BAM Forschungsberichtreihe
Filtern
Dokumenttyp
- Forschungsbericht (14)
Sprache
- Englisch (14) (entfernen)
Referierte Publikation
- nein (14)
Schlagworte
- Bio-no-tox oils (1)
- Bio-oils (1)
- Carbocyanine (1)
- Dephasing (1)
- EAL (1)
- Eco-lubricants (1)
- Energy relaxation (1)
- Engine oil (1)
- Ester (1)
- Exciton dynamics (1)
242
Glühentladung optischer Ausstrahlungsspektroskopie (GDOES) wurde ursprünglich für die elementare Analyse von Größenmaterialien entwickelt. Mehrere Gruppen führten diese Methode zur Analyse von Anstrichen, Laienstapeln und dünnen Filmen durch. In den frühen Neunzigern wurde eine ISO-TC 201-Arbeitsgruppe gegründet, um Normen für alle Formen der Glühentladungsspektroskopie (GDS) zu entwickeln und die Fähigkeiten der Oberflächenchemikalien-Analyse zu beurteilen, insbesondere für die Tiefe von gestuften Systemen. Die Quantifizierung von Tiefenprofilen, d.h. die Umwandlung von Intensitäts-Zeit- Profilen in Konzentrierungs-Tiefen-Profile ist für dc-mode entwickelt worden. 1997 wurde ein VAMAS TWA 2 Vorschlag für ein Referenzanstrich für GD-OES Tiefe gemacht. Entsprechend dem VAMAS Beurteilungsverfahren wurde dieser Vorschlag 1998 mit einigen geringfügigen Änderungen genehmigt.
30
Two introductory reports on a Systems approach to tribology, refs (1) and (2), have been discussed at the previous meeting of IRG-OECD (London, 1973). The new concepts derived from General Systems Theory, and Mathematical Systems Analysis are combined in the present report and applications in tribology are worked out in greater detail.
In introducing the subject it is pointed out once more:
(i) all tribo-mechanisms are by definition complex Systems;
(ii) friction and wear are operators of tribo-systems (in terms of either a verbal or a mathematical theory of sets);
(ii) therefore friction coefficients and wear rates cannot be instrinsic material properties.
The nature of complexity in the verbal description of tribo-mechanisms is analyzed, and logical ruies, needed in the analytical procedure, are given;the mathematics are summarized in the Appendix.
A general classification of tribo-mechanisms is developed by step-wise analysis, and mathematical expressions for friction and wear processes in steady state Systems are given.
The recent experimental advances made by IRG-OECD (refs (15) and (16)) on failure criteria in thin film lubrication are presented in the terminology of Systems analysis, but merely äs an example for the formalization of non-linear tribo-processes.
It is concluded that neither the verbal nor the mathematical Systems analysis have, at present, more predictive power than a conventional Interpretation of experimental results. However, dangerous logical errors in the concepts of friction and wear can now be eliminated and, by doing so, a new outlook on tribometry is gained. The practical engineering consequences for the future, functional control of tribo-machinery have already been predicted by Schlösser (ref. 18).
280
Permeable reactive barriers (PRBs) offer an alternative as opposed to more cost-intensive active methods for groundwater remediation, e.g. pump-and-treat. Long-term performance of PRBs, however, is crucial for the technology’s success. The paper summarises the results of long-term column experiments with elemental iron (Fe0) and hydroxyapatite (HAP) as reactive materials for the removal of uranium from groundwater. Good removal results have been achieved using elemental iron with possible reaction paths being reductive precipitation and adsorption on to corrosion products of Fe0.
235
The present work is focused on the study of the spectroscopic and complexometric behavior of different ion-sensitive fl uorescent probes. Three of the four types of probes studied follow a conventional principle of signal generation and their molecular constitution corresponds to either a fl uorescent ligand ( BP(OH)2), so-called intrinsic charge transfer (ICT) fl uorescent probes (donor- acceptor-substituted chalcones), or electron transfer (ET) fl uorescent probes (substituted triaryl-Δ2- pyrazolines). The latter two systems are designed in a modular way and thus, both the signal generating fl uorophore and the complexing receptor can be carefully tuned. Whereas in the case of the ICT probes both units are electronically conjugated, these moieties are more or less electronically decoupled in the ET probes and signal generation is based on the modifi cation of a long range electron transfer process. The fourth type of probe investigated, a boron dipyrromethene derivative (BDP), is also designed in a modular way. But here, due to the highly pretwisted constitution of the molecule, fl uorophore and receptor are only “virtually” decoupled. Besides employing this alternative mechanism of signal generation, control of the selectivity by carefully directed receptor design and improvement of the selectivity and sensitivity of fl uorometric metal ion analysis by recording time resolved emission spectra (TRES) were the main aims of these investigations. Furthermore, with the aid of various model compounds, NMR spectroscopy as well as quantum chemical calculations, a fundamental understanding of the photophysical behavior of the different classes of dyes was obtained. In accordance with its parent compound 2,2‘- bipyridyl, the fl uorescent ligand BP(OH)2 shows complexation induced changes of its absorption and emission behavior in the presence of heavy and transition metal ions. Whereas paramagnetic ions such as CuII or NiII (and also HgII) lead to static fl uorescence quenching, the diamagnetic ions ZnII and CdII form strongly fl uorescent complexes with ion specifi c fl uorescence lifetimes in the ns time range. Both complexes are stable in the excited state which is manifested by a strongly reduced rate constant of non radiative deactivation compared to that of the free ligand. Both the absorption and emission spectra of the complexes largely overlap and a discrimination with steady-state fl uorometry is very limited. Nevertheless, with time resolved fl uorometry a separation of both components is possible and for a series of synthetic ZnII/CdII containing samples this gain in selectivity by global analysis of the time resolved emission spectra (TRES) could be demonstrated. The intrinsic fl uorescent probes of chalcone type contain a cation selective receptor in the donor part of the molecule and show a strong decrease of the intramolecular charge transfer process due to complexation induced weakening of the donor. Depending on molecular probe design and solvent polarity, the fl uorescence of the uncomplexed molecule occurs either from a polar directly exicted (E*) or a highly polar charge transfer state (A*) which is populated via an excited state reaction involving single bond twisting. Here, competing processes include population of a non emissive polar (K*) or weakly polar (P*) transient state. Furthermore, the fl uorescence of these dyes can be quenched by energetically close lying nπ* states (in apolar solvents) or by enhanced internal conversion due to the decreasing energy gap between ground and excited state (in highly polar solvents). As mentioned above, the donor strength is reduced upon cation complexation in polar solvents and a moderate fl uorescence enhancement occurs. Besides increased fl uorescence quantum yields, this effect results in ion specifi c fl uorescence lifetimes of the complexes. Upon exchanging the aza oxa for an aza thia macrocycle in the receptor part of the system, the cation selectivity could be tuned from alkali and alkaline earth metal ions to the thiophilic metal ions AgI and HgII. Here, especially the fl uorescence enhancement in the presence of the well-known quencher HgII is analytically valuable. Upon cation binding the ET probes of the triaryl-Δ2-pyrazoline type show very small spectral shifts but much larger fl uorescence enhancement compared to the ICT probes. Again, by problem specifi c use of different receptors, the selectivities can be controlled. Based on a detailed investigation, for the 5-p-N,N-dialkylanilino-3-benzthiazol-1-phenyl-Δ2-pyrazolines, the intramolecular processes which lead to fl uorescence quencing in the unbound state and “switching on” of the fl uorescence in the complexed state could be identifi ed. For these molecules, the intramolecular charge transfer in the basic chromophore occurs in the sub ps time range and is quenched by an electron transfer process from the largely electronically decoupled receptor to the acceptor part of the basic chromophore on the ps time scale in highly polar solvents. “Virtually” decoupling fl uorophore and receptor in the BDP derivative fi nally makes it possible to yield extremely high complexation induced fl uorescence enhancement signals. For these highly pretwisted donor acceptor biaryls, the directly excited emissive state (LE) forms a highly polar, twisted charge separated charge transfer state (CT) in polar solvents. Emission of the latter is strongly forbidden and, depending on solvent polarity, is largely red shifted compared to the LE fl uorescence. Thus, a largely separated dual fl uorescence is already observed in solvents of medium polarity and in highly polar solvents both fl uorescence bands are nearly completely quenched. Metal ion complexation blocks off the CT process and leads to a “switching on” of the LE emission yielding fl uorescence enhancement factors > 1000. This process is so sensitive that for most of the cation complexes studied, two emissive complex conformers with strongly overlapping absorption and emission spectra occur which could be distinguished by their fl uorescence lifetimes.
193
The present Technical Report was written with the intention of fulfilling for needs: (i) for an introduction of research workers in the Technical Working Areas (TWAs) of VAMAS to modern statistical methods and techniques appropriate to improve the effectiveness of experimental research in the scope of the VAMAS co-operative projects in materials science and engineering; (ii) for illustrating the power of such approaches by giving an outline of more recent applications in science and technology; (iii) for developing a feeling on the role and importance of statistical consulting under these circumstances; and (iv) for presenting objectives and a programme to provide and promote statistical consulting within VAMAS by developing the TWA / Advisory Group “Statistical Techniques for Interlaboratory Studies and Relates Projects”.
259
Englische Übersetzung von BAM Forschungsbericht 237! Keramische Werkstoffe haben auf Grund ihrer herausragenden tribologischen Eigenschaften in verschiedenen Bereichen der Produktion Anwendung gefunden und dadurch klassische Werkstoffe verdrängt. Gegenüber Metallen bieten sie bei Mangelschmierung sowohl unter Gleit- als auch grundsätzlich unter Wälzbeanspruchung Schutz vor adhäsivem Versagen. Hohe Herstellungskosten, bedingt bei der Endbearbeitung von Konturen mit verschiedenen und veränderlichen Radien, behindern die breite Marktdurchdringung. Mit der Modellverschleißprüfung - angelehnt an die DIN 50 324 - kann der bearbeitungsbedingte Einfluss auf das tribologische Verhalten unter Wälzreibung untersucht werden.
245
Die Reduzierung von Schadstoffen im Grundwasser mit reaktiven Wänden ist eine neuartiges passives Sanierungsverfahren. Die am häufigsten angewandten Dekontaminierungsprozesse sind dabei chemische Reduktion, Oxidation, Ausfällung und Sorption, die im Bericht beispielhaft dargestellt sind. Blei, Chrom und insbesondere Uran werden unter den anorganischen Schadstoffen detailliert behandelt, da solche Grundwasserverunreinigung in vielen europäischen Ländern auftreten. Baumethoden für Dichtwände und reaktive Wände weisen gemeinsame Merkmale auf. Neben den gewöhnlichen Methoden werden Bohrverfahren, deep-soil-mixing, Strahltechnologien, Brunnengalerien, Injektionssysteme und Biobarrieren angewendet, um reaktive Wände zu errichten. Die Technik der reaktiven Wände besitzt ein großes Potential für die Sanierungstechnik der Zukunft.
289
Because they are laid underground and because their job is to connect widely distant places, pipelines have some particular technical safety features. Chemical industry installations have fixed and instantly recognisable sites. Pipeline routes must be adapted to the constraints of infrastructure and topography, and environmental protection must be taken into account, as well as the possibility that the pipe system may be damaged by external influences. Even minor leakages can have considerable effects on watercourses and the soil, and in many cases, people are also injured. Numerous incidents abroad have proved this. In the recent past, even Germany has not been spared from sudden damage to pipelines. However, not much notice was taken of these incidents, as the resulting damage was minor and there were no fatalities. With hindsight, when seeking the causes of the damage, it is often the case that the rupture of a pipeline is associated with certain recurring features. The scene of the damage is often located near traffic infrastructure. Pipelines must of necessity cross roads and railways or are laid in parallel to such lines of communication. As a result of vibrations caused by traffic, this proximity can lead to ruptures. Road or rail accidents can lead to stresses which pipelines are unable to withstand. But a pipeline failure can have many other causes which cannot be predicted with any certainty and which even show regional particularities. In the interests of safe transport and land planning, it would therefore be worthwhile to be able to evaluate at least the possible consequences in terms of damage that might result from a pipeline rupture. There are hardly any publications on pipeline accidents, at least in German speaking countries; most of what is available is in the form of reports by the fire services. However, these are not sufficient to provide an overview of the situation. For this reason, the Federal Institute for Materials Research and Testing has evaluated many international reports of investigations and publications and summarised what they have to say about the risks inherent in pipeline failures, particularly the damage that results. This report is the outcome of this work.
249
In der vorliegenden Arbeit wird die Ultraschallausbreitung in akustisch anisotropen, homogenen Werkstoffen mit stengelkristalliner Textur wie austenitischen Plattierungen und Schweißverbindungen, austenitischem Guss oder geschweißten Komponenten aus austenitischem Gus modelliert. Die Ergebnisse dieser Arbeit dienen als Vorgabe für Prüfanweisungen und Regelwerke, die besser als bisher an den Prüfgegenstand angepasst sind.
277
The use of alternative oils for the lubrication of automobile engines has a potential of ecological and technical advantages. It requires the detailed knowledge of several thermophysical and viscometric properties in a large temperature range (mapping). Therefore, the following properties of up to twenty-eight different oils have been measured in the temperature range from 22 °C to 150 °C: density, heat capacity, thermal conductivity, viscosity at ambient pressure, viscosity under shear rates above 10 6 s-1, and the viscosity at elevated pressures (maximum 100 MPa). The last two have been measured with a substantially improved and a newly developed apparatus, respectively. The pressure- viscosity coefficient has been measured on four hydrocarbon-based, factory-fill oils, a paraffin oil and twenty-three alternative oils. Nine of the alternative oils are based partly or completely on esters, the other fourteen on polyglycols, two of them additionally on water.