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Organisationseinheit der BAM
- 2 Prozess- und Anlagensicherheit (18)
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Wasserstoff als flexibel einsetzbarer und leicht transportierbarer Energieträger bildet eine Schlüsselkomponente auf dem Weg zu einer klimaneutralen Energiewende. Zur Speicherung von gasförmigem Wasserstoff kommen bei stationären und auch mobilen Anwendungen meist Druckbehälter aus Verbundwerkstoffen zum Einsatz. Dabei ist für den Betrieb der Behälter die Gewährleistung der Sicherheit von großer Relevanz. Structural Health Monitoring (SHM) bietet einen innovativen Ansatz, um sowohl die Sicherheit als auch die Zuverlässigkeit der Druckbehälter zu gewährleisten und kritische Versagensfälle zu vermeiden.
Zur kontinuierlichen Überwachung und Bewertung des Zustands eines Wasserstoffdruckbehälters wird in dem vorliegenden Beitrag eine aktive Methode präsentiert, die auf geführten Ultraschallwellen basiert. Dabei kommt das Pitch-Catch Verfahren zwischen Sender und Empfängern zur Überwachung der strukturellen Integrität zum Einsatz. Auf Grundlage des untersuchten Wellenausbreitungsverhaltens im Druckbehälter sowie der Geometrieeigenschaften wird ein Sensornetzwerk aus piezoelektrischen Flächenwandlern (PZT) zur Abdeckung des zu überwachenden Bereichs entworfen. Ziel ist es mit Hilfe eines Optimierungsalgorithmus eine größtmögliche Abdeckung bei gleichzeitiger Minimierung der Anzahl der Sensoren zu erreichen. Zudem soll eine gleichmäßige und platzsparende Verteilung im Vordergrund stehen, so dass zukünftig weitere Messmethoden auf dem Druckbehälter angewendet werden können (z. B. durch akustische oder faseroptische Sensoren).
Das für die Anwendung optimierte Sensornetzwerk wird anschließend hinsichtlich der Robustheit bei der Schadenserkennung und -lokalisierung durch Aufbringen von künstlichen Schäden evaluiert. Die Ergebnisse zeigen, dass die künstlichen Schäden am Wasserstoffdruckbehälter nachgewiesen werden können.
Introduction of H2Safety@BAM
(2021)
This contribution for the Open Forum of the 8th HSN Symposium introduces the SensRef activities of the Competence Centre H2Safety@BAM.
In this presentation the drivers for the rise of hydrogen technologies are outlined and main challenges for the market ramp-up are shown. Finally, the activities and capabilities of the competence center H2Safety@BAM are characterized and some of the current projects at BAM adressing the main challenges for hydrogen technologies are presented focussing on the hydrogen transport and infrastructure.
In the DECHEMA Virtual Talks, general aspects of the safety and acceptance of hydrogen technologies were presented. How can trust in new technologies be built when past accidents led to myths and fairy tales? The presentation does away with general prejudices and shows that handling hydrogen is neither more unsafe nor safer than handling other fuel gases. The basis for the safe handling of hydrogen is always a risk analysis.
The Gases Advisory Group is organized regularly by the Prevention Division of the German Employer's Liability Insurance Association for Raw Materials and the Chemical Industry. The event serves as an exchange between science and industry on current safety-related issues concerning oxygen and hydrogen. In this context, BAM presented an overview of its various activities of the competence center H2Safety@BAM, which are reflected in the entire hydrogen value chain. In addition, the plans for the expansion of the test infrastructure at BAM's Technical Safety Test Site were presented. The results of the DELFIN project on the safety of pressurized gas storage tanks, the release tests of liquid hydrogen as well as the underfiring of corresponding cryogenic storage tanks and the plans for the ModuH2Pipe@BAM project were also presented. The presentation concluded with the current recommendations of the Hydrogen Research Network.
Um die Absorption von Wasserstoff und dessen Verhalten in den Werkstoffen beim Einsatz unter Druck-H2 sowie die H- abhängigen Materialeigenschaften zu definieren, entwickelt die BAM mit ihrer langjährigen Erfahrung adäquate Prüfkonzepte, die einsatzrelevante Bedingungen und reale Beanspruchungen (Temperatur, Wasserstoff und mech. Beanspruchung) hierarchisch berücksichtigen. Der Vortrag gibt eine Einführung in das Thema von wasserstoffunterstützen Materialschäden durch die Problematik der Einspeisung von Wasserstoff in bestehende Erdgasnetze. Ferner wird auf die Hochdruck-Infrastruktur (sowie H2-Tankstellen) und die Entwicklung von Prüfkonzepten für die Gasinfrastruktur unter Druckwasserstoffbeaufschlagung eingegangen.
Sliding wear of martensitic steels in hydrogen – X30CrMoN15-1 and 100Cr6 – the role of water traces
(2016)
Initially the primary objective of the project has been the investigation of the influence of gaseous hydrogen on the wear of martensitic steels under heavy tribological stress. As a counter body an Al2O3 ball has been used because the material is inert and hard so that a low amount of wear was expected. If only the gas pressure is responsible for the absorption of hydrogen from the gas to pure α-iron it would require 15·105 MPa (~15 Mbar) to press 1 ppm into the material.
In the test series the Al2O3 balls showed in N2 and H2 atmosphere a higher wear compared to aerial experiments which showed a smaller wear track and a severer wear for the disc. Because of scattering and thereof following investigations it was shown that hydrogen has no noticeable influence but water traces in the gas are manipulating the outcome of the tests distinctly.
The BTU-BAM graduate school Trustworthy Hydrogen was presented at the online meeting of the Lausitz Hydrogen Network entitled "Business meets Science and Research". It is the first graduate school in Germany to focus on the trustworthiness of hydrogen and combines the unique competencies of BAM and BTU to train the next generation of
interdisciplinary hydrogen scientists.
Digital Calibration Certificates: Transforming Efficiency and Safety in Hydrogen Refuelling Station
(2023)
Digital Certificates have emerged as a pivotal element in automation and digitalisation. This presentation highlights the added value of a digitalised metrology, its impact on the workflows on the calibration service providing and receiving side as well as their significance in enhancing the quality infrastructure. An overview of digital calibration certificates (DCC) for temperature sensors, including their structure and role in establishing trust in hydrogen refuelling stations (HRS), will be discussed. Additionally, it explores the impact of DCC on optimising efficiency in the hydrogen refuelling process.
Exploring the paradigm shift brought about by Industry 4.0, where machines possess the ability to autonomously interpret digital certificate data, leads to streamlined safety checks and reduced human intervention. We will discuss how automated verification of machine-readable certificates contributes to maintaining and elevating safety standards over human-readable certificates. Furthermore, we will take a deep dive into the application of DCCs in HRS, showcasing how they enhance operational efficiency, accuracy, and maintenance by enabling real-time monitoring and adjustment of process data.
By exploring the interdependent relationship between digital certificates, machine-readable environments, and HRS optimisation, this presentation will provide valuable insights into harnessing cutting-edge technologies to create a safer, more efficient, and technologically empowered hydrogen refuelling process.
Hydrogen differs from most other flammable gases regarding the safety related properties. Mainly the minimum ignition energy (MIE) is particularly low and the burning velocity is particularly high. Hydrogen mixtures are formed in different hydrogen applications, for example if hydrogen is added to the existing natural gas grid, if synthetic gas (mixture of CO and H2) is produced or in biogas plants. Safety related properties of hydrogen mixtures were determined experimentally and are presented in this presentation. Moreover the accuracy of estimation methods for safety related properties of hydrogen mixtures is evaluated.”
In this lecture, the safety assessment of hydrogen gas storage systems is presented using the example of composite pressure vessels. The main element is a probabilistic approval approach based on five steps. Firstly, the testing and evaluation of properties at the beginning of life are shown. Secondly, methods for artificial aging and the effect on the residual strength are presented. Thirdly, testing against dedicated accidents is introduced. Fourthly, effects on the surveillance of production quality are discussed. Finally, degradation and the end of life are estimated. Background information and examples are given for each step. The assessment presented is a method applicable for many safety-related systems.
In this lecture, the safety assessment of hydrogen gas storage systems is presented using the example of composite pressure vessels. The main element is a probabilistic approval approach based on five steps. Firstly, the testing and evaluation of properties at the beginning of life are shown. Secondly, methods for artificial aging and the effect on the residual strength are presented. Thirdly, testing against dedicated accidents is introduced. Fourthly, effects on the surveillance of production quality are discussed. Finally, degradation and the end of life are estimated. Background information and examples are given for each step. The assessment presented is a method applicable for many safety-related systems.
In this lecture, the safety assessment of hydrogen gas storage systems is presented using the example of composite pressure vessels. The main element is a probabilistic approval approach based on five steps. Firstly, the testing and evaluation of properties at the beginning of life are shown. Secondly, methods for artificial aging and the effect on the residual strength are presented. Thirdly, testing against dedicated accidents is introduced. Fourthly, effects on the surveillance of production quality are discussed. Finally, degradation and the end of life are estimated. Background information and examples are given for each step. The assessment presented is a method applicable for many safety-related systems.
Hydrogen is a central component of the energy transition and the European Green Deal for a climate-neutral Europe. To be able to achieve the targets defined by 2045, the EU and the German government have drafted a framework for action and are making long-term investments in research, development and the rapid implementation of innovative hydrogen technologies.
The conditions for a successful energy transition and the economic use of green hydrogen as a clean energy carrier are Hydrogen readiness and a rapid market ramp-up, as well as the establishment of the necessary value chains in the national and European framework. Reliable quality and safety standards are the prerequisite for ensuring safety of supply and environmental compatibility and for creating trust in these technologies.
BAM has bundled its expertise in the field of hydrogen technologies into a competence center H2Safety@BAM to create confidence in the technology and to support the hydrogen strategies of the German government and the EU. The topic of hydrogen has been current at BAM for more than one hundred years and is also currently the focus of numerous research and cooperation activities. The competence centre H2Safety@BAM and its vision of “We build trust in hydrogen technologies” will be presented with its many safety-related topics, which can be found throughout the entire hydrogen value chain. Two deep dives will present the results on projects dealing with the design-to-cost issue of classical pressurized gas storage containments and the consequences of the release of liquid hydrogen, which will be roughly compared to the release of ammonia.
In this lecture, the safety assessment of hydrogen gas storage systems is presented using the example of composite pressure vessels. The main element is a probabilistic approval approach based on five steps. Firstly, the testing and evaluation of properties at the beginning of life are shown. Secondly, methods for artificial aging and the effect on the residual strength are presented. Thirdly, testing against dedicated accidents is introduced. Fourthly, effects on the surveillance of production quality are discussed. Finally, degradation and the end of life are estimated. Background information and examples are given for each step. The assessment presented is a method applicable for many safety-related systems.
Despite its contribution to tackling climate change by lightweight design, growing CFRP production also results in a global waste generation of 62 kt/a. Accordingly, the energy-intensive production process of carbon fibers (CF) necessitates sustainable recycling solutions.
Herein we will give an overview of current recycling processes, discuss their limitations and present a novel approach for safe treatment of CF unsuitable for material recovery . Our project CF Pyro examines feedstock recycling in pyrometallurgical processes, focusing on reactivity of CF, process stability and prevention of hazardous WHO fiber release. Besides fundamental experimental breakthroughs, their broader impact on circular economy will be presented.
Increasing environmental problems with conventional energy technology are stimulating the demand for alternative energy solutions. With air quality reaching catastrophic levels in large cities worldwide, Fuel Cell Electric Vehicles offer the ideal combination of clean power with the amenities of electric drives. Hydrogen use on vehicles, nevertheless, also raises some issues about safe handling. As fuel cells and hydrogen applications, including vehicles, approach technological maturity, developing their business cases becomes crucial in introducing them to the consumer markets.
The Joint European Summer School JESS 2021 addresses these issues by offering high quality graduate level courses on selected topics of vehicle technology, innovation & business development, safe handling of hydrogen, and modelling. This series of summer schools has been ongoing since 2004 and targets an audience of university students (MSc and PhD levels) and post-doctoral researchers. We also welcome more experienced researchers and engineers wishing to expand their general knowledge, for instance, to suit a newly acquired position or collect credits for Continuous Professional Development (CPD). The course content is tailored to the needs of a diverse audience: newcomers to the field, experienced students, and young professionals working at the forefront of fuel cell and hydrogen applications.
As a contribution to the national hydrogen strategy, 3.5 years ago, the Delfin research project started with the aim of developing a cost- and material-optimized hydrogen tank design for automotive application. Under the patronage of the National Organization Hydrogen and Fuel Cell Technology (NOW), a consortium consisting of 9 research institutes, component suppliers, engineering service providers and automobile OEMs is processing a wide range of work packages. The focus of BAM research sets on impact testing and safety-related characterization of pressure vessels of different development stages. Furthermore, the implementation of nondestructive testing methods is applied. The presentation shows an overview of the BAM work packages and an extraction of the results generated so far.
Die Optimierung und Validierung des digitalen Wasserstofftankstellenmanagements mit Sensortechnologien ist das übergeordnete Ziel des Teilprojekts Digitale Qualitätsinfrastruktur mit Sensortechnologien (QIST) am Use Case H2, im Rahmen der digitalen Qualitätsinfrastruktur (QI digital[1]). Hierfür sollen u.a. Sensornetzwerke mit digital-gestützten Auswertungsstrategien intelligent gestaltet werden (Stichwort KI bzw. digitaler Zwilling). Verschiedene, sich ergänzende Sensoren, Systemkomponenten und KI-Methoden stehen als Bausteine intelligenter Sensorsysteme zur Verfügung, mit dem Zweck, die physikalischen und chemischen Parameter an und in Anlagen umfassend und effizient zu überwachen sowie Fehlfunktionen zuverlässig zu detektieren und zu interpretieren, Abbildung 1.
Konkrete Arbeitsschritte sind, nach dem Aufbau der Versuchsplattform „Wasserstofftankstelle“, die Instrumentierung von Sensorik und deren digitale Integration in das Tankstellenmanagementsystem sowie die Validierung im Realbetrieb. Die somit erzielten Messergebisse sowie die Messunsicherheiten, Historien und Verfahren werden in digitaler Form aufbereitet, gespeichert und fortlaufend in die KI-basierte Datenauswertung einbezogen, inkl. der Anbindung an die metrologische Rückführungskette.
Ziele sind:
• Einführung eines neuen messtechnischen Ansatzes und eines digitalen Zwillings für den Anwendungsfall "Wasserstofftankstelle" auf Basis der H2-Sensorik sowie der Zustandsgrößen Druck und Temperatur
• Qualitätssicherung durch Applikationen zuverlässiger Gassensorik, Manometer und Thermometer sowie KI-Methoden zur Prozesskontrolle und Detektion von Fehlfunktionen
• Nutzung von digitalen Kalibrierscheinen (DCCs) insbesondere für die Messgröße Temperatur zur Realisierung der metrologischen Rückführung in einer digitalen Qualitätsinfrastruktur
H2Sense - Cost-effective and reliable Hydrogen Sensors for Facilitating the Safe Use of Hydrogen
(2016)
The H2SENSE (Cost-effective and reliable hydrogen sensors for facilitating the safe use of hydrogen) project promoted hydrogen primarily, but not exclusively, for its use as an alternative fuel. It brought together different stakeholders including sensor manufacturers, end-users, certification bodies and independent evaluators to ensure the optimum use of low-cost and reliable hydrogen sensors.
Project partners analysed sensor performance in real-life applications in industrial environments and identified increased requirements for sensors and for regulations, codes and standards. H2SENSE also facilitated the safe use and implementation of hydrogen as an alternative fuel by ensuring the correct use of effective hydrogen detection devices.
European scientists worked together with colleagues from the National Renewable Energy Laboratory (NREL) in Colorado, USA. They pooled their knowledge of developments in hydrogen sensor technology as well as deployment and commercialisation strategies. These benefits will be continued through trans-Atlantic inter-laboratory sensor testing programmes in which EU and US laboratories perform complementary tests and exchange results.
The following presentation provides an overview on some of the challenges with metallic materials used as structural materials in the energy sector for the transport and storage of hydrogen. The presentation contains explanations about the methodologies utilized to characterize the susceptibility of these materials for hydrogen.
Joining processes for components in hydrogen technologies: Current need and future importance
(2022)
This presentation gives an overview on the importance of joining processes for component fabrication in hydrogen technologies. For that reason, the current need and future research and developement activites are highlighted for the three technological fields: hydrogen storage, transport and use (in terms of the emerging field of additive manufacturing). Finally, some remarks are given for necessary changes in the standardization.
Experiments have been performed to determine whether a storage vessel containing LH2 and caught in a fire engulfing the vessel can result in a BLEVE (Boiling Liquid Expanding Vapour Explosion) and if so its effects. The tests were performed at the Test Site Technical Safety of the Bundesanstalt für Materialforschung und –prüfung (BAM) in Horstwalde, Germany.
Three tests were performed using double-walled vacuum insulated vessels of 1 m3 volume. The cylindrical Vessels differed in orientation (horizontal or vertical) and the insulation material used (perlite or multi-layer insulation (MLI)). The degree of filling of the vessels was approximately 35-40 % in each of the tests performed. The fire load was provided by a propane fed burner positioned under the storage vessel and designed to give a homogeneous fire load.
The conditions in the vessel (temperatures and pressure) as well as external effects (heat radiation, blast waves, flame ball development and fragmentation) were measured.
All vessels were equipped with K-type thermocouples at several locations: inside the inner vessel in the gas phase and the liquid phase, on the inner and outer side of the inner vessel and on the inner and outer side of the outer vessel. The pressure inside the inner vessel (both in liquid, as a level indicator, and gaseous phase), and in the space between the inner and outer vessels (vacuum pressure) was measured.
Bolometers were used to measure the heat radiation generated by both the propane fire and that generated by a possible fireball/BLEVE. To measure blast generated by the vessel burst/BLEVEs blast pencils were positioned at three locations in two directions. Weather conditions were monitored at two weather stations. Further several cameras were used to monitor the events: normal cameras, infrared (IR)-cameras, high-speed cameras also on board of a drone.
Two of these vessels, a horizontal and a vertical vessel both insulated with perlite withstood the fire loading for 1 hour 20 minutes and 4 hours respectively without catastrophic failure. A horizontal vessel insulated with MLI failed by bursting after 1 hour and 6 minutes resulting in a fireball, fragments, and blast waves.
Hydrogen-induced stress corrosion cracking (HSCC) is well known, and highly sensitive pre-stressing steels are normally not available on the market. But in the case of existing structures, it could be necessary to ensure their safety through special kinds of investigations. Those kinds of investigations are often not applicable in a non-destructive way.
Therefore, a once in a lifetime project was initiated.
In the course of the deconstruction of the "Bridge of the 20th anniversary of the GDR" at the Altstädter Bahnhof in Brandenburg a. d. Havel, new information on the initiation of hydrogen-induced stress cracks could obtained. The initial observation to do several investigations at this bridge are several meters long longitudinal cracks in the concrete web of the box girder above and below the tension duct. The BAM was commissioned by the Brandenburg State Road Administration to participate in a corresponding joint project which is financed by the Federal Ministry for Digital and Transport. The added value of the new information gained in this project goes beyond the specific structure. It describes unexpected new damage patterns that can be transferred to other structures with concentrated tendons (tendon block method and Baur-Leonhardt method) and were previously unknown in this form. These should be made known to other developers to enable them to initiate any necessary actions.
One of the major results is, the wire breaks observed at this bridge can be attributed to cracking as a result of HSCC and subsequent crack growth until breakage, due to cyclic loading from traffic and alternating restraint stresses. The probable trigger here was crevice corrosion processes at the contact points of the wires to the spacer plates in superposition with high tensile stresses due to prestressing after or with in grouting the duct. Tension wire breaks, which may have occurred before grouting and during prestressing, were not detected. The unfavorable gap situation at the spacer plates occurs over the entire cross-section of the prestressing channel and can thus affect each individual prestressing wire. Losses in the load-bearing capacity of the prestressed concrete structure can then be the result. A disadvantage of the prestressing block method in this respect is that a large number of individual wires can be affected at the same time (theoretically all wires), which can reduce the prestressing effect of the concentrated tendon accordingly. With the usual use of only one tendon per web, the possibility of load transfer to other tendons is thus not given (lack of redundancy).
Within a research cooperation between BAM and Gexcon as part of the SH2IFT program, large scale experiments have been performed at the Test Site Technical Safety of the Bundesanstalt für Materialforschung und –prüfung (BAM) to determine the hazards emerging from a vacuum insulated cryogenic storage vessel containing liquified hydrogen (LH2) is caught in a fire engulfing it.
Investigation of fuel cell materials and liquid water transport by means of synchrotron imaging
(2013)
Synchrotron imaging allows addressing various important issues in fuel cell research, for example water distribution and transport. The water distribution in polymer electrolyte membrane fuel cells (PEMFCs) was observed quasi in-situ directly after operation by means of synchrotron tomography. The 3D data set was compared with the tomogram of a dry cell in order to separate the water distribution from cell materials. Engineered transport pathways realized by perforating holes through the gas diffusion layer (GDL) are a recent approach to optimize water transport and cell performance. For some parameter sets a cell performance increase and an improvement of stabilization have already been proven. We present high resolution investigations of the water distribution in perforated GDLs of operating PEMFCs by means of in-situ synchrotron radiography. The surrounding areas of the holes exhibited a distinct hydrophilic character.
Glass
(2019)
Overview about the key activities of division 5.6 glass and the diversity of the material glass. For the vacuum hot extraction method (VHE-MS) some examples are presented e. g. for the measurement of water content or the determination of diffusion coefficient of hydrogen in glasses. Finally, an outlook is shown on the robot controlled glass screening device which will be available next year.
The presentation introduces the BAM as well as the experimental possibilites at the BAM TTS in the first part. The general possibilities regarding Power2Gas with respect to hydrogen production by electrolysis are preseneted. Furthermore the Hydrogen Strategy of Germany and the status quo regarding grenn energy solutions in the transport sector are given. In the last part of the presentation a short overview of relevant investigations in the field of hydrogen safety and alternative fuels for cars as well as perspectively planned investigations of the BAM in this area are presented.
This study gives an overview on the important field of joining processes for component fabrication in hydrogen technologies. For that reason, the current need and future research and developement activites are highlighted for the different technological field of hydrogen generation, storage, transport and use. In addition, the emerging field of additive manufacturing is included. Finally, some remarks are given for necessary changes in the standardization and its challenges.
Introduction: Mass transport at gas/liquid interfaces depends on many factors including the gas and liquid properties and hydrodynamics. The mass transport of a gas through the liquid is a limiting step in many chemical reactions. To gain a fundamental understanding of multiphase interfaces, the rate of mass transfer has been measured for pure gases (H2, N2, O2, He) into a thin liquid film with a well-defined surface area and velocity profile. This enables the mass transfer rate to be broken down into one parameter, which is the gas/liquid interfacial area (a), and a second parameter, which is the mass transfer coefficient (kL). Using gases with varying diffusion coefficients enables a comparison of the measured rates of mass transport to the rates predicted by film theory and penetration theory.
Method: A gravity-driven thin water film 0.000180 m in thickness flowing along the outer surface of a capillary was contacted with a gas phase inside a closed system. The liquid was circulated continuously until it was saturated with gas and the equilibrium pressure was reached. In this device, there is laminar flow, and therefore, the hydrodynamics of the liquid film are well defined.
Results: Penetration theory predicts a non-linear relationship between diffusion coefficient (DAB) and mass transfer coefficient (kL). by means of falling film reactor the actual rates of gas-liquid mass transfer are higher than those predicted by theory. Also, a linear relationship between DAB and kL is observed experimentally. The mass transfer coefficient can even, as a rule of thumb, be assumed to be relatively constant with a value of around 10-4 m/s for aqueous solutions.
The safety characteristics of flammable gases and liquids are required when identifying potentially explosive mixtures and taking appropriate actions concerning explosion protection. Examples are given in this review of the safe handling and evaluation of hazards during the processing, storage, transport, and disposal of flammable liquids and gases. The CHEMSAFE database is presented as a reliable source of safety characteristic data, and ist new open-access version is introduced. CHEMSAFE currently contains assessed properties for about 3000 flammable liquids, gases and mixtures. The lack of a broad experimental foundation in the extensive field of non-atmospheric conditions shows the need for further investigation and standardization. This review summarizes experimental evidence and estimation methods for safety characteristic data under non-atmospheric conditions pointing out current limitations. Suggestions for pre-normative research on safety data under nonatmospheric conditions are given.
In this presentation safety aspects of hydrogen transportation are discussed. At first, the regulatory background and level of safety are presented. In the second part, the modelling of consequence due to sudden rupture of pressure receptacles is explained. Finally, the results are used to define a limit for consequence to enable an acceptable and safe transport of hydrogen.
In this presentation the capabilities and different research activities at BAM in the field of hydrogen safety are outlined. A deep dive focussing the transport of hydrogen in pipelines adressing issues on material compatibility, gas quality and test methods is presented. Another deep dive is presented focussing on safety aspects of liquid hydrogen adressing issues of rapid phase transition (RPT) and Boiling liquid expanding vapour explosion (BLEVE). Finally a brief overview on other safety related research activities is given.
Sensor systems are widely used in hydrogen technologies. The lecture presents requirements and properties of sensor systems and shows application examples of these technologies for safety and process control for hydrogen technologies. The focus is on gas sensors as well as sensors for pressure, temperature and gas flow. These systems are applied, among other things, for monitoring and control of operating conditions, indication of hazardous conditions and triggering of alarms.
Germany has concluded energy partnerships with various countries, including Japan. During the 3rd meeting of the Hydrogen Working Group, the strategic approach of both countries on developments of hydrogen guidelines, certification and safety was presented and discussed. BAM gave a presentation on important topics in the field of safety research and on safety-related issues along the value chain. Furthermore, the work program and selected projects of the competence center H2Safety@BAM were presented.
Fibre-reinforced plastics (FRP) especially carbon-fibre-reinforced polymer (CFRP) and glass-fibre-reinforced polymer (GFRP) are commonly used materials in high pressure vessels and storage units for automotive and aerospace purposes. Optical fibres are suitable to be integrated or directly applied to the surface of FRP components. Using optical fibres it is possible to monitor the distributed strain profiles and changes within the fatigue life of a pressure vessel to ensure the operational safety. Within artificial ageing experiments we used swept wavelength interferometry (SWI) based distributed strain sensing for the monitoring of commercial high-pressure composite cylinder. This artificial ageing was performed using test conditions of 503bar pressure load (service pressure 300 bar) and 89 °C for 100 h. The polyimide coated optical fibres were glued to the surface externally in circumferential and axial direction. Using distributed strain sensing (DSS) material expansion of over 0.5% were monitored with sub-centimetre spatial resolution. Within the circumferential direction we observed up to 10 % local fluctuation compared to the median strain caused by inhomogeneous material expansion, which could cause local material fatigue. In addition, we determined material degradation manifested itself as localized remaining material expansion and/or contraction. Results have been validated by other non-destructive methods like digital strip projection.
Hydrogen might cause severe degradation of supermartensitic stainless steels, if they are activated during exposure to sour environments. Consistent and comprehensive data for hydrogen transport in these materials are thus required to support, in particular, modelling of hydrogen assisted cracking as a part of life time assessment of welded steel components. In addition to previously published diffusion coefficients and subsurface concentrations of a supermartensitic stainless steel further data dependent on heat treatment are provided by this contribution. Furthermore, a higher alloyed material has been investigated in the state as received and also in the quenched condition, in order to approach the influences of chemical composition on hydrogen transport in supermartensitic stainless steels. With respect to welding it turned out that the diffusion coefficient and the subsurface concentration are markedly dependent on heat treatment of the materials.
Introduction: Homogenously catalyzed reactions in multiphase systems, as they are used for example for the hydroformylation or reductive amination, offer a promising approach to produce base chemicals from renewable resources. The organic and gaseous educts react with the catalyst, which is designed to be soluble in water to provide a good separation from the likewise organic products. In the resulting gas/liquid/liquid systems, the reaction is controlled through interfacial and transport phenomena. These processes fail for long chained olefins – e.g. vegetable oils and fats – because of their low solubility in water. Therefore, surfactants can be added as an emulsifier to form micellar emulsion systems (MES) [1], increase reaction speed [2] and facilitate phase separation [3]. These systems form up to three liquid phases, depending on temperature and composition. For fast reactions, the gas/liquid mass transfer plays an important role. Due to the multiple phases present, the dispersion conditions of the particles and the resulting mass transfer are complex.
Methods: In this work, the mass transfer in MES is investigated. For simplicity, only the non-reactive material system without catalyst consisting of water, dodecane and the non-ionic surfactant Marlophen NP8 was investigated. Hydrogen was applied as gas phase. The phase behavior of the MES was characterized using settling experiments and by measuring the conductivity of the emulsions [4]. The mass transfer experiments were conducted in two different setups employing the dynamic pressure method.
In a pressurized stirred tank reactor, the mass transfer performance of the whole MES was determined under the complex dispersion conditions and a variety of different system parameters by measuring the volumetric mass transfer coefficient (kLa). The specific transfer area (a) was determined measuring gas hold-up and using optical endoscope measurements [5] to record bubble sizes. The non-spherical bubbles were analyzed with a trained convolutional neural network [6].
Using a falling film capillary in a closed pressurized system [7], the mass transfer of the single phases appearing in MES were quantified. The phases were removed and investigated separately after the settling experiments. A gravity-driven laminar flow with well-defined transfer area was established along the capillary and by measuring the pressure drop over time the mass transfer coefficient (kL) could be calculated.
Results: The mass transfer coefficients of hydrogen in the single phases of the micellar emulsion system covered a broad range. The kL of the aqueous phase was similar to pure water, while the third, bi-continuous phase forming in MES had very small kL values due to its high viscosity. The mass transfer coefficient of the organic phase was found to be far higher than of the aqueous phase.
In the stirred tank reactor, different phases formed the continuous phase in the whole MES mixture for the temperature range investigated. The fastest mass transfer was found for a continuous aqueous phase below 87 °C. At higher temperatures, a phase inversion occurred, and the organic phase became continuous. The high kL of the organic phase measured in the falling film contactor did not translate directly to a higher kLa in the stirred tank reactor as the value dropped compared to an aqueous continuous phase present. The change in continuous phase were found to affect the drop and bubble sizes in the system. For an organic continuous phase, the Sauter mean diameter of the bubbles were larger and the transfer area smaller, which was the main reason for the reduced kLa.
Composite pressure vessels for transporting dangerous goods and for hydrogen and natural gas vehicles consist of a load-bearing composite and a gas-tight, metallic or polymeric barrier layer (liner). To investigate the aging behavior of such composite pressure vessels, BAM carried out the interdisciplinary project COD-AGE. The aim of the project was the development of methods and models for the description and determination of the aging behavior of carbon fiber composites using the example of pressure vessels in order to better predict aging and safe working life. One focus of this project was the provision of suitable NDT methods. These included both test-related tests and the possible development of test equipment for later practical use.
In the lecture, test results of the age-related eddy current test on composite pressure vessels are presented.
In aging tests, pressure vessels made of an approximately 4 mm thick aluminum liner and approx. 8 mm thick CFRP layer were examined. Typical application of such pressure vessels are respiratory protective devices of the fire department. The pressure vessels were tested using conventional eddy current technology from the outer and inner side as well as with high-frequency eddy current technology. Both damage to the metallic liner and structures of the CFRP could be detected. A particular mechanical challenge was the inspection of the inside of the liners, since a cylindrical surface with an inside diameter of 150 mm has to be tested with an access of only 15 mm diameter.
In this talk, general aspects of the safety and acceptance of hydrogen technologies were presented. How can trust in new technologies be built when past accidents led to myths and fairy tales? The presentation does away with general prejudices and shows that handling hydrogen is neither more unsafe nor safer than handling other fuel gases. The basis for the safe handling of hydrogen is always a risk analysis.
To reduce the emission of carbondyoxide (CO2) of combustion engines, liquefied natural gas (LNG) is used as an alternative fuel. LNG is transported via truck, ship or railway for long distances. Double walled stainless steel tanks are used for transportation, which are heavy and expensive. The vacuum insulation between the two walled structure ensures that the LNG stays liquid over the transportation time (boiling point of LNG: -162 ◦C). This causes a high temperature difference between the transported good and the ambient air.
A simplified tank construction is used to reduce the weight and price of the tank. Instead of stainless steel, glass fiber reinforced plastic (GFRP) is used. The design is changed to a single walled construction with a solid insulation material outside on the GFRP structure.
Goal of this work is the characterization of a suitable insulation material and configuration as well as the analysis of the mechanical properties of GFRP under cryogenic conditions. Several experiments are carried out. Numerical models of these experiments can then be used for parameter studies.
The ongoing geo-political conflicts and the increasing need for the implementation of measures to improve the energetic system sustainability are increasing the importance of tanks for storing cryogenic fluids in the energy industry. The most common example of cryogenic tank applications is the transport of natural gas and hydrogen in their liquid form (LNG and LH2 respectively) for which, considering the same transport volume cryogenic storage ensures significantly higher transport capacities with respect storage based solely on overpressure.
A common feature of all cryogenic transported fluids is that their condition must be maintained minimizing heat leaks from the environment as much as possible. This is achieved by the implementation of thermal super Insulations (TSI) systems based on e. g. rock wool, perlites, microspheres, multilayer insulations (MLI), and vacuum which have proven to be effective in applications. However, due to the relatively short period of use in some applications, the small number of documented incidents, and the still few investigations carried out in the field, the exploitation of such systems in the cryogenic fluids transport sector still suffers from insufficient knowledge about the course and consequences of incidents. Accidents involving collisions, fires, and their combination are quite common in the transportation sector and may generate extraordinary loads on the tank and its insulation system, eventually leading to tank failure.
The present study focuses on the behavior of TSI systems in tanks when it is exposed to an external heat source representative of a hydrocarbon fire scenario. This may cause an increase of the heat flux into a tank by several orders of magnitude with respect to normal design conditions, thus inducing severe and in the TSI, causing the rapid release of flammable gas and even resulting in a Boiling Liquide Expanding Vapour Explosion (BLEVE).
To study such scenarios a test rig was developed at BAM that allows testing of TSI at industrial conditions and enables subsequent analysis of TSI samples. This test rig considers the typical double-walled design of tanks for cryogenic fluids with vacuum and an additional insulating material in the interspace. Adjustable electrical heating elements simulate the fire on one side of the double wall. This process allows the implementation of repeatable heat loads of up to 100 kW/m². The other side of the double wall is represented by a fluid-supported heat exchanger, which allows the simulation of cold or cryogenic conditions in the test rig, and to determine the heat flux transmitted through the double wall. Thus, the test rig allows thermal loading and performance analysis of TSI samples at the same time.
In the presentation, the results of diverse tested TSI systems will be presented and discussed. As a result of this study, the list of advantages and disadvantages for the choice of tested TSI expands. Within the test, all samples degraded as a consequence of a hydrocarbon fire-orientated thermal load. Strong differences in the behavior of the tested TSI systems over temperature, location, and time were observed. Additionally, the tested MLI insulations were significantly more resistant to their base materials. These results are relevant for the design, the definition of national and international regulations, the Risk assessment, and the development of safety concepts for cryogenic tanks.
Mechanical friction, impact or abrasion is one of the ignition sources that must be avoided in hazardous zones with explosive atmospheres. The effectiveness of mechanical impacts as ignition source is dependent from several parameters including the minimum ignition energy of the explosive atmosphere, the properties of the material pairing, the kinetic impact energy or the impact velocity. By now there is no standard procedure to determine the effectiveness of mechanical impacts as ignition source. In this work the effectiveness of mechanical impacts with defined and reproducible kinetic impact energy as ignition source for hydrogen containing atmospheres was studied systematically in dependence from the inhomogeneous material pairing considering materials with practical relevance like stainless steel, low alloy steel, concrete, and non-iron-metals. It was found that ignition can be avoided, if non-iron metals are used in combination with different metallic materials, but in combination with concrete even the impact of non-iron-metals can be an effective ignition source if the kinetic impact energy is not further limited. Moreover, the consequence of hydrogen admixture to natural gas on the effectiveness of mechanical impacts as ignition source was studied. In many cases ignition of atmospheres containing natural gas by mechanical impacts is rather unlikely. No influence could be observed for admixtures up to 25% hydrogen and even more. The results are mainly relevant in the context of repurposing the natural gas grid or adding hydrogen to
the natural gas grid.
In this investigation, synchrotron X-ray imaging was used to investigate the water distribution inside newly developed gas diffusion media in polymer electrolyte membrane fuel cells. In-situ radiography was used to reveal the relationship between the structure of the microporous layer (MPL) and the water flow in a newly developed MPL equipped with randomly arranged holes. A strong influence of these holes on the overall water transport was found. This contribution provides a brief overview to some of our recent activities on this research field.
Elastomer seals are widely used as barrier seals in containers for low and intermediate level radioactive waste and in some countries for spent fuel transportation casks. Depending on the area of use, the rubber materials have to demonstrate proper sealing performance with regard to mechanical, thermal and environmental conditions as well as irradiation during the entire operation period.
In Germany the low and intermediate level radioactive waste is planned to be disposed in the Konrad repository in standardized containers. Many of these containers use an elastomer seal between lid and container body. Depending on the radiactive inventory and a possible containment of the waste in inner barrels and/or concrete structures, such containers may require a specific leak tightness. In such cases, specified leakage rates are shall not be exceeded by the the seals to keep potential activity releases from the inventories well below defined limits.
Generally, all waste containers have to fulfill the waste acceptance criteria for the Konrad repository as defined by the reports BfS SE-IB-29/08 and SE-IB-30/08. From these criteria several requirements for seal performance are derived. The seals have to:
- ensure full functionality until final container disposal,
- maintain its function in case of a thermal or mechanical accident,
- ensure encapsulation also at -20 °C.
This combination of requirements is challenging especially as a seal exchange, which is typical for many other applications, is hardly possible and thus a sound understanding of how to perform safety evaluation of containers is required. Therefore BAM has initiated investigations on elastomer seal behaviour. This work focuses on low temperature behaviour and sealing performance concerning static conditions as well as partial loss of compression and ageing of elastomer seals. Concerning ageing, property changes caused by long-term thermooxidative conditions as well as gamma irradiation are investigated.
This contribution presents an overview and explanation of the aims of the ongoing research and gives an update of the most relevant results.
The introduction reflects the political background in Germany and worldwide concerning hydrogen as energy carrier. This leads to available hydrogen strategies and the reaction of BAM by launching the competence centre H2Safety@BAM. Fokus is set on the competence area TestCert, the special role of the division “Safety of Gas Storage Systems” there and its increasing success in research activities.
The main part explains the needs for a risk-controlled market ramp-up concerning hydrogen products and appropriate measures being under development in division 3.5: risk control, tools for consequence estimation and limitation, probabilistic assessment of end of safe life, the efficiency assessment and optimization of current regulations, the structural health monitoring (SHM) with necessary improvement of measures for quality management in the digital world of safety assessment. Last but not least, the wide range of full-scale testing and simulation of worst-case scenarios is explained.
This paper describes the testing methods used to determine the thermal properties of insulation materials and mechanical properties of materials used for the load-bearing structure for pressure tanks (up to 4 bar, relative) and cryogenic liquids (LNG, −166 °C to -157 °C at atmospheric pressure). Goal is to design a transportation tank that does not exceed 4 bars (relative) within 10 h, starting at atmospheric pressure. PUR-foam is a suitable material for the insulation. A 12,5 l small scale tank prototype reached 4 bar (relative) within 87 minutes, which is, regarding the influence of the size, a satisfying result. The mechanical properties change significantly at cryogenic temperatures. The bending modulus is similar at first, but decreases at a certain point by appr. 50 %. However, the maximum stress is much higher and could not be reached within this testing setup.
The 3-dimensional spatial distribution of liquid water in different gas diffusion layer (GDL) materials was analyzed using synchrotron X-ray tomography. The capability of the method was demonstrated by virtually separating the GDL components in order to facilitate individual analysis of fiber material, liquid water and gas filled pore spaces. The influence of hydrophobic surface treatment on the water distribution in the GDL was illustrated by analyzing three GDL materials with different degrees of hydrophobicity. In the least hydrophobic sample, liquid water tends to form larger clusters which stretch out about several hundred µm inside the porous GDL. In contrast, only small water clusters were found in the strongly hydrophobic material with high Polytetrafluoroethylene (PTFE)-content as the liquid is partially pressed out of the GDL. Additionally, the influence of fiber orientation on the water distribution in the felt material was demonstrated.
This study gives an overview on the important field of joining processes for component fabrication in hydrogen technologies. The current main issues and future perspectives are highlighted for the different technological field of hydrogen generation, storage, transport and use. In addition, the emerging field of additive manufacturing is included. Some remarks are given for standardization and regulations.
The testing of gas and humidity sensors is essential for the application of sensing devices. The testing determines properties of an investigated humidity sensor or gas sensor. In testing, the sensor property is the observed response of a sensing system to an input stimulus in comparison to a reference within a test procedure. This tutorial is structured into six chapters. The first chapter is about basics of hygrometry and gas sensing. It includes definitions, sensor classification, overview of application categories, as well as construction and functional principles. The chapter on requirements of deployed sensors focus on stability, response time, cross-sensitivity, electrical and mechanical requirements, and other. The sensing performance is characterised by determinations of parameters like accuracy, repeatability, detection limits (low and high), and response/recovery time. The description of testing signals on specified qualitative and quantitative characteristics, and the adequately estimated measurement uncertainty is the content of the analysis chapter. All chapters contain examples of testing procedures from testing/calibration labs for hygrometers and gas sensors which are essential for implementation into quality management systems.
This tutorial provides an overview of the utilization of sensor systems in hydrogen technologies. It discusses the necessary criteria and characteristics of sensor systems, and also demonstrates practical applications of these technologies in terms of safety and process control. Emphasis is placed on various types of sensors such as gas sensors, pressure sensors, temperature sensors, and gas flow sensors. These systems find application in monitoring and regulating operational parameters, detecting potentially dangerous situations, and activating alarm systems.
High strength structural steels are susceptible to hydrogen embrittlement. A critical combination of stress, amount of diffusible hydrogen and microstructure is believed to cause cold cracking. Especially during welding of high strength structural steels high tensile residual stresses may develop. Therefore, a feasibility study was conducted using synchrotron X-ray diffraction in order to analyze the stress–strain behavior during tensile loading. For that purpose two types of steel showing different hardening mechanisms were used. On the one hand a thermo-mechanically treated S1100MC and on the other hand a quenched and tempered S1300Q were chosen. The samples were electrochemically charged with hydrogen and subsequently stored in liquid nitrogen to prevent effusion. Tensile tests of the samples were conducted in a special load frame allowing for tilting the samples while applying constant loads. High energy synchrotron radiation was used for energy dispersive X-ray diffraction (EDXRD) analysis in transmission geometry. This method offers the possibility for measuring several diffraction lines of all contributing crystalline phases of the material. Strains as well as stresses applying the sin²ψ-method were determined for varying load situations. This feasibility study shows how the interaction of hydrogen and the stress/strain response may be assessed by diffraction methods. Examples are presented showing that hydrogen alters the load distribution as well as the strain behavior between different lattice planes in high strength steels.
Many new technologies are based on applications in extreme conditions, such as at low temperatures or in hydrogen environment. This involves new requirements on material properties, in particular regarding their operability and reliability. To fulfil this demand, the tribological behaviour of PTFE- and PEEK-matrix composites filled with carbon fibres were investigated at cryogenic temperatures and in hydrogen by means of surface analyses. For a better understanding of the tribological behaviour, and because of the temperature-dependent characteristics of polymer materials, thermal and mechanical properties of selected composites were initially investigated at low temperatures. Thermal shock experiments as well as cryo- and hydrogen treatments were carried out. Different coefficients of thermal expansion within the composite lead to debondings of particles, particularly in the case of PTFE materials. Tensile tests indicate that the YOUNG'S modulus increases at T= 77 K compared to room temperature. However, this improvement at low temperatures is moderate for PEEK composite which is already under its glass transition at room temperature. In the main investigation, tribological experiments were carried out at first at T= 77 K to observe the influence of the matrix, fillers and fibres on the material behaviour comparing to room temperature. The reduction of the friction coefficient and wear at low temperatures has been attributed to the low temperature properties of the polymer in particular due to the higher YOUNG'S modulus at T= 77 K. Whereas at room temperature friction and wear depend strongly of the CF content, the quantity of fillers and fibres does not have a significant effect on the tribological behaviour at low temperatures. At T= 77 K, the tribological behaviour of PTFE and PEEK composites is mainly influenced by the matrix. PEEK composites have a better tribological performance than PTFE materials especially regarding the wear resistance. Furthermore, the influence of the cryogenic medium was determined with experiments carried out in LN2 (T= 77 K), LH2 (T= 20 K) and LHe (T= 4.2 K), as well as in helium at T= 77 K and hydrogen at room temperature. The thermal properties of the cryogenic medium have a significant influence on the tribological performances of the composites. Due to the lower frictional heat at low sliding speed, the effect of low temperatures on the tribological behaviour of these composites was more clearly detected in this case, with a change in wear mechanism from mainly adhesive to more abrasive. Experiments in LN2 give the best friction and wear performance at low as well as at high sliding speed. The behaviour of these composites in LHe does not benefit from the low temperature properties of polymers due to the low heat of evaporation of LHe. The influence of hydrogen was particularly seen after the tribological experiments performed in LH2 on the surface of the disc. The reduction effect of hydrogen may have an influence on the tribochemical reactions which appear during sliding, enhancing the formation of iron fluorides, but no influence of the metal fluorides on the tribological performance could be determined in this study.
Hydrogen assisted stress corrosion and cold cracking represent still a major topic regarding the safety of welded steel components against failure in many industrial branches. Hydrogen might be introduced during fabrication welding or might be taken up from an environment during sour service or at cathodic protection. Additionally, understanding and avoidance of hydrogen entry into weld microstructures from gaseous pressurized environments becomes increasingly important for renewable energy components. There are two types of metallurgical mechanisms associated with hydrogen assisted cracking, i.e. the cracking as well as hydrogen transport and trapping mechanisms. For numerical modelling, it has to be considered that both types are not independent of each other, that the mechanisms are not yet completely clarified and that validation of such models strongly depends on implementation of the correct hydrogen related materials properties. However, quite significant achievements have been made in modelling of hydrogen assisted cracking by indirect coupling of thermal, stress-strain as well as hydrogen uptake and diffusion analyses. After a brief introduction into the subject and by revisiting various proposed cracking mechanisms, the present contribution focuses on recent developments of a numerical model based on a comparison of actual hydrogen concentrations and mechanical loads with respective hydrogen dependent material properties as crack initiation and propagation criteria. The basic procedure for numerical simulation of crack initiation and propagation is outlined and it is shown how such numerical simulations can be validated experimentally. Furthermore, it is highlighted how such a procedure has been extended to a comprehensive model for life time prediction of welded steel pipeline components and experimentally verified. Finally, it is outlined how the model can be extended to simulate cracking in heterogeneous steel microstructures on the different scales.
Monte-Carlo-Analysis of Minimum Burst Requirements for Composite Cylinders for Hydrogen Service
(2021)
For achieving Net Zero-aims hydrogen is an indispensable component, probably the main component. For the usage of hydrogen, a wide acceptance is necessary, which requires trust in hydrogen based on absence of major incidents resulting from a high safety level. Burst tests stand for a type of testing that is used in every test standard and regulation as one of the key issues for ensuring safety in use. The central role of burst and proof test is grown to historical reasons for steam engines and steel vessels but - with respect for composite pressure vessels (CPVs) - not due an extraordinary depth of outcomes. Its importance results from the relatively simple test process with relatively low costs and gets its importance by running of the different test variations in parallel. In relevant test und production standards (as e. g. ECE R134) the burst test is used in at least 4 different meanings. There is the burst test on a) new CPVs and some others b) for determining the residual strength subsequent to various simulations of ageing effects. Both are performed during the approval process on a pre-series. Then there is c) the batch testing during the CPVs production and finally d) the 100% proof testing, which means to stop the burst test at a certain pressure level. These different aspects of burst tests are analysed and compared with respect to its importance for the resulting safety of the populations of CPVs in service based on experienced test results and Monte-Carlo simulations. As main criterial for this the expected failure rate in a probabilistic meaning is used. This finally ends up with recommendations for relevant RC&S especially with respect to GTR 13.
In a future energy supply system based on renewable sources hydrogen technology will play a key role. Because the amount of energy from renewable sources, such as wind or solar power, differs seasonally and regionally, an energy storage method is necessary.
Hydrogen, as an environmentally friendly energy carrier, can fill this gap in an ideal way, in particular for mobile applications (Wurster et al., 2009). Already today, in Germany the amount of hydrogen as a byproduct in chemical industry is enough for fuelling about 1 Mio passenger cars1. Excess electrical power can be used to produce hydrogen by electrolysis. On demand, this hydrogen can be used for mobile or stationary fuel cells. Beside this new developing technology, hydrogen is used as fuel for rocket engines and in chemical industry since a long time. Table 1 comprises some physical parameters of hydrogen. It can be seen that hydrogen gas has a very low density which makes storage at high pressure or in liquid form (LH2) necessary.
For the hydrogen-based energy economy of tomorrow, the construction of the necessary infrastructure will play a central role. Most materials used to date, such as welded steels, can be prone to hydrogen embrittlement under certain conditions. This includes the classic delayed cold cracking during welding as well as degradation phenomena during service of components in hydrogen-containing environment. For the evaluation of any hydrogen effect, for example, on the mechanical properties of a welded metallic material, the hydrogen content must be precisely determined. In the case of weld seams, the carrier gas hot extraction (CGHE) according to ISO 3690 is meanwhile state-of-the-art. CGHE is based on accelerated hydrogen degassing due to the thermal activation of hydrogen at elevated temperatures. In addition to the quantification of hydrogen, thermal desorption analysis (TDA) with varying heating rates can be used to determine and evaluate the hydrogen trapping at microstructural defects in the material. For both techniques, experimental and metrological influences must be considered, which have a major effect on the result. For example, ISO 3690 suggests different sample geometries and minimum extraction times for CGHE. This study summarizes the results and experiences of numerous investigations at the Federal Institute for Materials Research and Testing (BAM) with different sample temperatures and geometries (ISO 3690 type B and cylindrical TDA samples) regarding the influence of the sample surface (polished/welded), measurement accuracy depending on the sample volume and the insufficient monitoring of the effect of PI control on the extraction temperature. A deviating extraction temperature from the target temperature can significantly falsify the measurement results. Based on the results, methods are shown which allow the desired extraction temperature to be reached quickly without physically interfering with the measuring equipment. This serves to significantly improve the reliability of the hydrogen measurement through increased signal stability and accelerated hydrogen desorption. In general, an independent temperature measurement with dummy samples is recommended for the heating procedure of choice to exclude possible undesired temperature influences before the measurement. The methods described can be transferred directly to industrial applications
The study provides an overview of the aspects of joining and its importance in manufacturing of components for the more and more important field of hydrogen as key factor for the energy transition to a decarburized future. To this end, the fundamentals of the technology fields of hydrogen production, storage, transport, and application are presented and the state of the art of manufacturing of components for hydrogen technologies by joining is summarized. Based on representative examples from practice, research and development, the importance of joining technology in hydrogen technologies is clearly highlighted and perspectives for the future are derived. From a macroeconomic perspective, the focal points, or trends of joining technologies here include: the erection of new infrastructure for hydrogen storage and transport, and the safe conversion of existing natural gas infrastructure and its challenges for welded materials. In addition, we show the problems that are anticipated with in-service repair welding of hydrogen pipelines. In hydrogen applications, the efficient mass production of fuel cells and electrolysers is becoming increasingly important. For that reason, the importance of additive manufacturing is highlighted. Finally, the challenges for technical regulations and standardization by using hydrogen are shown.
Competence Centre H2Safety@BAM – Safeguarding the Quality Infrastructure in the Hydrogen Economy
(2022)
Hydrogen is a central component of the energy transition and the European Green Deal for a climate-neutral Europe. To achieve the goals defined for 2050, the EU and the German government have developed a framework for action and are making long-term investments in research, development, and the rapid implementation of innovative hydrogen technologies.
With the Competence Centre "H2Safety@BAM", BAM is creating the safety-related prerequisites for the successful implementation of hydrogen technologies at national as well as European level.
To this end, BAM conducts research, testing and consulting in a holistic and inter-disciplinary manner under one roof – in the Competence Centre H2Safety@BAM. The activities of the competence centre focus on ensuring the safety of infra-structures, plants, and processes as well as innovative hydrogen transport and storage systems based on digital quality testing and the experimental testing of components and systems. It thus creates the prerequisites for the implementation and adaptation of legal framework conditions as well as for standardization. Closely related to this are investigations into the properties and compatibility of metallic materials and polymers as well as friction systems for the safe operation of components, plants, processes, and systems. This interdisciplinary and holistic approach is complemented by the development of gas analytics and suitable sensors, online measurements of gas properties in process control, test scenarios under real conditions as well as impact assessments of accidents and risk assessments and risk management systems derived from them. With its portfolio of tasks and competences, BAM builds trust in the safety and reliability of technical system solutions for hydrogen.
Low-alloyed heat-resistant steels have a fundamental contribution to the currently applied steel grades in pressurized and temperature loaded components like membrane walls(water walls)or pressure vessels. Here, the main advantages of the low-alloy concept can be used in terms of superior high temperature mechanical properties, workability and decreased amounts of expensive alloy elements. The main challenge for the future is to further increase the power plant thermal efficiency independent of the type of power plant concept, i.e. fossil-fired or nuclear power plant, where the material selection can directly affect reduction of CO2 emissions.
In power plant design, welding is the most applied manufacturing technique in component construction. The necessary weld heat input causes metallurgical changes and phase transitions in the heat affected zone (HAZ) of the base materials and in the deposited weld metal. The weld joint can absorb hydrogen during welding or in later service - This absorption can cause degradation of mechanical properties of the materials, and in certain loading conditions, hydrogen-assisted cold cracks can occur. This cracking phenomenon can appear time delayed due to the temperature dependency of the hydrogen diffusion and
the presence of a “critical” hydrogen concentration. Additionally, each specific weld microstructure shows a certain hydrogen diffusion and solubility that contribute to susceptibility of the cracking phenomenon. Therefore hydrogen cannot be neglected as possible failure effect, which was identified recently in the case of T24 creep-resistant tubeto-tube weld joints. It is necessary to identify and assess the hydrogen effect in weld joints of low-alloyed steel grades for to improve further early detection of possible failures.
For each specific weld joint microstructure, it is necessary to separate the interdependencies between mechanical load and the hydrogen concentration. The
diffusivity and solubility must be considered to identify hydrogen quantities in the material at any given time. In this case, the effects of mechanical loading were dealt with independently. For the characterization of the mechanical properties, hydrogen charged tensile specimens were investigated for the base materials and thermally simulated HAZ
microstructures. The hydrogen diffusion was characterized with the permeation technique at room temperature and at elevated temperature ranges up to 400°C - It was investigated by interpreting the hydrogen effusion behavior with carrier gas hot extraction technique (CGHE). For realistic determination of the hydrogen diffusion coefficients, an improved
method was developed encompassing accelerated specimen heating and hydrogen determination via mass spectrometer (MS). Simultaneously, the corresponding temperature
dependent trapped and total hydrogen concentrations were determined.
The determined experimental results showed increased susceptibility to the hydrogen affected
degradation of the HAZ compared to the base material, which is independent of the investigated alloy composition. In particular, the martensitic coarse grain HAZ is the most susceptible microstructure to hydrogen-affected degradation. The results of the tensile
tests allowed the definition of consistent microstructure specific failure criteria (envelope curves) versus quantified hydrogen concentrations for the reactor pressure vessel 16MND5 steel (20MnMoNi-5-5) and the creep-resistant T24 steel (7CrMoVTiB10-10). The procedure of quantifying hydrogen concentrations in HAZ microstructures is novel and supports a new method of analysis for hydrogen degradation effects. Further investigations with the T22
steel (10CrMo9-10), as compared to the creep-resistant T24 steel (7CrMoVTiB10-10),
confirmed the beneficial effect of Vanadium as an alloying element to improve the resistance to degradation. In general, Mn-Mo-Ni base material grades show a higher resistance compared to Cr-Mo steels that do not include Vanadium alloying.
The investigations showed the decreased diffusion coefficient of the HAZ microstructure compared to the base material microstructure. This is caused by the stronger trapping effects that are present which simultaneously increase the hydrogen solubility as well. In
general, trapping effects above 100°C are negligible. It is noted that after testing the T24 grade, these trapping effects were observed above 100°C and must be considered. At elevated temperatures, the calculated hydrogen diffusion coefficients are sometimes greater than those in literature. This is primarily due to the unique applied specimen heating procedure resulting in a varied hydrogen effusion from the specimen.
The significance of the obtained results can be characterized in three perspectives. First, the direct comparison of the degradation was possible in terms of microstructure-specific hydrogen effects on the mechanical properties. Second, consistent failure criteria were established to quantify degradation vs. the hydrogen concentration. Third, the determination of more accurate hydrogen diffusion coefficients is now available.
From a scientific point of view, important contributions were made to further interpret the hydrogen effects on the macroscopic mechanical properties, with respect to the alloy composition and the microstructure. From a procedural standpoint, the mentioned deviation in the elevated temperature diffusion coefficients can be caused by the calculation method. This can be an explanation for the reported data scatter in the references.
In terms of an economic view, the presented experimental results contribute to a safe and reliable weld workability of the steel grades. Thus, the identified temperature levels of hydrogen trapping can be applied in the definition of minimum preheat, interpass or postheat temperatures. In addition, recommendations for suitable dehydrogenation heat treatment (DHT) procedures, with accurate temperature values and holding times, can be derived from these results. In the future, the application of the mechanical and diffusion data is intended to support numerical analysis methods to provide an improved prediction of hydrogen effects on material degradation in weld microstructures.
Fluoride compounds have gained a considerable importance in wood preservation, especially in Germany and some other countries of Europe. They are used as single compounds or in mixtures of different compounds. The International Research Group on Wood Preservation which continues the activities of a former O.E.C.D.- Group, was aslced to prepare a survey on fluorides in wood preservation together with other papers on the present state of knowledge of wood preservatives and methods of application.
Monofluorides and silicofluorides have been used in the field of wood preservation for about 60 years and special development and application of bifluorides (hydrogen fluorides) have been going on for 30 years. Much scientific work has been carried out on fluorides and much experience in practical use is available. It thus seems to be useful briefly to summarise the information on this group of compounds in wood preservation. Due to the voluminous literature, i.e. some 270 papers which are cited in the references, only an introduction into the Problems and main results but not a detailed review of the publications is possible. The subjects dealt with in the publications are indicated in the references.
With some exceptions the brief survey is limited to the compounds and mixtures without chromium, which remain leachable in the wood. Questions of toxicity to human beings, animals and plants are not discussed in this paper.
The discovery and design of high performance Pd-alloys is of great interest for the use of hydrogen as a future energy carrier. Therefore hydrogen has to be detected, separated from other gases and stored. In this respect this thesis presents the combinatorial synthesis and characterization of the ternary Pd-Ni-Co alloy System over a wide composition range based on so-called thin film alloy libraries. Those libraries are model systems to characterize a large number of alloy compositions at the same time. The sputter-deposition process is optimized for the gradient of the Pd concentration on the surface of the alloy library by the use of electron-excited Auger electron spectroscopy. The scientific goal of this work is the experimental Investigation of adsorbate-induced surface segregation phenomena on alloy libraries.
The surface and bulk compositions of an alloy library are studied after deposition, H2 exposure and H2S poisoning. The co-segregation of Ni and Co to the surface is observed. The segregation process is influenced by the oxidation of Ni and Co due to the contact with ambient air, by H2 and by H2S poisoning. Also at very high Pd concentrations in the range of 87 at.% to 97 at.%, which is interesting for the detection of very low H2-Concentrations in air, the co-segregation of Ni and Co takes place. The poisoning effects were investigated in detail on a pre-selected Pd-Ni-Co alloy by photoelectron spectroscopy (XPS, HAXPES) in addition to AES and EDX. The composition profile of the alloy on the nm scale is acquired and the surface and bulk chemistry is discussed before and after poisoning. The composition of the alloy only changed within the first 3 nm due to H2S exposure. In the ternary Pd-Ni-Co alloy system Pd is present in its metallic state, while Ni and Co show several oxidation states. The presented concepts of ternary alloy development pave the way for the systematic synthesis and characterization of new ternary transition metal alloy systems.
Replacement of expensive duplex stainless steel and conventional carbon steel by a new generation of supermartensitic stainless steel has been taken into account since the last decade corresponding to the "Fitness for Purpose" concept in order to meet the technical- economical challenge for transportation flowlines of unprocessed oil and gas products in offshore technology, in particular. Supermartensitic stainless steels can provide appropriate material properties such as: improved strength-to-weight ratio, enhanced useful corrosion resistance as well as application at relatively low cost. With decreased carbon content and increased molybdenum content compared to traditional martensitic stainless steel, hydrogen assisted stress corrosion cracking (HASCC) problems have been found during service caused by hydrogen being taken up during from sour service environments by cathodic protection. Hydrogen assisted cold cracking in supermartensitic stainless steel can also occur during fabrication welding with hydrogen picked up during welding, since this steel is relatively crack-susceptible by hydrogen. Therefore, effects of hydrogen assisted cracking (HAC), i.e. HASCC and HACC, on characteristic susceptibility of girth welds of supermartensitic stainless steel pipelines are studied in the present thesis by numerical modelling, which is developed using a available commercial finite element program. Firstly, numerical modelling for simulation of HASCC based on the NACE-TM 0177-96 approach is carried out for providing a basic understanding of the crack propagation behaviour. Secondly, a two dimensional finite element according to the gauge length cross-section of the orbitally welded pipeline is created for numerical modelling in order to calculate the time to failure of welded the component exposed to the NACE electrolyte solution with various H2S saturation. Externally applied loads of a series of constant strain rates and of the load history of full scale testing are also taken into account. Finally, numerical modelling is carried out under three specific aspects, i.e. thermal analysis, structural analysis, and hydrogen diffusion analysis, in order to simulate HACC in supermartensitic stainless steel pipelines welded orbitally by four layers of matching filler wires with an interpass temperature of 40°C.
This thesis investigated gas sensing by means of surface plasmon resonance enhanced ellipsometry. Surface plasmons were excited in a 40 - 50 nm gold layer by a He-Ne-laser using the Kretschmann configuration, which was arranged on a self-made copper measuring cell. A fixed angle of incidence and the ellipsometric parameter Δ as the measured value were used to monitor changes in the gas phase. Different types of gases were investigated: flammable (hydrocarbons and hydrogen), oxidising (oxygen and ozone), toxic (carbon monoxide) and inert (helium and nitrogen). The gas types can be distinguished by their refractive indices, whereas the sensor responds instantly relative to the reference gas with an increase or a decrease in Δ. Diluting the analyte gas with a reference gas (nitrogen or air) allowed the detection limits to be determined, these lay in the low % range. The sensor stability was also enhanced as well as the sensitivity by modifying the gold layers with a 3-10 nm additional layer. These additional layers consisted of the inorganic materials TiO2, ZrO2, MgF2 and Fe: SnO2 which were deposited by different coating processes. Surface investigations were made of every utilised layer: scanning electron microscope and atomic force microscope measurements for surface topology and spectroscopic ellipsometry mapping to determine the optical constants and the layer thicknesses. All applied materials protected the gold layer from contaminations and thus prolonged the life span of the sensor. Furthermore, the detection limits were reduced significantly, to the low ppm range. The material Fe: SnO2 demonstrates a special behaviour in reaction with the toxic gas carbon monoxide: Due to the iron doping, the response to carbon monoxide is extraordinary and concentrations below 1 ppm were detected. In order to approach a future application in industry, the sensor system was adapted to a stainless steel tube. With this measuring arrangement, pulse and pressure experiments could be performed. The probable mechanisms occuring at the sensor surface and feasible applications in the future are discussed in this thesis.
Plasma chemical methods are well suited for introducing functional groups to the surface of chemically inert polymers such as polyolefins. However, a broad variety of functional groups is often formed. Unfortunately, for further chemical processing such as grafting of molecules for advanced applications a highly dense and monotype functionalized polyolefin surface is needed. Therefore, the main task was to develop a selective surface functionalization process, which forms preferably one type of functional groups at the surface in high and variable concentration. Amongst the novel plasma methods, the under-water plasma process (UWP) is one of most attractive to solve the problem of monotype functionalization. Such plasma is an efficient source of ions, electrons, UV-radiation, high frequency shock waves, radicals such as hydroxyl radical and reactive neutral molecules such as hydrogen peroxide, hydrogen and oxygen. It was found that underwater plasma and the closely related glow discharge electrolysis are interesting new methods for polymer surface functionalization. An effective modification into the topmost surface chemistry of polymer layer was observed by the collective effect of wet-chemistry, electrochemistry, atmospheric gas discharges, irradiation, and shock waves. Underwater capillary discharge was seen more effective in -OH functionalization and was largely seen as a flow dominated process because of the shock wave turbulences. Using such water-based plasma a fraction of 25-40% of all O-functional groups was produced as OH-groups in comparison to <10% OH produced in the oxygen low- pressure plasma. The exact concentration of the OH functionality was studied by TFAA gas phase derivatization and measuring the respective fluorine concentration by photoelectron spectroscopy (XPS). In contrast to established gas phase glow discharge processes, the water phase absorbs and therefore limits the particle and radiation energy and thus the energy input into the polymer. Extensive oxidation, degradation, cross-linking and radical formation in the polymer is more limited than under gas plasma exposure because of the liquid water environment, which moderates high energetic plasma species. The variety of plasma produced species in the water phase is also much smaller because of the limited reaction possibilities of the plasma with water. The possibility to admix a broad variety of chemical additives makes underwater plasma additionally highly attractive for the chemist. At last, the water removes all low-molecular weight oxidized products formed by plasma-induced polymer degradation. Hydrogen peroxide and the catalyst (Fe-ZSM5) should influence or increase the equilibrium concentration of OH radicals in the underwater process. It was supposed that these radicals play the most important role for OH functionalization of polyolefin surfaces. Hydrogen peroxide was believed to be the most prominent precursor for OH group formation in the UWP. The catalyst should modulate the steady state of OH group formation and recombination, and thus accelerate the functionalization. This was confirmed by an increased oxidation rate. Owing to the detection limit of XPS the C-O bond selectivity was defined as clearly resolvable subpeak within the C1s signal assigned to C-OH, C-O-C and other singly C-O bonded species. This bondamounts 47 C-O bonds/100 O atoms with pure UWP system and enhances to a maximum of the 81 C-O bonds/100 O atoms using the Fe-ZSM5 catalyst system. Therefore, this method exhibits a great progress for a start. However, after TFAA derivatization the fraction of desired OH groups could not be significantly increased. In the continuation acetic acid, acrylic acid, maleic and itaconic acid were used as additive monomers. The chemical selectivity in -COOH bond formation using bi-carboxylic additives was seen inferior. Acetic acid is not a chemically polymerizing monomer but it could polymerize by monomer/molecular fragmentation and recombination to a cross linked layer. The other monomers form preferably water-soluble polymers on a preferred chemical way. Only the fragmented fraction of these monomers could form an insoluble coating by cross linking to substrate. The XPS analysis was used to track the alterations in COO- bond percentage on the PP surface. To identify the -COOH groups on substrate surface unambiguously, which have survived the plasma polymerization process, the gas phase derivatization with trifluoroethanol was performed. A much higher yield in COOH groups was achieved using the glow discharge electrolysis and acrylic acid.
Glass has different outstanding material-specific properties which offer theoretically the application of thin-walled hollow fibers in the field of high pressure gas storage. Especially the storage of hydrogen as renewable and environmental friendly energy carrier is possible. Glass is an amorphous material which is characterized by a theoretical tensile strength much higher than this of other materials. However, in practice the tensile strength is decreased significantly by defects on the glass surface or in the material and its network structure. As part of this thesis the burst pressures of hollow glass fibers were determined. The burst pressure correlates very well with the tensile strength of hollow glass fibers. By using the Weibull statistic the results of different test series were evaluated in respect to failure probabilities and compared to each other. Thereby the influence of various parameters on the pressure resistance was investigated. Beside the influence of the chemical composition of the material the aging by environmental and their effect on the pressure resistance was investigated. Additionally hollow glass fibers were loaded dynamically and statically with different gases. Afterwards the burst pressure was determined and the effect of used gas on the pressure resistance could be determined as well as the impact of method and duration of loading. A further influence of the dimension of hollow glass fibers on their resistance against inner pressure load is the ratio between wall thickness and inner diameter which was investigated as well as the combination of different glasses and the utilization of their disparate coefficient of thermal expansion which lead to prestressing of the hollow glass fiber. Finally, the impact of the variation of several production parameters on the pressure resistance was determined experimentally as like as the influence of surface coatings. These shall protect the glass surface from subsequently procured defects and, hence, increase the pressure resistance. As essential part of current thesis the defect analysis of test samples of various series was done whereby the differentiation between material and production dependent defects was important. Not only a light microscope but a scanning electron microscope was used for the investigation, as well. Beside volume defects like bubbles or inclusions surface defects in the form of scratches or spalling can be detected and observed. A calculation of the failure-causing defect size from measured burst pressure is possible. Dependent on the dimension and determined burst pressure value of each single fiber defect sizes of less than one micron were calculated. Particularly the geometry of the test samples inappropriate for many examination methods and the fact that the calculated defect size occurs only under loaded conditions at actual burst pressure the local detection of corresponding defect rendered impossible. In the end, the present thesis shows the pressure resistance of hollow glass fibers and their potential to store safely gases under high pressure.
Glass is an amorphous material. When compared to steel, both its density and weight is three times lower. Its high theoretical strength makes it stand out as a premier material for a variety of applications. One such application is acting as a pressure resistant vessel for gas storage. Because glass has a high theoretical strength this makes it potentially suitable to withstand much higher pressures than steel or composite vessels. As a result of its brittle character, glass breaks when reaching a critical stress level. Therefore, the stress distribution during pressure load needs to be homogeneous without local stress peaks. At those peaks an initial crack will occur and the material will break. This PhD thesis is primarily concerned with the determination of the strength of several structures made of single hollow glass fibers during inner pressure treatment. Therefore, different kinds of hollow glass structures with varying parameters of shape and dimension were examined concerning their strength by determining the burst pressure. The burst pressure method was compared to the tensile test method, which poses the common test method for examining the strength of a material. The conclusion reached was that both test methods lead to comparable results and therefore, the burst pressure method poses an adequate tool for examining the strength of a hollow material against inner pressure. Another tool used in this thesis is the Finite Elements Method (FEM) simulation of internal stress and expansion of glass structures during pressure treatment. FEM was used to validate the burst pressure test results. A few selected material parameters needed to be incorporated, most notably the Young’s Modulus. Therefore, the expansion of single glass fibers was measured with light microscope during pressure load. Within the parameters of expansion, wall thickness and applied pressure, the Young’s Modulus was calculated with the Barlow’s Formula. According to the results, different two-dimensional models from single fibers to complex structures with up to 1000 single fibers were constructed and simulated with the CFD software Comsol Multiphysics. The expansion as well as the principal stress during pressure load was calculated. Different dimensions as well as different geometries of the glasses were considered to find a structure with the highest possible free volume and at the same time as less stress peaks as possible. This calculation was made in order to determine the best structure for gas storage. For this purpose the calculations were done with different dimensions of round single fibers right up to hexagonal structures consisting of more than one thousand round single fibers, which resulted in constant expansion of the structure. Furthermore, the problem of occurring interspaces between round single fibers, regarding their burst pressure-decreasing influence, was approached. Closing these interspaces with glass or other materials to avoid unsolicited pressure load led to increased strength of the structure and low storage capacities due to the increased weight and less free inner volume. The behavior of hexagonal fibers was determined as single fiber as well as in bundled condition. The walls between two hexagonal single fibers with applied inner pressure showed homogeneously distributed stress. Merely the outer walls without counter pressure showed high deformation and high structural stress. Based on that knowledge, several structures were modeled varying in different aspects. The fibers with hexagonal shape showed optimal stress distribution and high storage capacities because of high free inner volume, provided that these fibers are surrounded by additional fibers with identical inner pressure. Reducing the wall thickness for even higher free inner volume led to similar distribution but higher stress and expansion. To overcome the problem with the high stress at the outer fibers, the influence of outer fibers with different shape and dimension was simulated as well as the influence of solid glass fibers at the outer layer of the structure. The results showed that a structure with hexagonal thin-walled fibers should be surrounded by round fibers with higher wall thickness. This way the high stress peaks at the outer fibers are lowered. The examined practical strength of glass is about 100 to 1000 times lower than the theoretical strength. This is caused by defects, which may occur at the glass surface by handling or inside the material by defective production. Since the modeled results are based on the theoretical strength, the optimal wall thickness with a good compromise of strength and free inner volume needs to be found in practical tests. If further handling of the structures is necessary, an outer layer of solid fibers works as a protection layer against damages at the outer hollow glass fibers and increases the strength. Additionally, the influence of collapsing fibers inside a structure on the remaining system has been modeled as well as the influence of defects like holes or cracks at the surface or manufacturing induced defects inside the material. Any kind of defect leads to areas of high stress, whereby failure occurrence will be encouraged. In order to approve the theoretical results, the simulated structures were compared to the previously manufactured and tested ones. Due to the burst pressure test results, the tested structures showed low strength compared to the theoretical strength. This was primarily caused by the existence of defects in the material and on the surface of the glass structures. Therefore, the production process needs to be optimized in order to prevent such defects. Furthermore, an additional protection against outer influence like air humidity or the physical contact to other materials is required.
Experimental investigation and CFD simulation of organic peroxide pool fires (TBPB and TBPEH)
(2010)
Time averaged mass burning rate (m˙′′f ), flame length (H), temperature (T ), irradi- ance (E) and surface emissive power (SEP ) of TBPB (tert -butyl peroxybenzoate) and TBPEH (tert-butyl peroxy-2-ethylhexanoate) pool fires are measured for six pool di- ameters (d = 0.059 m, 0.107 m, 0.18 m, 0.5 m, 1 m and 3.4 m) at BAM in house and outside test facility. The measured heats of combustion (–Δhc) of TBPB and TBPEH are 30113 kJ/kg and 34455 kJ/kg and the specific heat capacities at constant pressure (cp) are 1.8 kJ/(kg K) and 2.1 kJ/(kg K) respectively. The measured m˙′′f of TBPB and TBPEH pool fires are in the range of 0.37 kg/(m2 s)≤ m˙ ′′ f ≤ 0.83 kg/(m2 s) and show little dependence on the pool diameter d, and are four to sixty times higher (for d = 1 m) than that of hydrocarbon pool fires. It is shown that the mass burning rates of the investigated organic peroxides can be represented as an exponential function of the self-accelerating decomposition temperature (SADT). Low SADT implies that the organic peroxide pool fires burn at a much higher m˙′′f than hydrocarbon pool fires. Fuel Froude numbers (Frf) of TBPB and TBPEH are 5 to 100 times (depending on d) higher than for hydrocarbon pool fires. Due to higher Frf the H of TBPB and TBPEH (measured with a S-VHS Videocamera) are found to be two times larger (d = 1 m) than corresponding pool fires of hydrocarbons. Heskestads flame length correlation predicts the Hd (d = 3.4 m) of TBPB and TBPEH pool fires much better than Thomas and Fay correlations. The measured time averaged flame temperatures T (d = 3.4 m) for TBPB and TBPEH pool fires are in the range of 1400 K ≤ T ≤ 1500 K and are 200 K to 300 K higher than for JP-4, kerosene and gasoline. The irradiances of the TBPB and TBPEH pool fires measured by radiometers are E (Δy/d = 0.3) = 45 kW/m2 and E = 98 kW/m2 which are two to ten times higher in comparison to the corresponding n-pentane, super gasoline and diesel pool fires. So the thermal safety distances for organic peroxide pool fires are larger by a factor four in comparison to the hydrocarbon pool fires. An infrared thermography system is used for the determination of SEP of TBPB and TBPEH pool fires. The values of surface emissive power for TBPB and TBPEH are SEP (d = 3.4 m) = 196 kW/m2 and SEP = 258 kW/m2 and thus the SEP are by a factor of approximately two higher than for hydrocarbon pool fires. A self-sustained pulsating Hd (’W’-Effect) is found in TBPB pool flames and is further analysed to explain the reason of occurance on the basis of chemical structure of the fuel and discontinuous heat flux back from flame to the liquid pool. CFD simulations of TBPB and TBPEH pool fires at d = 0.18 m, 0.5 m, 1 m, 3.4 m and 8 m are carried out using the Unsteady Reynolds Averaged Navier Stokes (URANS) equa- tions. The three-dimensional geometries have been discritized with unstructured hybrid grids, with the number of cells in the range of 1 million. Depending on the grid resolu- tion and the pool diameter time steps of 0.0001 s ≤ Δt ≤ 0.01 s for the CFD simulations are used. For solving the discritized equations a finite volume based implicit solver AN- SYS CFX has been used. For modelling the combustion, stoichiometric combustion for both peroxides are assumed. The temperature dependence of the reaction rate has been determined by the Arrhenius approach. For modelling the combustion eddy dissipation concept (EDC) model has been used. For turbulence buoyancy modified k- � and SAS (Scale Adaptive Simulation) turbulence models are used. For the thermal radiation and soot mass fraction discrete transfer radiation model and Magnusson soot model have been used. A new method is suggested for the prediction of mass burning rate (m˙′′f ) by CFD simula- tion. Both peroxide pool fires show approximately constant mass burning rate indepen- dent of d whereas m˙′′f of TBPEH are under predicted at the beginning but show relatively good agreement with measurements for large pool diameters (d = 1 m). In case of TBPB the CFD simulation over predicts the mass burning rate m˙′′f of small TBPB pool fires and shows a continuous decrease with d. CFD predicts the flame length H close to the measured data provided that the constants in Thomas equation are modified. The CFD predicted time averaged surface emission flame temperatures of TBPB and TBPEH pool fires (d = 3.4 m, 1437 K and 1542 K) are in good agreement with the measured time averaged flame temperatures. The CFD predicted SEP for TBPB and TBPEH pool fires (d = 3.4 m, 217 kW/m2 and 288 kW/m2) are also in agreement with the measured values. From the CFD predicted irradiance ECFD it is possible to determine the thermal safety distances from large pool fires of hydrocarbons and organic peroxides.
A promising technology in photovoltaics is based on micro-concentrator solar cells, where the photovoltaic active area is realized as an array of sub-millimeter sized cells onto which the incident light is focused via microlenses. This approach allows to increase the cell efficiency and to realize much more compact modules compared to macroscopic concentrator devices. At the same time, expensive raw materials can be saved, which is of interest, for example, with respect to indium in the case of copper-indium-gallium-diselenide (CIGSe) thin film solar cells. Two methods to produce micro-sized precursors of CIGSe absorbers on molybdenum are presented using 30-fs laser pulses at 790 nm wavelength. On the one hand, a multi pulse surface structuring of the molybdenum film or the underlying glass substrate and a subsequent physical vapor deposition were used for a site-selective aggregation of indium droplets. On the other hand, a single pulse laser-induced forward transfer was utilized to selectively deposit combined copper-indium precursor pixels on the molybdenum back contact of the solar cell. Post-processing (selenization, isolation, contacting) of the laser-generated micro-sized precursors results in functional CIGSe solar cells.
The purpose of "The Metallographist":
The results of the important researches regarding metallography are disseminated throughout the scientific papers and transactions of scientific societies chiefly of France, England, Germany and the United States, and even if the busy engineer or metallurgist, the metal producer or consumer in general, had the necessary knowledge of the three languages, and easy access to these publications, he could not possibly find time to go over such an amount of literature in order to extract from it what is of interest and importance to him. This is precisely the work which The Metallographist proposes to do for its readers by presenting to them every three months a clear, exhaustive and comprehensive review of what has been accomplished in metallography during the previous quarter.
The most important articles and memoirs will be reproduced in full, while those of minor importance will be condensed, accompanied in every case by such explanatory notes as will make them comprehensible and fruitful for others besides specialists. The Metallographist will publish moreover, besides the results of the investigations carried on in the Boston Testing Laboratories, original articles by eminent authorities and active workers who have kindly promised their collaboration. The editor will never lose sight of the fact that the importance of these investigations, to the world at large, lies chiefly in their ability to lead to deductions of industrial value, and his presentation of the subject will be conducted accordingly.
Featuring a detailed analysis of current approval requirements and the relevant safety assessment methods for gas cylinders in general and with main focus on composite cylinders for storing ompressed natural gas and hydrogen, this book demonstrates how current regulations and standards limit the ability to reduce cost and weight. Based on this data, it then highlights the potential offered by the proposed approval procedure based on probabilistic safety assessment.
After addressing the economic potential of probabilistic safety assessments, the book details working procedures and improving cycles and (slow) bursts as methods for assessing residual strength. It then discusses methods for statistically evaluating test data, as well as sample- size and distribution character considerations. A definition of sample strength is elaborated in terms of the performance sheets developed by the author. On this basis, it discusses safety as a property of service life and interpreted as an issue of degradation, and explores aspects of artificial aging for simulating the end-of-life reliability level. Lastly, the book considers control and inspection aspects: quality of production, degradation prediction using destructive sample tests parallel to operation, retesting periods and correcting for underand overestimates of safe lifetime.
Presented in schematic diagrams, illustrations and tables, this information enables manufacturers and operators to use this new approach in practice and supports the improvement of current regulations and standards.