storage efficiency value of 38.15% was obtained which means the technology is competitive with intensively developed pure hydrogen energy storage technologies. The results obtained for the hybrid system were compared to the results obtained for three reference systems each of which uses hydrogen generators. The first is a typical Power-to-H2-to-Power system which integrates hydrogen generators with a fuel cell system. The other two additionally use a compressed air energy storage installation. In the first case the compressed air energy storage system consists of a diabatic system. In the second case the compressed air energy storage system is adiabatic. The article has discussed the disadvantages and advantages of all the analyzed systems.
Magnesium Gasar as a Potential Monolithic Hydrogen Absorbent
Feb 2021
Publication
The study focuses on the aspect of using the structure of gasars i.e. materials with directed open porosity as a potential hydrogen storage. The structure of the tested gasar is composed of a large number of thin open tubular pores running through the entire longitudinal section of the sample. This allows hydrogen to easily penetrate into the entire sample volume. The analysis of pore distribution showed that the longest diffusion path needed for full penetration of the metal structure with hydrogen is about L = 50–70 μm regardless of the external dimensions of the sample. Attempts to hydrogenate the magnesium gasar structure have shown its ability to accumulate hydrogen at a level of 1 wt%. The obtained results were compared with the best result was obtained for the ZK60 alloy after equal channel angular pressing (ECAP) and crushed to a powder form. The result obtained exceeded 4 wt% of hydrogen accumulated in the metal structure at theoretical 6.9 wt% maximum capacity. A model analysis of the theoretic absorption capacity of pure magnesium was also carried out based on the concentration of vacancies in the metal structure. The theoretical results obtained correlate well with experimental data.
The Energy Approach to the Evaluation of Hydrogen Effect on the Damage Accumulation
Aug 2019
Publication
The energy approach for determining the durability of structural elements at high temperature creep and hydrogen activity was proposed. It has been shown that the approach significantly simplifies research compared with the known ones. Approbation of the approach was carried out on the example of determining the indicators of durability of the Bridgman sample under conditions of creep and different levels of hydrogenation of the metal. It was shown that with an increase of hydrogen concentration in the metal from 2 to 10 ppm the durability of the test sample decreased from 22 to 58%.
Tests of the Vehicle’s Powertrain with Hydrogen Fuel Cells at a Low Temperature
Sep 2019
Publication
The article discusses issues related to the operation of fuel cells stack fed with hydrogen at low temperature. The test object was a Toyota Mirai passenger car equipped with this type of powertrain. Tests were carried out in a thermoclimatic chamber at the Cracow University of Technology. They had an initial character and their aim was to evaluate the work of individual subassemblies of the propulsion system including the hydrogen supply system in terms of operational safety.
Impact of Depth on Underground Hydrogen Storage Operations in Deep Aquifers
Mar 2024
Publication
Underground hydrogen storage in geological structures is considered appropriate for storing large amounts of hydrogen. Using the geological Konary structure in the deep saline aquifers an analysis of the influence of depth on hydrogen storage was carried out. Hydrogen injection and withdrawal modeling was performed using TOUGH2 software assuming different structure depths. Changes in the relevant parameters for the operation of an underground hydrogen storage facility including the amount of H2 injected in the initial filling period cushion gas working gas and average amount of extracted water are presented. The results showed that increasing the depth to approximately 1500 m positively affects hydrogen storage (flow rate of injected hydrogen total capacity and working gas). Below this depth the trend was reversed. The cushion gas-to-working gas ratio did not significantly change with increasing depth. Its magnitude depends on the length of the initial hydrogen filling period. An increase in the depth of hydrogen storage is associated with a greater amount of extracted water. Increasing the duration of the initial hydrogen filling period will reduce the water production but increase the cushion gas volume.
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