Spain
New Combustion Modelling Approach for Methane-Hydrogen Fueled Engines Using Machine Learning and Engine Virtualization
Oct 2021
Publication
The achievement of a carbon-free emissions economy is one of the main goals to reduce climate change and its negative effects. Scientists and technological improvements have followed this trend improving efficiency and reducing carbon and other compounds that foment climate change. Since the main contributor of these emissions is transportation detaching this sector from fossil fuels is a necessary step towards an environmentally friendly future. Therefore an evaluation of alternative fuels will be needed to find a suitable replacement for traditional fossil-based fuels. In this scenario hydrogen appears as a possible solution. However the existence of the drawbacks associated with the application of H2 -ICE redirects the solution to dual-fuel strategies which consist of mixing different fuels to reduce negative aspects of their separate use while enhancing the benefits. In this work a new combustion modelling approach based on machine learning (ML) modeling is proposed for predicting the burning rate of different mixtures of methane (CH4 ) and hydrogen (H2). Laminar flame speed calculations have been performed to train the ML model finding a faster way to obtain good results in comparison with actual models applied to SI engines in the virtual engine model framework.
Hydrogen-assisted Fatigue Crack Growth: Pre-charging vs In-situ Testing in Gaseous Environments
Mar 2023
Publication
We investigate the implications of conducting hydrogen-assisted fatigue crack growth experiments in a hydrogen gas environment (in-situ hydrogen charging) or in air (following exposure to hydrogen gas). The study is conducted on welded 42CrMo4 steel a primary candidate for the future hydrogen transport infrastructure allowing us to additionally gain insight into the differences in behavior between the base steel and the coarse grain heat affected zone. The results reveal significant differences between the two testing approaches and the two weld regions. The differences are particularly remarkable for the comparison of testing methodologies with fatigue crack growth rates being more than one order of magnitude higher over relevant loading regimes when the samples are tested in a hydrogen-containing environment relative to the pre-charged samples. Aided by finite element modelling and microscopy analysis these differences are discussed and rationalized. Independent of the testing approach the heat affected zone showed a higher susceptibility to hydrogen embrittlement. Similar microstructural behavior is observed for both testing approaches with the base metal exhibiting martensite lath decohesion while the heat affected zone experienced both martensite lath decohesion and intergranular fracture.
Notch-induced Anisotropic Fracture of Cold Drawn Pearlitic Steels and the Associated Crack Path Deflection and Mixed-mode Stress State: A Tribute to Masaccio
Jul 2018
Publication
This paper deals with notch-induced anisotropic fracture behavior of progressively cold drawn pearlitic steels on the basis of their microstructural evolution during manufacturing by multi-step cold drawing that produces slenderizing and orientation of the pearlitic colonies together with densification and orientation of the Fe/Fe3C lamellae reviewing previous research by the author. Results of fracture test using notched specimens of cold drawn pearlitic steels with different degrees of cold drawing (distinct levels of strain hardening) in air and hydrogen environment shows: (i) the key impact of the colonies and lamellae alignment and orientation on notch-induced fracture producing anisotropic fracture behavior with its related crack path deflection (or fracture path deviation); (ii) the necessity of both stress triaxiality (constraint) and microstructural orientation (colonies/lamellae) alignment to produce fracture path deflection; (iii) hydrogen presence (the circumstance) promotes crack path deviation in addition to the inherent microstructural anisotropy created by cold drawing; (iv) the anisotropic fracture path with a stepped profile in cold drawn pearlitic steel consisting of deflections and deviations from the initial transverse fracture path in mode I resembles Masaccio’s Tribute Money painting with its mountains at the background so that the present paper can be considered as a Tribute to Masaccio.
Analysis of the Environmental Degradation Effects on the Cables of “La Arena” Bridge (Spain)
Sep 2017
Publication
After nearly 25 years of service some of the wires of the tendons of “La Arena” bridge (Spain) started to exhibit the effects of environmental degradation processes. “La Arena” is cable-stayed bridge with 6 towers and a reference span between towers of about 100 meters. After a maintenance inspection of the bridge evidences of corrosion were detected in some of the galvanized wires of the cables. A more in-deep analysis of these wires revealed that many of them exhibited loss of section due to the corrosion process. In order to clarify the causes of this degradation event and to suggest some remedial actions an experimental program was designed. This program consisted of tensile and fatigue tests on some strand samples of the bridge together with a fractographic analysis of the fracture surfaces of the wires its galvanized layer thickness and some hydrogen measurements (hydrogen embrittlement could be another effect of the environmental degradation process).Once the type and extension of the flaws in the wires was characterized a structural integrity assessment of the strands was performed with the aim of quantifying the margins until failure and establishing some maintenance recommendations.
Resilience-oriented Schedule of Microgrids with Hybrid Energy Storage System using Model Predictive Control
Nov 2021
Publication
Microgrids can be regarded as a promising solution by which to increase the resilience of power systems in an energy paradigm based on renewable generation. Their main advantage is their ability to work as islanded systems under power grid outage conditions. Microgrids are usually integrated into electrical markets whose schedules are carried out according to economic aspects while resilience criteria are ignored. This paper shows the development of a resilience-oriented optimization for microgrids with hybrid Energy Storage System (ESS) which is validated via numerical simulations. A hybrid ESS composed of hydrogen and batteries is therefore considered with the objective of improving the autonomy of the microgrid while achieving a rapid transition response. The control problem is formulated using Stochastic Model Predictive Control (SMPC) techniques in order to take into account possible transitions between grid-connected and islanded modes at all the sample instants of the schedule horizon (SH). The control problem is developed by considering a healthy operation of the hybrid ESS thus avoiding degradation issues. The plant is modeled using the Mixed Logic Dynamic (MLD) framework owing to the presence of logic and dynamic control variables.
A Unified European Hydrogen Infrastructure Planning to Support the Rapid Scale-up of Hydrogen Production
Jun 2024
Publication
Hydrogen will become a key player in transitioning toward a net-zero energy system. However a clear pathway toward a unified European hydrogen infrastructure to support the rapid scale-up of hydrogen production is still under discussion. This study explores plausible pathways using a fully sector-coupled energy system model. Here we assess the emergence of hydrogen infrastructure build-outs connecting neighboring European nations through hydrogen import and domestic production centers with Western and Central European demands via four distinct hydrogen corridors. We identify a potential lock-in effect of blue hydrogen in the medium term highlighting the risk of longterm dependence on methane. In contrast we show that a self-sufficient Europe relying on domestic green hydrogen by 2050 would increase yearly expenses by around 3% and require 518 gigawatts of electrolysis capacity. This study emphasizes the importance of rapidly scaling up electrolysis capacity building hydrogen networks and storage facilities deploying renewable electricity generation and ensuring coherent coordination across European nations.
Optimal Dispatch Model for PV-electrolysis Plants in Self-consumption Regime to Produce Green Hydrogen: A Spanish Case Study
May 2022
Publication
The production of green hydrogen from renewable energy by means of water electrolysis is a promising approach to support energy sector decarbonization. This paper presents a techno-economic model of plants with PV sources connected to electrolysis in self-consumption regime that considers the dynamics of electrolysis systems. The model calculates the optimal hourly dispatch of the electrolysis system including the operational states (production standby and idle) the load factor in production and the energy imports and exports to the electricity grid. Results indicate that the model is a useful decision support tool to operate electrolysis plants connected to PV plants in self-consumption regimes with the target of reducing hydrogen production costs.
Integration of Hydrogen and Synthetic Natural Gas within Legacy Power Generation Facilities
Jun 2022
Publication
Whilst various new technologies for power generation are continuously being evaluated the owners of almost-new facilities such as combined-cycle gas turbine (CCGT) plants remain motivated to adapt these to new circumstances and avoid the balance-sheet financial impairments of underutilization. Not only are the owners reluctant to decommission the legacy CCGT assets but system operators value the inertia and flexibilities they contribute to a system becoming predominated with renewable generation. This analysis therefore focuses on the reinvestment cases for adapting CCGT to hydrogen (H2 ) synthetic natural gas (SNG) and/or retrofitted carbon capture and utilization systems (CCUS). Although H2 either by itself or as part of SNG has been evaluated attractively for longer-term electricity storage the business case for how it can be part of a hybrid legacy CCGT system has not been analyzed in a market context. This work compares the power to synthetic natural gas to power (PSNGP) adaptation with the simpler and less expensive power to hydrogen to power (P2HP) adaptation. Both the P2HP and PSNGP configurations are effective in terms of decarbonizations. The best results of the feasibility analysis for a UK application with low CCGT load factors (around 31%) were obtained for 100% H2 (P2HP) in the lower range of wholesale electricity prices (less than 178 GBP/MWh) but in the higher range of prices it would be preferable to use the PSNGP configuration with a low proportion of SNG (25%). If the CCGT load factor increased to 55% (the medium scenario) the breakeven profitability point between P2HP and PSNGP decreased to a market price of 145 GBP/MWh. Alternatively with the higher load factors (above 77%) satisfactory results were obtained for PSNGP using 50% SNG if with market prices above 185 GBP/MWh.
Green Hydrogen Storage in an Underground Cavern: A Case Study in Salt Diapir of Spain
Jun 2022
Publication
The Poza de la Sal diapir is a closed circular depression with Cretaceous Mesozoic materials formed by gypsum Keuper clays and a large extension of salt in the center with intercalations of ophite. The low seismic activity of the area the reduced permeability and porosity of the salt caverns and the proximity to the Páramo de Poza wind park make it a suitable place for the construction of a facility for underground storage of green hydrogen obtained from surplus wind power. The design of a cavern for hydrogen storage at a depth of 1000 m takes into account the differences in stresses temperatures and confining pressures involved in the salt deformation process. During the 8 months of the injection phase 23.0 GWh can be stored in the form of hydrogen obtained from the wind energy surplus to be used later in the extraction phase. The injection and extraction ratio must be developed under the conditions of geomechanical safety of the cavity so as to minimize the risks to the environment and people by conditioning the gas pressure inside the cavity to remain within a given range.
Hydrogen Assisted Cracking in Pearlitic Steel Rods: The Role of Residual Stresses Generated by Fatigue Precracking
May 2017
Publication
Stress corrosion cracking (SCC) of metals is an issue of major concern in engineering since this phenomenon causes many catastrophic failures of structural components in aggressive environments. SCC is even more harmful under cathodic conditions promoting the phenomenon known as hydrogen assisted cracking (HAC) hydrogen assisted fracture (HAF) or hydrogen embrittlement (HE). A common way to assess the susceptibility of a given material to HAC HAF or HE is to subject a cracked rod to a constant extension rate tension (CERT) test until it fractures in this harsh environment. This paper analyzes the influence of a residual stress field generated by fatigue precracking on the sample’s posterior susceptibility to HAC. To achieve this goal numerical simulations were carried out of hydrogen diffusion assisted by the stress field. Firstly a mechanical simulation of the fatigue precracking was developed for revealing the residual stress field after diverse cyclic loading scenarios and posterior stress field evolution during CERT loading. Afterwards a simulation of hydrogen diffusion assisted by stress was carried out considering the residual stresses after fatigue and the superposed rising stresses caused by CERT loading. Results reveal the key role of the residual stress field after fatigue precracking in the HAC phenomena in cracked steel rods as well as the beneficial effect of compressive residual stress.
Analysis of Environmentally Assisted Cracking Processes in Notched Steels Using the Point Method
Sep 2019
Publication
This paper proposes the use of the Point Method (PM) to analyse Environmentally Assisted Cracking (EAC) processes in steels containing U-shaped notches. The PM a methodology included within the Theory of Critical Distances (TCD) has been extensively validated by many authors for the analysis of fracture and fatigue phenomena of different types of materials containing notches. However it has never been applied to other critical or subcritical cracking processes such as EAC or creep crack propagation.<br/>This work provides a PM-based analysis of EAC emanating from notches which is validated by testing CT notched specimens of X80 and S420 steels subjected to aggressive environments under hydrogen embrittlement conditions.<br/>The results reveal that the PM accurately predicts the crack propagation onset condition as well as the evolution of the material’s apparent EAC resistance.
A Novel Self-Assembly Strategy for the Fabrication of Nano-Hybrid Satellite Materials with Plasmonically Enhanced Catalytic Activity
Jun 2021
Publication
The generation of hydrogen from water using light is currently one of the most promising alternative energy sources for humankind but faces significant barriers for large-scale applications due to the low efficiency of existing photo-catalysts. In this work we propose a new route to fabricate nano-hybrid materials able to deliver enhanced photo-catalytic hydrogen evolution combining within the same nanostructure a plasmonic antenna nanoparticle and semiconductor quantum dots (QDs). For each stage of our fabrication process we probed the chemical composition of the materials with nanometric spatial resolution allowing us to demonstrate that the final product is composed of a silver nanoparticle (AgNP) plasmonic core surrounded by satellite Pt decorated CdS QDs (CdS@Pt) separated by a spacer layer of SiO2 with well-controlled thickness. This new type of photoactive nanomaterial is capable of generating hydrogen when irradiated with visible light displaying efficiencies 300% higher than the constituting photo-active components. This work may open new avenues for the development of cleaner and more efficient energy sources based on photo-activated hydrogen generation.
Influence of Microstructural Anisotropy on the Hydrogen-assisted Fracture of Notched Samples of Progressively Drawn Pearlitic Steel
Dec 2020
Publication
In this study fracture surfaces of notched specimens of pearlitic steels subjected to constant extension rate tests (CERTs) are analyzed in an environment causing hydrogen assisted fracture. In order to obtain general results both different notched geometries (to generate quite distinct stress triaxiality distributions in the vicinity of the notch tip) and diverse loading rates were used. The fracture surfaces were classified in relation to four micromechanical models of hydrogen-assisted micro-damage. To this end fractographic analysis in each fracture surface was carried out with a scanning electron microscopy. Generated results increase the number of micromechanical models found in the scientific literature.
Evaluation of Strength and Fracture Toughness of Ferritic High Strength Steels Under Hydrogen Environments
Sep 2017
Publication
The susceptibility of high strength ferritic steels to hydrogen-assisted fracture in hydrogen gas is usually evaluated by mechanical testing in high-pressure hydrogen gas or testing in air after pre-charging the specimens with hydrogen. We have used this second methodology conventionally known as internal hydrogen. Samples were pre-charged in an autoclave under 195 bar of pure hydrogen at 450ºC for 21 hours.<br/>Different chromium-molybdenum steels submitted to diverse quenching and tempering heat treatments were employed. Diverse specimens were also used: small cylindrical samples to measure hydrogen contents and the kinetics of hydrogen egression at room temperature tensile specimens notched tensile specimens with a sharp notch and also compact fracture toughness specimens. Fractographic examination in SEM was finally performed in order to know the way hydrogen modify fracture micromechanisms.<br/>The presence of hydrogen barely affects the conventional tensile properties of the steels but it clearly alters their notched tensile strength and fracture toughness. This is due to the strong effect that stress triaxiality (dependent also on the steel yield strength) has on the accumulation of hydrogen on the notch/crack front region being the displacement rate used in the test another important variable to be controlled due to its influence on hydrogen diffusion to the embrittled process zone. Moreover the modification of fracture micromechanisms was finally determined being ductile (initiation growth and coalescence of microvoids) in the absence of hydrogen and brittle and intergranular under the material conditions of maximum embrittlement.
Techno-Economics Optimization of H2 and CO2 Compression for Renewable Energy Storage and Power-to-Gas Applications
Nov 2021
Publication
The decarbonization of the industrial sector is imperative to achieve a sustainable future. Carbon capture and storage technologies are the leading options but lately the use of CO2 is also being considered as a very attractive alternative that approaches a circular economy. In this regard power to gas is a promising option to take advantage of renewable H2 by converting it together with the captured CO2 into renewable gases in particular renewable methane. As renewable energy production or the mismatch between renewable production and consumption is not constant it is essential to store renewable H2 or CO2 to properly run a methanation installation and produce renewable gas. This work analyses and optimizes the system layout and storage pressure and presents an annual cost (including CAPEX and OPEX) minimization. Results show the proper compression stages need to achieve the storage pressure that minimizes the system cost. This pressure is just below the supercritical pressure for CO2 and at lower pressures for H2 around 67 bar. This last quantity is in agreement with the usual pressures to store and distribute natural gas. Moreover the H2 storage costs are higher than that of CO2 even with lower mass quantities; this is due to the lower H2 density compared with CO2 . Finally it is concluded that the compressor costs are the most relevant costs for CO2 compression but the storage tank costs are the most relevant in the case of H2.
Absence of Spillover of Hydrogen Adsorbed on Small Palladium Clusters Anchored to Graphene Vacancies
May 2021
Publication
Experimental evidence exists for the enhancement of the hydrogen storage capacity of porous carbons when these materials are doped with metal nanoparticles. One of the most studied dopants is palladium. Dissociation of the hydrogen molecules and spillover of the H atoms towards the carbon substrate has been advocated as the reason for the enhancement of the storage capacity. We have investigated this mechanism by performing ab initio density functional molecular dynamics (AIMD) simulations of the deposition of molecular hydrogen on Pd6 clusters anchored on graphene vacancies. The clusters are initially near-saturated with atomic and molecular hydrogen. This condition would facilitate the occurrence of spillover since our energy calculations based on density functional theory indicate that migration of preadsorbed H atoms towards the graphene substrate becomes exothermic on Pd clusters with high hydrogen coverages. However AIMD simulations show that the H atoms prefer to intercalate and absorb within the Pd cluster rather than migrate to the carbon substrate. These results reveal that high activation barriers exist preventing the spillover of hydrogen from the anchored Pd clusters to the carbon substrate.
Spin Pinning Effect to Reconstructed Oxyhydroxide Layer on Ferromagnetic Oxides for Enhanced Water Oxidation
Jun 2021
Publication
Producing hydrogen by water electrolysis suffers from the kinetic barriers in the oxygen evolution reaction (OER) that limits the overall efficiency. With spin-dependent kinetics in OER to manipulate the spin ordering of ferromagnetic OER catalysts (e.g. by magnetization) can reduce the kinetic barrier. However most active OER catalysts are not ferromagnetic which makes the spin manipulation challenging. In this work we report a strategy with spin pinning effect to make the spins in paramagnetic oxyhydroxides more aligned for higher intrinsic OER activity. The spin pinning effect is established in oxideFM/oxyhydroxide interface which is realized by a controlled surface reconstruction of ferromagnetic oxides. Under spin pinning simple magnetization further increases the spin alignment and thus the OER activity which validates the spin effect in rate-limiting OER step. The spin polarization in OER highly relies on oxyl radicals (O∙) created by 1st dehydrogenation to reduce the barrier for subsequent O-O coupling.
Optimal Energy Management System Using Biogeography Based Optimization for Grid-connected MVDC Microgrid with Photovoltaic, Hydrogen System, Electric Vehicles and Z-source Converters
Oct 2021
Publication
Currently the technology associated with charging stations for electric vehicles (EV) needs to be studied and improved to further encourage its implementation. This paper presents a new energy management system (EMS) based on a Biogeography-Based Optimization (BBO) algorithm for a hybrid EV charging station with a configuration that integrates Z-source converters (ZSC) into medium voltage direct current (MVDC) grids. The EMS uses the evolutionary BBO algorithm to optimize a fitness function defining the equivalent hydrogen consumption/generation. The charging station consists of a photovoltaic (PV) system a local grid connection two fast charging units and two energy storage systems (ESS) a battery energy storage (BES) and a complete hydrogen system with fuel cell (FC) electrolyzer (LZ) and hydrogen tank. Through the use of the BBO algorithm the EMS manages the energy flow among the components to keep the power balance in the system reducing the equivalent hydrogen consumption and optimizing the equivalent hydrogen generation. The EMS and the configuration of the charging station based on ZSCs are the main contributions of the paper. The behaviour of the EMS is demonstrated with three EV connected to the charging station under different conditions of sun irradiance. In addition the proposed EMS is compared with a simpler EMS for the optimal management of ESS in hybrid configurations. The simulation results show that the proposed EMS achieves a notable improvement in the equivalent hydrogen consumption/generation with respect to the simpler EMS. Thanks to the proposed configuration the output voltage of the components can be upgraded to MVDC while reducing the number of power converters compared with other configurations without ZSC.
Flammability Reduction in a Pressurised Water Electrolyser Based on a Thin Polymer Electrolyte Membrane through a Pt-alloy Catalytic Approach
Jan 2019
Publication
Various Pt-based materials (unsupported Pt PtRu PtCo) were investigated as catalysts for recombining hydrogen and oxygen back into water. The recombination performance correlated well with the surface Pt metallic state. Alloying cobalt to platinum was observed to produce an electron transfer favouring the occurrence of a large fraction of the Pt metallic state on the catalyst surface. Unsupported PtCo showed both excellent recombination performance and dynamic behaviour. In a packed bed catalytic reactor when hydrogen was fed at 4% vol. in the oxygen stream (flammability limit) 99.5% of the total H2 content was immediately converted to water in the presence of PtCo thus avoiding safety issues. The PtCo catalyst was thus integrated in the anode of the membrane-electrode assembly of a polymer electrolyte membrane electrolysis cell. This catalyst showed good capability to reduce the concentration of hydrogen in the oxygen stream under differential pressure operation (1–20 bar) in the presence of a thin (90 μm) Aquivion® membrane. The modified system showed lower hydrogen concentration in the oxygen flow than electrolysis cells based on state-of-the-art thick polymer electrolyte membranes and allowed to expand the minimum current density load down to 0.15 A cm−2 . This was mainly due to the electrochemical oxidation of permeated H2 to protons that were transported back to the cathode. The electrolysis cell equipped with a dual layer PtCo/IrRuOx oxidation catalyst achieved a high operating current density (3 A cm−2 ) as requested to decrease the system capital costs under high efficiency conditions (about 77% efficiency at 55 °C and 20 bar). Moreover the electrolysis system showed reduced probability to reach the flammability limit under both high differential pressure (20 bar) and partial load operation (5%) as needed to properly address grid-balancing service
Light-Driven Hydrogen Evolution Assisted by Covalent Organic Frameworks
Jun 2021
Publication
Covalent organic frameworks (COFs) are crystalline porous organic polymers built from covalent organic blocks that can be photochemically active when incorporating organic semiconducting units such as triazine rings or diacetylene bridges. The bandgap charge separation capacity porosity wettability and chemical stability of COFs can be tuned by properly choosing their constitutive building blocks by extension of conjugation by adjustment of the size and crystallinity of the pores and by synthetic post-functionalization. This review focuses on the recent uses of COFs as photoactive platforms for the hydrogen evolution reaction (HER) in which usually metal nanoparticles (NPs) or metallic compounds (generally Pt-based) act as co-catalysts. The most promising COF-based photocatalytic HER systems will be discussed and special emphasis will be placed on rationalizing their structure and light-harvesting properties in relation to their catalytic activity and stability under turnover conditions. Finally the aspects that need to be improved in the coming years will be discussed such as the degree of dispersibility in water the global photocatalytic efficiency and the robustness and stability of the hybrid systems putting emphasis on both the COF and the metal co-catalyst.
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