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Eingeladener Vortrag
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Im Zuge der Anwendung des Schadens-Toleranz-Prinzips wird ein adäquates zerstörungsfreies Prüfsystem benötigt um strukturelle Integrität sicher zu stellen. Wenn ein zerstörungsfreies Prüfsystem jedoch bis zu den Grenzen der Detektionsfähigkeit beansprucht wird, liefert es keine übereinstimmende Indikationen der Defektentdeckung (Hit/Miss). Deshalb wird dessen Fähigkeit Defekte zu entdecken als Entdeckungswahrscheinlichkeit (POD Probability of Detection) ausgedrückt. In der herkömmlichen 'Signal Response' Signal-Antwort-Zuverlässigkeitsanalyse wird die Entdeckungswahrscheinlichkeit als eine Funktion der Defektgröße angegeben. Die Eignung des Prüfsystems wird durch den Vergleich der Größe des Defektes, der zuverlässig entdeckt wird, mit der des größten zulässigen Defektes, der die strukturelle Integrität nicht gefährdet, verifiziert. Analysen moderner Strukturen zeigen aber, dass auch andere Parameter den Schweregrad des Defektes bzgl. der Integrität der Struktur bestimmen können. Im Rahmen der Multi-Parameter-Zuverlässigkeitsanalyse kann die Entdeckungswahrscheinlichkeit als eine Funktion verschiedener Einflussparameter ausgedrückt werden. Wenn die Eignung des zerstörungsfreien Prüfsystems bestimmt wird, muss die Fähigkeit des Systems Defekte zu entdecken gegenüber dem kritischen Wert genau des Parameters ausgedrückt und geprüft werden, der den Schweregrad des Defektes für die Integrität der Struktur bestimmt. Die Nichterfüllung dieser Forderung kann zur Ablehnung von intakten Teilen oder der Akzeptanz von schlechten Teilen führen. Das Prinzip wird anhand von longitudinalen Ultraschall-Sende-Empfangs-Prüfdaten der Gußeisenmatrix mit oberflächenoffenen, semi-elliptischen, rißartigen Defekten demonstriert.
Das Ziel des Artikels ist es eine Übersicht über neue methodische Ansätze und Verfahren zur Bewertung der Zuverlässigkeit von ZfP-Systemen in Übereinstimmung mit den spezifischen Anforderungen verschiedener industrieller Anwendungen zu geben. Nach einem Überblick über die in den vergangenen Jahrzehnten erreichten Fortschritte, wird der Fokus auf die gegenwärtigen Entwicklungen gerichtet. Für hohe Sicherheitsanforderungen wurde die quantitative Fehlerauffindwahrscheinlichkeit (probability of detection, POD) basierend auf 'hit/miss'- oder 'Signal-Response'-Analysen und die ROC-Analyse (Receiver Operating Characteristics) als typische Werkzeuge entwickelt. Im Rahmen des modularen Modells für die ZfP-Zuverlässigkeit unterscheidet man zwischen den rein physikalisch-technischen Einflussfaktoren, den industriellen Anwendungsfaktoren und den menschlichen Faktoren. Es hilft zum Beispiel zu erkennen, welche dieser Faktoren man in Modellierungsrechnungen bzw. mittels offenen oder Blindversuchen untersuchen kann. Ein neues Paradigma wird für die Betrachtung der POD als eine Funktion der gewählten Systemparameter und somit als Optimierungswerkzeug verwendet, anstelle sie für die endgültige Beurteilung zu nehmen. Zur Handhabung der Zuverlässigkeitsuntersuchung von realen Defekten in einer realistischen Umgebung werden ökonomisch vertretbare, aber dennoch präzise genug arbeitende Methoden, wie der Ansatz von Bayes oder modellbasierte Methoden vorgestellt. Die menschlichen Faktoren sind oft von ausschlaggebender Wichtigkeit für die Gesamtzuverlässigkeit. Hier hilft ein systematischer psychologischer Ansatz die Engpässe und Verbesserungsmöglichkeiten zu finden.
In a systematic approach we synthesized a new series of fluorescent probes incorporating donor–acceptor (D-A) substituted 1,2,3-triazoles as conjugative π-linkers between the alkali metal ion receptor N-phenylaza-[18]crown-6 and different fluorophoric groups with different electron-acceptor properties (4-naphthalimide, meso-phenyl-BODIPY and 9-anthracene) and investigated their performance in organic and aqueous environments (physiological conditions). In the charge-transfer (CT) type probes 1, 2 and 7, the fluorescence is almost completely quenched by intramolecular CT (ICT) processes involving charge-separated states. In the presence of Na+ and K+ ICT is interrupted, which resulted in a lighting-up of the fluorescence in acetonitrile. Among the investigated fluoroionophores, compound 7, which contains a 9-anthracenyl moiety as the electron-accepting fluorophore, is the only probe which retains light-up features in water and works as a highly K+/Na+-selective probe under simulated physiological conditions. Virtually decoupled BODIPY-based 6 and photoinduced electron transfer (PET) type probes 3–5, where the 10-substituted anthracen-9-yl fluorophores are connected to the 1,2,3-triazole through a methylene spacer, show strong ion-induced fluorescence enhancement in acetonitrile, but not under physiological conditions. Electrochemical studies and theoretical calculations were used to assess and support the underlying mechanisms for the new ICT and PET 1,2,3-triazole fluoroionophores.
The internal friction of hydrated soda-lime-silica glasses with total water content (CW ) up to 1.9 wt. % was studied by dynamic mechanical analysis (DMA) using temperature-frequency sweeps from 723 K to 273 K and from 1 s-1 to 50 s-1. Total water content and concentrations of H2O molecules (CH2O ) and OH groups (COH) in the DMA specimens were determined by infrared spectroscopy. For low water contents (CW ≈ COH < 0.25 wt. %) two discrete internal friction peaks below the glass transition (α relaxation) were assigned to the low-temperature motion of alkali ions (γ relaxation) and cooperative movements of dissimilar mobile species under participation of OH at higher temperature (βOH relaxation). For large water contents (CW > 1 wt. %), where significant amounts of molecular water are evident (CH2O > 0.15 wt. %), however, internal friction spectra change unexpectedly: the βOH peak heights saturate and a low temperature shoulder appears on the β-relaxation peak. This emerging relaxation mode (βH2O relaxation) was assigned to the motions of H2O molecules. βH2O relaxation was found to be faster than βOH but slower than γ relaxation. Activation energy of the different relaxation modes increased in the order γ < βH2O < βOH < α.
POD is the most often used approach for the evaluation of the reliability of non-destructive testing methods in critical areas. But especially for those cases the requirements for a sufficient amount of data, adequate type of defects and the statistical requirements are high. The claim for checking these requirements is not new, but never the less often ignored. Especially the large amount of data for critical real defects seems too often to be not really solvable. In this presentation we show an approach to use real defect data with knowledge from former testing results with the same equipment, in a useful adequate way. Furthermore we introduce a method to evaluate the real defect description parameters for the radiographic testing. This approach was used for a joint project with the company POSIVA, which is building a final depository for spent nuclear fuel in Finland. Radiographic testing is one of the NDT-methods they use to test the electron beam weld of the copper canister. The copper canister will be used in the deposit as a corrosion barrier within the deposit concept. Through the high sophisticated manufacturing methods of the canister there are almost no material defects, which could be used for reliability evaluation. In this context the idea of Bayesian Updating of the POD with real defect data with former results from artificial defect data was born to get a useful evaluation.
Using the Modular Reliability Model the three different main influencing elements, i.e. intrinsic capability (IC), application parameters (AP) and the human factors (HF), are, in the first instance, investigated separately. The intrinsic capability stands for the pure physical-technological process of the signal detection caused by the waves or the rays from a material defect in the presence of noise (driven by the material and the devices). This intrinsic capability is the upper bound of the possible reliability. Already when measuring this intrinsic capability for thick walled components the original one-parameter POD must be extended to a multiparameter POD, where, in addition to the defect size, a number of additional physical parameters, such as the grain size distribution (or attenuation), defect depth, and angle or surface roughness, must be considered. For real life cycle assessments it is necessary to evaluate the signal response from real defects. The industrial application factors, e.g. coupling conditions, limited accessibility, heat and environmental vibrations, diminish the reliability. The amount of reduction can be determined quantitatively, if the underlying conditions are controlled. In case they are not controlled it is necessary to count for a fluctuation in the reliability in the field anyway. The third group of important influencing factors are the human factors, which do not only cover the individual performance capability of the inspectors but also the design of the working place,the procedure, the teamwork quality, interaction with systems, the organization, and finally, the relationship between the companies involved in the inspection process and to which extend the responsible parties are aware of it. When comparing an “ideal inspection” with a “real inspection” it is worth while to look how the existing practices, rules and standards support reliable testing and where the “delta” is. In the context of vigor, with respect to the industrial end user, it needs to be shown how the level of reliability of NDE, influenced by the different factors, has an impact on acceptance or rejection of safety critical parts.
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.
The production of agglomerate-free SiO2 particles exhibiting a monomodal distribution of particle sizes of around 300 nm by means of direct laser fuming of micrometric SiO2 powders has been successfully demonstrated. With a 12 kW cw CO2 laser system, a production rate of up to 1 kilogram powder per hour was achieved. Almost ideal spherical amorphous SiO2 particles in a broad particle size distribution between 10 nm and several 100 nm (d50 ≈ 300 nm) were synthesized. Several observations suggest weak agglomeration forces between the particles. A temperature reduction of 200 °C for sintering powder compacts was observed.
The report 'Probability of Defect Detection of Posiva's electron beam weld' describes POD curves of four NDT methods radiographic testing, ultrasonic testing, eddy current testing and visual testing. POD-curves are based on the artificial defects in reference blocks. The results are devoted to the demonstration of suitability of the methods for EB weld testing. Report describes methodology and procedure applied by BAM.
Report creates a link from the assessment of the reliability and inspection performance to the risk assessment process of the canister final disposal project. Report ensures the confirmation of the basic quality of the NDT methods and their capability to describe the quality of the EB-weld.
The probability of detection curves are determined based on the MIL-1823 standard and it's reliability guidelines. The MIL-1823 standard was developed for the determination of integrity of gas turbine engines for the US military.
In the POD-process there are determined as a key parameter for the defect detectability the a90/95 magnitudes, i.e. the size measure a of the defect, for which the lower 95 % confidence band crosses the 90 % POD level. By this way can be confirmed that defects with a size of a90/95 will be detected with 90 % probability. In case the experiment will be repeated 5 % might fall outside this confidence limit.
We present a synchrotron X-ray tomographic study on the morphology of carbon fiber-based gas diffusion layer (GDL) material under compression. A dedicated compression device is used to provide well-defined compression conditions. A flat compression punch is employed to study the fiber geometry at different degrees of compression. Transport relevant geometrical parameters such as porosity, pore size and tortuosity distributions are calculated. The geometric properties notably change upon compression which has direct impact on transport conditions for gas and fluid flow. The availability of broad 3D paths, which are most important for the transport of liquid water from the catalyst layer through the GDL, is markedly reduced after compression. In a second experiment, we study the influence of the channel-land-pattern of the flow-field on shape and microstructure of the GDL. A flow-field compression punch is employed to reproduce the inhomogeneous compression conditions found during fuel cell assembly. While homogenously compressed underneath the land the GDL is much less and inhomogeneously compressed under the channel. The GDL material extends far into the channel volume where it can considerably influence gas and fluid flow. Loose fiber endings penetrate deeply into the channel and form obstacles for the discharge of liquid water droplets.
The H2 effusion from H2 saturated glass powders, H2 permeation through the wall of blown glass bulbs, and H2 permeation through the wall of glass capillaries were applied to evaluate the permeability of hydrogen gas in a barium-aluminoborosilicate (BABS) glass. To validate these methods, two commercial glasses (vitreous silica and borosilicate) were used as a reference. Permeation values obtained from the different experiments agreed within a factor of 3 or less. The H2 permeability of BABS glass at temperatures close to ambient was found to be at least 3 orders of magnitude below that of borosilicate and silica glasses. The powder method, which requires minimal sample preparation efforts, turned out to provide easy access to the measurement of H2 permeability of glasses down to P = 3.9 × 10- 21 mol s- 1 Pa- 1 m- 1.
Since the beginnings of the European American Workshops (EAW) in 1997, the aim was to gather the experts in NDE reliability and discuss burning topics with the aim of identifying crucial problems and suggesting ways to move forward. This was usually achieved during the so-called break-out sessions, in which predetermined topics were discussed. During the 5th EAW, held in Berlin in 2013, this approach was replaced by an Open Space Technology (OST) approach. The benefit of this approach is seen in the freedom of topic choices, i. e., the topics are not predetermined but rather arise at that moment in that space and by the participants choice. The following topics arose: new reliability methods (Bayesian, MAPOD,
), structural health monitoring, definition of requirements of NDE by customer versus provider, what value of POD is good enough?, human factors, manual versus automated inspection, and basic concepts of reliability of NDE. The participants were encouraged to walk from one session to another and openly express their opinions. These were in the end summarized by a chosen group of moderators and presented in this paper.
Forest fires start mostly in partial combustion. In this paper we present a hydrogen sensor to defect early stages of forest fires. First indoor experiments in a smoke density chamber with wood samples, proved that the sensor produce a strong signal change when the smouldering of wood starts, already before the CO concentration, measured in FTIR spectrometry, exceeds 10 ppm. In outdoor experiments we were able to detect forest fire in a distance of 110 m.
The inspection of the sealing weld is an important phase for the evaluation of the acceptability of final disposal canister, but the weld is only a part of the 3D shielding of copper shell. The main tasks for reliable NDT evaluation requires an extensive evaluation of the parameters which contains typical inspection related items like repeatability, S/N ratio, POD, setting up the equipment for inspection, and all practices for inspections. The other parameters are material parameters, their variation must be taken into account in the evaluation of NDT reliability. Further parameters include human factors, i. e. human inspectors and their interaction with technical systems; their effects were studied on an example of the evaluation of eddy current data. Final parameters are related to evaluation of detected defects, which means sizing and base for acceptance and this can be done in different ways. Some examples are given and results are compared with different methods for instance between radiographic testing and ultrasonic testing by raw data analysis and PA-SAFT results. Also, preliminary curves for the evaluation of metallographic results of 55 defects will be shown by EB weld measurements. Some practical items concerning copper inspections will be also discussed related to acceptability.
Bispidines for dual imaging
(2014)
The efficient transformation of the hexadentate bispidinol 1 into carbamate derivatives yields functional bispidines enabling convenient functionalization for targeted imaging. The BODIPY-substituted bispidine 3 combines a coordination site for metal ions, such as radioactive 64CuII, with a fluorescent unit. Product 3 was thoroughly characterized by standard analytical methods, single crystal X-ray diffraction, radiolabeling, and photophysical analysis. The luminescence of ligand 3 was found to be strongly dependent on metal ion coordination: CuII quenches the BODIPY fluorescence, whereas NiII and ZnII ions do not affect it. It follows that, in imaging applications with the positron emitter 64CuII, residues of its origin from enriched 64Ni and the decay products 64NiII and 64ZnII, efficiently restore the fluorescence of the ligand. This allows for monitoring of the emitted radiation as well as the fluorescence signal. The stability of the 64CuII–3 complex is investigated by transmetalation experiments with ZnII and NiII, using fluorescence and radioactivity detection, and the results confirm the high stability of 64CuII–3. In addition, metal complexes of ligand 3 with the lanthanide ions TbIII, EuIII, and NdIII are shown to exhibit emission of the BODIPY ligand and the lanthanide ion, thus enabling dual emission detection.
The present study is dealing with the basic physics for a novel way to generate a free-formed ceramic body, not like common layer by layer, but directly by Selective Volume Sintering (SVS) in a compact block of ceramic powder. To penetrate with laser light into the volume of a ceramic powder compact it is necessary to investigate the light scattering properties of ceramic powders. Compared with polymers and metals, ceramic materials are unique as they offer a wide optical window of transparency. The optical window typically ranges from below 0.3 up to 5 µm wave length. In the present study thin layers of quartz glass (SiO2) particles have been prepared. As a function of layer thickness and the particle size, transmission and reflection spectra in a wave length range between 0.5 and 2.5 µm have been recorded. Depending on the respective particle size and by choosing a proper relation between particle size and wave length of the incident laser radiation, it is found that light can penetrate a powder compact up to a depth of a few millimeters. With an adjustment of the light absorption properties of the compact the initiation of sintering in the volume of the compact is possible.
As subcritical crack growth (SCCG) can reduce tensile strength of glasses by many orders of magnitude, the potential for improvement of fatigue behaviour is most intriguing in developing ultra-strong glasses. An essential bottleneck is the basic understanding of the numerous interplaying pressure-, temperature- and water-affected relaxation phenomena at the crack tip and related toughening strategies. Therefore, the present project aims to advance the basic understanding of structural relaxation effects and local properties caused by increased water concentration and tensile stresses at the crack tip as they are a key for structural toughening designs to develop SCCG-free glasses and glass surfaces.
Our first studies give clear evidence that glass structure and dynamics is strongly modified upon hydration of glasses. These changes are highly related to the nature of network formers but are affected as well by the counter ions (network modifier). Results of the 1st project part suggest that structural relaxation below glass transition temperature, i.e. overlapping of short-range (beta) and long-range (alpha) interactions can contribute to SCCG in water-free environments and that structurally dissolved water in the glasses can have decisive impact on this effect.
In the 2nd project stage specific glasses compositions will be investigated to gain an improved understanding on the relation of sub-Tg relaxation and inert SCCG as well as to shed light to the related effects of dissolved water and its speciation. These glasses cover a broader range of different glass topologies and binding partners, whereby the coupling of alpha and beta relaxations is varied systematically by alkali-, alkaline earth ions and water species concentrations. Preparation of hydrous glasses (up to 8 wt% water) will be performed by high pressure syntheses. Structure will be resolved by NMR, Raman and IR spectroscopy while structural relaxation is accessed in the temperature and frequency domain using dynamic mechanical spectroscopy and ultrasonic damping. We will focus on measurements of inert SCCG (region III) conducting experiments in vacuum and dry gas atmospheres using indentation techniques and stressing of glass specimens in DCB geometry.
Experimental data on SCCG will be provided to SPP groups, which deals with fatigue in metallic glasses and vice versa we will test theoretical predictions of ab-initio simulations of partner within SPP 1594 in order to quantify the effect of water on the crack tip. In summa topological factors controlling the subcritical crack growth with respect to water will be identified from which structural toughening designs for highly fatigue resistant-glasses can be derived.
As subcritical crack growth (SCCG) can reduce tensile strength of glasses by many orders of magni-tude, the potential for improvement of fatigue behaviour is most intriguing in developing ultra-strong glasses. An essential bottleneck is the basic understanding of the numerous interplaying pressure-, temperature- and water-affected relaxation phenomena at the crack tip and related toughening strat-egies. Therefore, the present project aims to advance the basic understanding of structural relaxa-tion effects and local properties caused by increased water concentration and tensile stresses at the crack tip as they are a key for structural toughening designs to develop SCCG-free glasses and glass surfaces.
Our first studies give clear evidence that glass structure and dynamics is strongly modified upon hy-dration of glasses. These changes are highly related to the nature of network formers but are affect-ed as well by the counter ions (network modifier). Results of the 1st project part suggest that struc-tural relaxation below glass transition temperature, i.e. overlapping of short-range (beta) and long-range (alpha) interactions can contribute to SCCG in water-free environments and that structurally dissolved water in the glasses can have decisive impact on this effect.
In the 2nd project stage specific glasses compositions will be investigated to gain an improved un-derstanding on the relation of sub-Tg relaxation and inert SCCG as well as to shed light to the relat-ed effects of dissolved water and its speciation. These glasses cover a broader range of different glass topologies and binding partners, whereby the coupling of alpha and beta relaxations is varied systematically by alkali-, alkaline earth ions and water species concentrations. Preparation of hy-drous glasses (up to 8 wt% water) will be performed by high pressure syntheses. Structure will be resolved by NMR, Raman and IR spectroscopy while structural relaxation is accessed in the temper-ature and frequency domain using dynamic mechanical spectroscopy and ultrasonic damping. We will focus on measurements of inert SCCG (region III) conducting experiments in vacuum and dry gas atmospheres using indentation techniques and stressing of glass specimens in DCB geometry.
Experimental data on SCCG will be provided to SPP groups, which deals with fatigue in metallic glasses and vice versa we will test theoretical predictions of ab-initio simulations of partner within SPP 1594 in order to quantify the effect of water on the crack tip. In summa topological factors con-trolling the subcritical crack growth with respect to water will be identified from which structural toughening designs for highly fatigue resistant-glasses can be derived.
We present an experimental approach to study the three-dimensional microstructure of gas diffusion layer (GDL) materials under realistic compression conditions. A dedicated compression device was designed that allows for synchrotron-tomographic investigation of circular samples under well-defined compression conditions. The tomographic data provide the experimental basis for stochastic modeling of nonwoven GDL materials. A plain compression tool is used to study the fiber courses in the material at different compression stages. Transport relevant geometrical parameters, such as porosity, pore size, and tortuosity distributions, are exemplarily evaluated for a GDL sample in the uncompressed state and for a compression of 30 vol.%. To mimic the geometry of the flow-field, we employed a compression punch with an integrated channel-rib-profile. It turned out that the GDL material is homogeneously compressed under the ribs, however, much less compressed underneath the channel. GDL fibers extend far into the channel volume where they might interfere with the convective gas transport and the removal of liquid water from the cell.
The Collaborative Research Center InPROMPT aims to establish a novel process concept for the hydroformylation of long-chained olefins, using a rhodium complex as catalyst in the presence of syngas. Recently, the hydroformylation in micro-emulsions, which allows for the efficient recycling of the expensive rhodium catalyst, was found to be feasible. However, the temperature and concentration sensitive multi-phase system demands a continuous observation of the reaction to achieve an operational and economically feasible plant operation. For that purpose, we tested the potential of both NMR and Raman spectroscopy for process control assistance. The lab-scale experiments were supported by sampling for off-line GC-analysis as reference analytics. The results of the NMR experiments will be part of another contribution.
Hydroformylation represents an important homogeneous catalyzed process, which is widely used within chemical industry. Usually applied with simple alkenes like Propene and Butene aldehydes obtained from alkenes >C6 are relevant intermediates in production of plasticizers, surfactants and polymers. Today the active catalyst species is often based on valuable Rhodium complexes in aqueous solution. This implies the problem of limited water solubility of the reactands, which is acceptable for short chain lengths, but states a problem in case of higher alkenes. Along with that efficient separation and recycling of the catalyst becomes more complicated. There are different approaches tackling this problem, e.g., by using of salt formation in the BASF process or downstream distillation within the Shell process
Currently at Deutsche Bahn (DB) ultrasonic inspections in maintenance procedures for wheelset axles with a bore hole are, to the greatest possible extent, carried out using automated ultrasonic inspection system. Although the acceptance levels are in accordance with DIN 27201 part 7, the testing results have shown in recent years that in the case of true indications, the effective defect sizes were far below the level of acceptance. Due to this experience it can be assumed that the automated ultrasonic inspection systems are testing substantially more sensitively than required. This increased sensitivity leads to an increase in false indications, generally resulting in the unnecessary demounting of wheelsets. In Research cooperation between Federal Institute for Materials Research and Testing (BAM) and DB the effective flaw detection sensitivity of existing automated ultrasonic inspection system will be determined and the true/false indication ratio optimised. Through systematic investigations with the Probability of Detection method on the existing automated ultrasonic inspection system the results could be directly applied to the optimisation of existing ultrasonic inspections of wheelset axles with a bore hole in maintenance procedures and the level of reliability can be considerably increased.
In context with Japanese disposal and transport container safety assessment the German Federal Institute for Materials Research and Testing (Bundesanstalt für Materialforschung und -prüfung) per-formed extensive drop test series with prototypes of RAM packages in recent years.
The paper presents two cooperative projects focused on project management, testing performance and experimental results.
In the first project, a full-scale prototype of a package for transport and storage of spent fuel elements with a total mass of 127,000 kg and its reduced-scale model which was similar to the prototype in both geometry and design were drop tested in 9 m and 1 m puncture tests at various drop orientations under regulatory conditions. In context with a corresponding research project the test data was used in combination with numerical methods to investigate the phenomenon of internal cask- content collisions during drop tests. Here, technological gaps between basket or radioactive content and cask body or primary lid can be a reason for significant high dynamic loadings of cask components and its internals due to additional impact interactions in the cask cavity caused by inner relative movement between content and cask. Further investigations were carried out in the field of similarity mechanics comparing experimental drop test data of the full-scale prototype and reduced-scale model in regard to the transferability of package impact response from reduced-scale models to full-scale packages.
In the second project, drop tests with a waste container for intermediate depth disposal were per-formed being contracted by Kobe Steel, Ltd. and a consortium of Japanese electric power plant com-panies. The drop test program comprised three single 8-m drop tests in a specimen’s corner edge orientation. For drop tests according to legal regulations for interim storage or final disposal it is often necessary to use a target which represents the real ground of the storage facility. In such cases the container hits directly onto a well-defined concrete slab on top of the IAEA target. Here, the directly impact target for the drop tests were concrete slabs manufactured in Japan and connected by mortar to the impact pad of the unyielding IAEA target.
In the present study we have investigated whether the effect of water on properties of borate glasses resembles that of alkali oxide. Soda-lime-borate glasses with nominal compositions of x Na2O, 10 CaO, (90-x) B2O3 (x = 5, 15 and 25 mol%) were doped with up to 8 wt.% H2O by processing glass powder + distilled water in platinum capsules in an internally heated gas pressure vessel at 1523 K and 500 MPa. The water content of hydrous glasses was determined by Karl-Fischer titration and near-infrared spectroscopy. The glass transition temperature T-g. was derived from DTA and micropenetration experiments for which the effect of water loss at the surface of the hydrous glasses was studied. Heating glass samples at 10 K min(-1) in the DTA resulted in T-g values which are close to T-12 isokom temperatures confirming the equivalence of enthalpy relaxation and viscous relaxation for borate glasses. For all three glass series it is shown that T-g strongly decreases whereas the liquid fragility strongly increases upon the addition of water. These findings reveal that H2O primarily causes breaking of B-O-B bonds rather than supporting 4-fold coordinated boron as it is well-known for alkali oxides in this concentration range. (C) 2015 Elsevier B.V. All rights reserved.
3-Aminovinylquinoxalines are readily accessible from (hetero)aryl glyoxylic acids or heterocyclic π-nucleophiles by consecutive four- and fivecomponent syntheses in the sense of an activation-alkynylation-cyclocondensation-addition sequence or glyoxylation-alkynylation-cyclocondensation-addition sequence in good yields. The title compounds are highly fluorescent with pronounced emission solvatochromicity and protochromic fluorescence quenching. Time-resolved fluorescence spectroscopy furnishes radiative and nonradiative fluorescence decay rates in various solvent polarities. The electronic structure is corroborated by DFT and TD-DFT calculations rationalizing the observed spectroscopic effects.
Condensed-phase mechanisms play a major role in fire-retardant polymers. Generations of development have followed the concept of charring to improve fire properties. Whereas the principal reactions are believed to be known, the specific description for multicomponent systems is lacking, as is the picture across different systems. A two-step approach is proposed in general, and also presented in greater detail. The second step covers the specific reactions controlling charring, whereas the actual reactants are provided in the preceding step. This model consistently incorporates the variety of structureproperty relationships reported. A comprehensive case study is presented on seven phosphorus flame retardants in two epoxy resins to breathe life into the two-step approach.
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.
A series of twelve 3-piperazinyl propenylidene indolone merocyanines was synthesized in a one-pot fashion using a consecutive three-component insertion-coupling-Michael addition sequence. Physicalorganic treatment of the absorption data of a consanguineous series of this library allows semiquantitative Linear Free Energy Relationships (LFERs) to be established and confirmation of the positive Absorption solvatochromicity. All Boc-substituted piperazinyl merocyanines display aggregation induced Emission (AIE), which was corroborated for two solvent systems. In particular, crystallization-induced Emission enhancement (CIEE) induced by ultrasonication could be shown for a model chromophore by confocal laser scanning microscopy (CLSM).
Development of theranostic concepts that include inductively coupled plasma mass spectrometry (ICP-MS) and laser ablation ICP-MS (LA-ICP-MS) imaging can be hindered by the lack of a direct comparison to more standardly used methods for in vitro and in vivo evaluation; e.g. fluorescence or nuclear medicine. In this study a bimodal (or rather, hybrid) tracer that contains both a fluorescent dye and a chelate was used to evaluate the existence of a direct link between mass spectrometry (MS) and in vitro and in vivo molecular imaging findings using fluorescence and radioisotopes. At the same time, the hybrid label was used to determine whether the use of a single isotope label would allow for MS-based diagnostics.
Within the Collaborative Research Center InPROMPT a novel process concept for the hydroformylation of long-chained olefins is studied in a mini-plant, using a rhodium complex as catalyst in the presence of syngas. Recently, the hydroformylation in micro¬emulsions, which allows for the efficient recycling of the expensive rhodium catalyst, was found to be feasible. However, the high sensitivity of this multi-phase system with regard to changes in temperature and composition demands a continuous observation of the reaction to achieve a reliable and economic plant operation. For that purpose, we tested the potential of both online NMR and Raman spectroscopy for process control. The lab-scale experiments were supported by off-line GC-analysis as a reference method.
A fiber optic coupled probe of a process Raman spectrometer was directly integrated into the reactor. 25 mixtures with varying concentrations of olefin (1-dodecene), product (n-tridecanal), water, n-dodecane, and technical surfactant (Marlipal 24/70) were prepared according to a D-optimal design. Online NMR spectroscopy was implemented by using a flow probe equipped with 1/16” PFA tubing serving as a flow cell. This was hyphenated to the reactor within a thermostated bypass to maintain process conditions in the transfer lines.
Partial least squares regression (PLSR) models were established based on the initial spectra after activation of the reaction with syngas for the prediction of unknown concentrations of 1-dodecene and n-tridecanal over the course of the reaction in the lab-scale system. The obtained Raman spectra do not only contain information on the chemical composition but are further affected by the emulsion properties of the mixtures, which depend on the phase state and the type of micelles. Based on the spectral signature of both Raman and NMR spectra, it could be deduced that especially in reaction mixtures with high 1-dodecene content the formation of isomers as a competitive reaction was dominating. Similar trends were also observed during some of the process runs in the mini-plant. The multivariate calibration allowed for the estimation of reactants and products of the hydroformylation reaction in both laboratory setup and mini-plant.
Reaction monitoring in disperse systems, such as emulsions, is of significant technical importance in various disciplines like biotechnological engineering, chemical industry, food science, and a growing number other technical fields. These systems pose several challenges when it comes to process analytics, such as heterogeneity of mixtures, changes in optical behavior, and low optical activity. Concerning this, online nuclear magnetic resonance (NMR) spectroscopy is a powerful technique for process monitoring in complex reaction mixtures due to its unique direct comparison abilities, while at the same time being non-invasive and independent of optical properties of the sample. In this study the applicability of online-spectroscopic methods on the homogeneously catalyzed hydroformylation system of 1-dodecene to tridecanal is investigated, which is operated in a mini-plant scale at Technische Universität Berlin. The design of a laboratory setup for process-like calibration experiments is presented, including a 500 MHz online NMR spectrometer, a benchtop NMR device with 43 MHz proton frequency as well as two Raman probes and a flow cell assembly for an ultraviolet and visible light (UV/VIS) spectrometer. Results of high-resolution online NMR spectroscopy are shown and technical as well as process-specific problems observed during the measurements are discussed.
The in situ analysis of the damage evolution in a metal Matrix composite (MMC) using synchrotron X-ray refraction radiography (SXRR) is presented. The investigated material is an Al alloy (6061)/10 vol% Al2O3 MMC after T6 heat treatment.
In an interrupted tensile test the gauge section of dog bone-shaped specimens is imaged in different states of tensile loading. On the basis of the SXRR images, the relative change of the specific surface (proportional to the amount of damage) in the course of tensile loading was analyzed. It could be shown that the damage can be detected by SXRR already at a stage of tensile loading, in which no Observation of damage is possible with radiographic absorption-based imaging methods.
Moreover, the quantitative analysis of the SXRR images reveals that the amount of damage increases homogeneously by an average of 25% with respect to the Initial state. To corroborate the experimental findings, the damage distribution was imaged in 3D after the final tensile loading by synchrotron X-ray refraction computed tomography (SXRCT) and absorption-based synchrotron X-ray computed tomography (SXCT). It could be evidenced that defects and damages cause pronounced indications in the SXRCT images.
Borosilicate glasses (16Na2O–10B2O3–74SiO2, NBS) with water contents up to 22 mol% H2O were prepared to study the effect of water on structural relaxation using DTA, viscometry and internal friction measurements. The results show that the glass transition temperature Tg of DTA and the isokom temperature T12, of viscometry are in excellent agreement, confirming the equivalence of enthalpy and viscous relaxation for NBS glass. Combining Tg data with water speciation data demonstrates that OH groups are mainly responsible for the decrease of Tg with increasing hydration, while molecular water plays only a minor role. Internal friction spectra at 7.125 Hz confirm the decisive influence of water on mechanical relaxation. The temperature range of α-relaxation (glass transition) strongly decreases while two β-relaxation peaks (sub-Tg) progressively appear with increasing water content. A high temperature β-relaxation peak, attributed to the presence of OH groups, shifts from 670 to 450 K as total water content increases from 0.01 to 5 wt%. A low temperature β-relaxation peak, attributed to molecular water, appears at 380 K and 330 K in glasses containing 3 and 5 wt% H2O, respectively. These findings suggest that relaxation mechanism of different hydrous species at low temperature may contribute to fatigue of stressed glasses.
Aggregation-induced emission (AIE) has been meanwhile observed for many dye classes and particularly for fluorophores containing propeller-like groups. Herein, we report on the AIE characteristics of a series of four hydrophobic pyrrolidinylvinylquinoxaline (PVQ) derivatives with phenyl, pyrrolyl, indolyl, and methoxythienyl substituents used to systematically vary the torsion angle between this substituent at the quinoxaline C2 position and the planar PVQ moiety. These molecules, which are accessible via four- or five-component one-pot syntheses, were spectroscopically studied in organic solvents and solvent−water mixtures, as dye aggregates, solids, and entrapped in polystyrene particles (PSP). Steady-state and time-resolved fluorescence measurements revealed a strong fluorescence enhancement for all dyes in ethanol−water mixtures of high water content, accompanying the formation of dye aggregates with sizes of a few hundred nm, overcoming polarity and H-bonding-induced fluorescence quenching of the chargetransfer-type emission of these PVQ dyes. The size and shape of these dye aggregates and the size of the AIE effect are controlled by the water content and the substituent-dependent torsion angle that influences the nucleation process and the packing of the molecules during aggregation. Staining of 1 μm-sized carboxy-functionalized PSP with the PVQ dyes resulted also in a considerable increase in the fluorescence quantum yield and lifetime, reflecting the combined influence of the restricted molecular motion and the reduced polarity of the dye microenvironment.
For the first time, X-ray refraction techniques are proven for the identification of void formation in Ti-6Al-4V parts produced by selective laser melting. The topology and volume fraction of pores are measured in samples produced with different laser energy density. Unique X-ray refraction methods identify different kinds of defects, characteristic to the regions below and above the Optimum laser energy density, namely unprocessed powder (unmolten powder particles, balling effect, and Fusion defects) from empty keyhole pores. Furthermore, it is possible to detect small inhomogeneities (voids or cracks) with sizes below the spatial resolution of optical microscopy and X-ray computed tomography.
Microstructure characterisation of advanced materials via 2D and 3D X-ray refraction techniques
(2018)
3D imaging techniques have an enormous potential to understand the microstructure, its evolution, and its link to mechanical, thermal, and transport properties. In this conference paper we report the use of a powerful, yet not so wide-spread, set of X-ray techniques based on refraction effects. X-ray refraction allows determining internal specific surface (surface per unit volume) in a non-destructive fashion, position and orientation sensitive, and with a nanometric detectability. We demonstrate showcases of ceramics and composite materials, where microstructural parameters could be achieved in a way unrivalled even by high-resolution techniques such as electron microscopy or computed tomography. We present in situ analysis of the damage evolution in an Al/Al2O3 metal matrix composite during tensile load and the identification of void formation (different kinds of defects, particularly unsintered powder hidden in pores, and small inhomogeneity’s like cracks) in Ti64 parts produced by selective laser melting using synchrotron X-ray refraction radiography and tomography.
The water management in proton exchange membrane fuel cells (PEMFC) is strongly influenced by the design of the gas diffusion layers (GDL). Limiting current measurements in small-scale cells operating at high stoichiometries are useful to determine the oxygen transport resistance. The oxygen transport resistance increases, once water condenses inside the GDL. In this study a new electrochemical method for voltage loss estimation of GDL induced oxygen transport losses are presented. This new method, referred to as “transient limiting current” (TLC), is compared with the literature method. TLC allows a direct estimation of oxygen transport resistance at an arbitrarily conditioned state. This study also presents a case study of liquid water visualization of a PEM fuel cell with varying GDLs types.
With the help of quasi in-situ synchrotron X-ray computed tomography and time resolved radiography measurements we investigate appearance and distribution of liquid water inside the GDLs under limiting current conditions.
Glass-ceramics are noted for their unusual combination of properties and manifold commercialized products for consumer and specialized markets. Evolution of novel glass and ceramic processing routes, a plethora of new compositions, and unique exotic nano- and microstructures over the past 60 years led us to review the Definition of glass-ceramics. Well-established and emerging processing methods, such as co-firing, additive manufacturing, and laser patterning are analyzed concerning the core requirements of processing glass-ceramics and the Performance of the final products. In this communication, we propose a revised, updated definition of glass-ceramics, which reads “Glass-ceramics are inorganic, non-metallic materials prepared by controlled crystallization of glasses via different processing methods. They contain at least one type of functional crystalline phase and a residual glass. The volume fraction crystallized may vary from ppm to almost 100%”.
Issues that prevent Structural Health Monitoring (SHM) based on Guided Waves (GW) from being a part of today’s monitoring solutions in industry are not all obvious to the scientific community. To uncover and overcome these issues, scientists working on SHM and GW problems joined in an expert committee under the patronage of the German Society for Non-Destructive Testing. An initiated online survey among more than 700 experts and users reveals the hurdles hindering the practical application of GWbased SHM. Firstly, methods for proof of reliability of SHM approaches are missing.
Secondly, detailed understanding of phenomenological described wave-damage interactions is needed. Additionally, there are significant unsolved implementation issues and unsolved problems of signal processing including handling of environmental influences.
To enable substantial proof of reliability without unaffordable experimental effort also efficient simulation tools including realistic damage interaction are needed, enabling the joint use of experimental and simulated data to predict the capabilities of the Monitoring system. Considering these issues, the committee focusses on simulation, signal processing, as well as probability of detection and standardization. In the presented work, recent activities of the expert committee starting with survey results are summarized. An open access data basis of life-like measurements is presented to allow testing and comparison of signal processing and simulation algorithms. Finally, a strategy for efficient proof of reliability increasing the acceptance of SHM in industry and for successful Integration of SHM into real-world engineering structures is proposed.
Hydrogen gas diffusivity of fourteen glasses of the Na2O-Al2O3-SiO2 system are studied along the joins quartzalbite-jadeite-nepheline (Qz-Ab-Jd-Np, fully polymerized) and albite-sodium disilicate (Ab-Ds, depolymerized).
Density measurements show that ionic porosity decreases from 54.4% (Qz) to 51.5% (Np) and from 52.4% (Ab) to 50.2% (Ds). Hydrogen diffusivity D follows similar trends but at another scale. D at 523 K decreases from 4×10−12 to 3×10−14m2 s−1 (Qz-Np) and from 4×10−13 to 3×10−15m2 s−1 (Ab-Ds). Charge compensating Na+ acting as a filling agent in fully polymerized network structures leads to up to one order of Magnitude higher diffusivities as depolymerized glass structures of the same SiO2 content where Na+ takes the role of a
modifier ion. Temperature dependence of the diffusivity indicates that both the activation energy involved with the moving H2 molecule as well as the accessible volume in the structure contribute to this compositional trend.
Due to the stochastic nature of crack nucleation by Vickers indentation, a statistical analysis of propagation rates of 185 radial cracks was performed. Crack growth was observed directly using a video camera with high Image acquisition rate. It is found that propagation rates are controlled by the environmental reactions at the crack-tip shortly after their initiation (< 1 s). Calibration of the stress intensity KI showed that the residual stress factor χ and the exponent n of the equation KI==χPc−n (with P==load and c==crack length) are broadly distributed among the 185 analyzed cracks, ranging from 10−16 to 104 and from 0.1 to 5, respectively. For the most frequent crack, the equation KI==0.052Pc−1.47 holds. The results show that correlations of indentation-induced crack length to stress intensity necessitate the use of statistical significant data that are calibrated by the environmental reactions at the crack-tip.
To understand the impact of dissolved water on structure and properties, four boron-rich glasses of molar compositions 15-x Na2O x CaO 15 SiO2 70 B2O3 (with x=0, 7.5, 10) and 10 Na2O 15 SiO2 75 B2O3 were prepared and subsequently hydrated (up to 8 wt% H2O). Density measurements show a non-linear trend upon hydration implying large structural changes in particular at water contents<2 wt%. Near-infrared spectroscopy shows hydroxyl groups are the dominant species in all glasses upon the entire range of water content. Molecular H2O is detectable only at total water contents>2 wt%. 11B MAS NMR spectra show that the abundance of BO4 species is mainly controlled by ratio of (Na2O+CaO)/B2O3 while incorporation of water plays a minor role.
Compared to borate glasses, the efficiency of formation of BO4 tetrahedra is favored by crosslinking of the network by SiO4-units. The glass transition temperatures, determined by differential thermal analysis, decreases continuously with water content due to breakage of B-O-B bonds by hydrolysis. However, compared to Silicates and aluminosilicates, the effect of dissolved water is less pronounced which can be explained by weaker B-O-B bonds in comparison to Si-O-Si bonds.
The effect of structural water on density, elastic constants and microhardness of water-bearing soda-lime-silica glasses of up to 21.5 mol% total water is studied. It is found that the Poisson ratio and the water content are positively correlated, while density and the elastic moduli decrease with increasing water content. Vickers hardness decreases by approximately 27% from the dry to the most hydrous glass. For water fractions <3 mol%, the dependencies are non-linear reflecting the non-linear change in the concentrations of OH and H2O molecules dissolved, whereas for water fractions >3 mol% linear dependencies are found. To distinguish the effect of structural water and environmental water, indentations were performed in toluene, nitrogen gas and air. Timedependent softening was evident for testing dry glasses in humid atmospheres as well as for tests of hydrous glasses in dry atmospheres. This indicates that the response times of dissolved water species are effectively equal in both scenarios.
Wild bees are important pollinators for agricultural crops and solitary species such as Osmia bicornis are particularly suitable for pollination management. Wild bees share floral resources with managed honey bees and may be exposed to emerging infectious diseases. Although studies have explored the prevalence of pathogens in solitary wild bee species, data regarding the impact of pathogens on solitary bee health are lacking.
We carried out experiments examining whether the solitary bee species O. bicornis is susceptible to infection with the emerging pathogen The results obtained indicate that N. ceranae may be able to infect O. bicornis but its impact on host fitness is negligible: survival rates did not differ between Control and inoculated bees, although male survival was marginally lower after infection. To explore the possible field-relevance of our findings, we collected wild bees near an infected and a non-infected hive and showed that N. ceranae was shared between managed and wild bees, although only the in presence of infected honey bees.
The findings of the present study show that O. bicornis is susceptible to pathogen spillover and could act as a potential reservoir host for N. ceranae in pollinator networks. Additional studies on this species incorporating sublethal effects, multiple infections and other interacting stressors are warranted.
Wild bees are important pollinators of wild plants and agricultural crops and they are threatened by several environmental stressors including emerging pathogens. Honey bees have been suggested as a potential source of pathogen spillover. One prevalent pathogen that has recently emerged as a honey bee disease is the microsporidian Nosema ceranae. While the impacts of N. ceranae in honey bees are well documented, virtually nothing is known about its effects in solitary wild bees.
The solitary mason bee Osmia bicornis is a common pollinator in orchards and amenable to Commercial management. Here, we experimentally exposed larvae of O. bicornis to food contaminated with N. ceranae and document spore presence during larval development. We measured mortality, growth parameters, and timing of pupation in a semi-field experiment. Hatched individuals were assessed for physiological state including fat body mass, wing muscle mass, and body size. We recorded higher mortality in the viable-spore-exposed group but could only detect a low number of Spores among the individuals of this treatment. Viable-spore-treated individuals with higher head capsule width had a delayed pupation start. No impact on the physiological status could be detected in hatched imagines. Although we did not find overt evidence of O. bicornis infection, our findings indicate that exposure of larvae to viable N. ceranae spores could affect bee development.
To explore the impact of ambient and structural water on static fatigue, the initiation and growth of 3279 Vickers induced median radial cracks were automatically recorded and analyzed. We find that humidity is more efficient in initiating cracks and promoting their growth than water, which is dissolved in the glass structure. In particular for slow crack growth (< 3x10-6 m s-1), tests in dry nitrogen showed a considerable decrease in the crack growth exponent with increasing water content of the glasses. On the other hand, if tests were performed in humid air, the crack growth exponent was independent of the water content of the hydrous glasses, while stress intensity decreased slightly. These observations indicate that water promotes the processes at the crack-tip regardless of its origin. However, ambient water is more efficient.