BAM Dissertationsreihe
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- Antibody (1)
- Automation bias (1)
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- Degradation of Mechanical Properties (1)
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- Failure modes and effects analysis (1)
154
Pharmacologically active compounds are omnipresent in contemporary daily life, in our food and in our environment. The fast and easy quantification of those substances is becoming a subject of global importance. The fluorescence polarization immunoassay (FPIA) is a homogeneous mix-and-read format and a suitable tool for this purpose that offers a high sample throughput. Yet, the applicability to complex matrices can be limited by possible interaction of matrix compounds with antibodies or tracer.
Caffeine is one of the most frequently consumed pharmacologically active compounds and is present in a large variety of consumer products, including beverages and cosmetics. Adverse health effects of high caffeine concentrations especially for pregnant women are under discussion. Therefore, and due to legal regulations, caffeine should be monitored. Automated FPIA measurements enabled the precise and accurate quantification of caffeine in beverages and cosmetics within 2 min. Samples could be highly diluted before analysis due to high assay sensitivity in the low μg/L range. Therefore, no matrix effects were observed.
The antiepileptic drug carbamazepine (CBZ) is discussed as a marker for the elimination efficiency of wastewater treatment plants and the dispersion of their respective effluents in surface water. The development of a FPIA for CBZ included the synthesis and evaluation of different tracers. Using the optimum tracer CBZ-triglycine-5-(aminoacetamido) fluorescein, CBZ concentrations in surface waters could be measured on different platforms: one sample within 4 min in tubes or 24 samples within 20 min on microtiter plates (MTPs). For this study, a commercially available antibody was used, which led to overestimations with recovery rates up to 140% due to high cross-reactivities towards CBZ metabolites and other pharmaceuticals.
For more accurate CBZ determination, a new monoclonal antibody was produced. In this attempt, methods for improving the monitoring during the production process were successfully applied, including feces screening and cell culture supernatant screening with FPIA. The new monoclonal antibody is highly specific for CBZ and showed mostly negligible cross-reactivities towards environmentally relevant compounds. Measurements at non-equilibrium state improved the sensitivity and selectivity of the developed FPIA due to slow binding kinetics of the new antibody. Additionally, this measure enables for CBZ determination over a measurement range of almost three orders of magnitude. The comprehensively characterized antibody was successfully applied for the development of sensitive homogeneous and heterogeneous immunoassays.
The new antibody made the development of an on-site measurement system for the determination of CBZ in wastewater possible. After comprehensive optimization, this automated FPIA platform allows the precise quantification of CBZ in wastewater samples only pre-treated by filtration within 16 min. Recovery rates of 61 to 104% were observed. Measurements in the low μg/L range are possible without the application of tedious sample preparation techniques.
Different FPIA platforms including MTPs, cuvettes and tubes were successfully applied. For the choice of the right format, the application field should be considered, e.g. desired sample throughput, usage for optimization or characterization of antibodies or if a set-up for routine measurements is sought for. For high sample throughput and optimization, FPIA performance on MTPs is advantageous. The best results for the application to real samples were obtained using kinetic FP measurements in cuvettes.
152
Trans-Zearalenone(ZEN)is a non-steroidal estrogenic mycotoxin which frequently contaminates cereal grains worldwide. Ingestion of food and feed containing ZEN causes numerous mycotoxicoses in animals and possibly humans with pronounced estrogenic effects. Due to the trans-configurated double bond, ZEN isomerizes to the cis-configuration upon the influence of light. This work investigates the instrumental analysis, metabolism and toxicity of ZEN and cis- ZEN. The first part focused on the determination of ZEN in edible oils. Due to a maximum level of 400 µg/kg ZEN in the European Union (EU), reliable analytical methods are needed. A comprehensive method comparison proved dynamic covalent hydrazine chemistry (DCHC) to be the most suitable approach. Thus, an automated solid phase extraction (SPE) coupled online to high performance liquid chromatography (HPLC) was developed with the novelty of a covalent SPE step comprising the DCHC principle. The automated online system allows an accurate, selective and reliable quantification of ZEN in edible oils in compliance with EU performance criteria while significantly reducing workload and thereby personnel costs. In contrast to ZEN, reference standards and analytical methods are missing for cis- ZEN which causes a lack of data on the occurrence, fate and risks of cis-ZEN. Therefore, a native and an isotopically labeled cis-ZEN standard were synthesized and implemented in an existing stable isotope dilution analysis HPLC tandem mass spectrometry (HPLC-MS/MS) method. Using this method, a large extent of cis-ZEN formation was observed for ZEN contaminated maize germ oils when exposed to daylight which confirms that cis-ZEN can be a relevant food contaminant and should be considered in the analysis of food and feed. Furthermore, this work investigated the in vitro phase I metabolism of ZEN and cis-ZEN in rat and human liver microsomes by using HPLC-MS and -MS/MS analyses. The metabolic pathways of cis-ZEN were found to be essentially similar to ZEN including reduction and oxidation reactions generating α- and β-cis- zearalenol as well as 13- and 15-OH-cis-ZEN. A previously unidentified oxidative metabolic pathway for both isomers of ZEN results in the formation of cis-ZEN-11,12-oxide and ZEN-11,12-oxide in human liver microsomes. The estrogenicity of cis-ZEN and its reductive metabolites was assessed using the E-Screen assay. cis-ZEN proved to be slightly more estrogenic than ZEN. Biotransformation of cis-ZEN to β-cis-ZEL corresponds to a detoxification, whereas metabolism to α-cis-ZEL resembles a metabolic activation as its estrogenicity considerably exceeds that of cis-ZEN. The catecholic metabolites can be expected to show a decreased estrogenicity as demonstrated for 15-OH- ZEN. Independent of the estrogenic effects, the catecholic and epoxidic metabolites identified in this work can be expected to act genotoxic and carcinogenic. The epoxides in particular could fundamentally change the widely accepted view of ZEN causing adverse effects exclusively through endocrine disrupting actions.
148
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.
145
Non-destructive testing (NDT) is regarded as one of the key elements in ensuring quality of engineering systems and their safe use. A failure of NDT to detect critical defects in safetyrelevant components, such as those in the nuclear industry, may lead to catastrophic consequences for the environment and the people. Therefore, ensuring that NDT methods are capable of detecting all critical defects, i.e. that they are reliable, is of utmost importance. Reliability of NDT is affected by human factors, which have thus far received the least amount of attention in the reliability assessments. With increased use of automation, in terms of mechanised testing (automation-assisted inspection and the corresponding evaluation of data), higher reliability standards are believed to have been achieved. However, human inspectors, and thus human factors, still play an important role throughout this process, and the risks involved in this application are unknown. The overall aim of the work presented in this dissertation was to explore for the first time the risks associated with mechanised NDT and find ways of mitigating their effects on the inspection performance. Hence, the objectives were to (1) identify and analyse potential risks in mechanised NDT, (2) devise measures against them, (3) critically address the preventive measures with respect to new potential risks, and (4) suggest ways for the implementation of the preventive measures. To address the first two objectives a risk assessment in form of a Failure Modes and Effects Analysis (FMEA) was conducted (Study 1). This analysis revealed potential for failure during both the acquisition and evaluation of NDT data that could be assigned to human, technology, and organisation. Since the existing preventive measures are insufficient to defend the system from identified failures, new preventive measures were suggested. The conclusion of the study was that those preventive measures need to be carefully considered with respect to new potential risks, before they can be implemented, thus serving as a starting point for further empirical studies. To address the final two objectives, two preventive measures, i.e. human redundancy and the use of automated aids in the evaluation of NDT data, were critically assessed with regard to potential downfalls arising from the social interaction between redundant individuals and the belief in the high reliability of automated aids. The second study was concerned with the potential withdrawal of effort in sequential redundant teams when working collectively as opposed to working alone, when independence between the two redundant individuals is not present. The results revealed that the first redundant inspector, led to believe someone else will conduct the same task afterwards, invested the same amount of effort as when working alone. The redundant checker was not affected by the information about the superior experience of his predecessor and—instead of expected withdrawal of effort—exhibited better performance in the task. Both results were in contradiction to the hypotheses, the explanations for which can be found in the social loafing and social compensation effects and in the methodological limitations. The third study examined inappropriate use of the aid measured in terms of (a) agreement with the errors of the aid in connection to the frequency of verifying its results and in terms of (b) the overall performance in the task. The results showed that the information about the high reliability of the aid did not affect the perception of that aid’s performance and, hence, no differences in the actual use of the aid were to be expected. However, the participants did not use the aid appropriately: They misused it, i.e. agreed with the errors committed by the aid and disused it, i.e. disagreed with the correct information provided by the aid, thereby reducing the overall reliability of the aid in terms of sizing ability. Whereas aid’s misuse could be assigned to low propensity to take risks and reduced verification behaviour because of a bias towards automation, the disuse was assigned to the possible misunderstanding of the task. The results of these studies raised the awareness that methods used to increase reliability and safety, such as automation and human redundancy, can backfire if their implementation is not carefully considered with respect to new potential risks arising from the interaction between individuals and complex systems. In an attempt to minimise this risk, suggestions for their implementation in the NDT practice were provided.
144
This thesis addresses numerical simulations of self-compacting concrete (SCC) castings and suggests a novel modelling approach that treats reinforcement zones in a formwork as porous media.
As a relatively new field in concrete technology, numerical simulations of fresh concrete flow can be a promising aid to optimise casting processes and to avoid on-site casting incidents by predicting the flow behaviour of concrete during the casting process. The simulations of fresh concrete flow generally involve complex mathematical modelling and time-consuming computations. In case of a casting prediction, the simulation time is additionally significantly increased because each reinforcement bar occurring in succession has to be considered one by one. This is particularly problematic when simulating SCC casting, since this type of concrete is typically used for heavily reinforced structural members. However, the wide use of numerical tools for casting prediction in practice is possible only if the tools are user-friendly and simulations are time-saving.
In order to shorten simulation time and to come closer to a practical tool for casting prediction, instead to model steel bars one by one, this thesis suggests to model zones with arrays of steel bars as porous media. Consequently, one models the flow of SCC through a reinforcement zone as a free-surface flow of a non-Newtonian fluid, propagating through the medium. By defining characteristic parameters of the porous medium, the influence on the flow and the changed (apparent) behaviour of concrete in the porous matrix can be predicted. This enables modelling of any reinforcement network as a porous zone and thus significantly simplifies and fastens simulations of reinforced components’ castings.
Within the thesis, a computational model for SCC flow through reinforced sections was developed. This model couples a fluid dynamics model for fresh concrete and the macroscopic approach for the influence of the porous medium (formed by the rebars) on the flow. The model is implemented into a Computational Fluid Dynamics software and validated on numerical and experimental studies, among which is a large-scale laboratory casting of a highly reinforced beam. The apparent rheology of concrete within the arrays of steel bars is studied and a methodology to determine unknown input parameters for the porous medium is suggested. Normative tables defining characteristic porous medium parameters as a function of the topology of the rebar zone for different reinforcement cases are generated. Finally, the major contribution of this work is the resulting numerical package, consisting of the numerical solver and the parameter library. The thesis concludes on the ability of the porous medium analogy technique to reliably predict the concrete casting behaviour, while being significantly easier to use and far less time consuming than existing tools.
143
In order to meet the goal of reducing CO2 emissions, automotive industry places significant importance on downsizing components to achieve greater efficiency through lower weight and reduced friction. As friction reductions are associated with energy efficiency and wear protection with resource conservation, ever greater attention has been given to adamantine carbon-
based coatings and high-alloyed steels. Such applications are, however, associated with high production costs and energy expenditures, as well as many technical difficulties. Therefore a key issue in meeting the goals of friction reduction, wear protection and development of comprehensive lightweight strategies is whether or not the functional profiles of state-of-the art alloys can be enhanced by affordable solutions.
The running-in phase of mechanical systems is inevitable and, from a tribological standpoint, critical for the lifetime of such systems, though receives little attention and is poorly understood.
The growth of micro-cracks accelerates premature material failure and wear during this phase of heightened friction. With this in mind, the ultimate goal of this current work is to transfer the running-in phase into the final step of the mechanical finishing process through the targeted pre-conditioning of novel, high toughness steel bearings without thermo-chemical treatments and compare these to conventional, case-hardened steels. Two mechanisms were
investigated:
a. Cold work hardening and
b. Chemical tribofilm formation.
Steels that showed a tendency toward work hardening and tribofilm formation in previous testing were chosen for this investigation. Thorough characterization of the chosen Steels was carried out before any pre-conditioning techniques were applied. The widely used 20MnCr5, seen as a reference gear steel, underwent case-hardening and subsequent deep freezing treatments in an attempt to yield discrete sample groups with respect to residual austenite.
This allowed for a more thorough investigation into the effects of residual austenite on the properties of this material. The high-performance alternative steels, 36NiCrMoV1-5-7 (hot working steel) and 45SiCrMo6 (spring steel), were heat treated as recommended by their respective manufacturers, and were not case-hardened. The selection of materials with and materials without case-hardening allows for an investigation into whether or not case-hardening is even necessary to deliver acceptable friction behaviour and wear performance. Elemental
analyses were conducted by multiple methods to ensure accurate results. Residual Austenite contents of the steels and the depth profiles of residual stresses were determined by X-Ray diffraction (XRD), for 20MnCr5 ranging from approximately 6 – 14 vol.%, and under 2 vol.% for
the alternative alloys. Hardness profiles were taken from the testing surfaces into the material core. The carburization of 20MnCr5 led to higher hardness and the greater concentration of carbon in the carburization zone more representative of a hardened SAE E52100, or
100Cr6/102Cr6, than of a non-case-hardened 20MnCr5. Residual stresses from machining and case-hardening were measured directly at the sample surface. The high-performance Steels fulfilled manufacturer expectations in terms of elemental content, with hardness values between
50 – 55 HRC and strongly martensitic microstructure character. With characterization of the chosen materials complete, the materials could then be subjected to pre-conditioning.
The first pre-conditioning method involved targeted generation of cold work hardening as induced boundary layers to protect the contact zone against wear. Work hardening was identified both by variations in residual stress profiles, i.e. the introduction of beneficial compressive residual stresses, and hardness increases in the contact zone, providing enhanced wear resistance. Parameters for work hardening were further optimized to reduce damage to the surface substrates of the treated materials. The second pre-conditioning method involved
the targeted generation of chemically reactive tribolayers (tribofilms) on twin disk testing rigs.
The lubrication strategies were based on:
a. CaCO3, which is predominant in engine oils, and
b. MoDTC, which is commonly used in engine and gear oils.
The films generated in pre-conditioning were analyzed by SEM-EDX with Element-Mapping, Raman spectroscopy, and XPS to elucidate their molecular composition and concentration on the sample surfaces. The combination of these methods of analysis gave a clear indication that 104 cycles were sufficient to generate stable and lasting tribofilms. CaO and CaCO3 were the main components of the tribofilm from the first lubricant package, while MoS2, MoO2 and MoO3
were the main components from the second lubricant package.
Finally, slip-rolling endurance testing (T = +120 °C, 107 cycles, approximately 19 days in
a factory fill engine oil) was carried out on all materials. It was shown that both pre-conditioning methods could achieve significant reductions in friction and wear during testing at up to and including P0Mean =1.94 GPa (P0Max = 2.91 GPa, FN = 2,000 N). Ultimately, this research showed that:
1. non-case-hardened high-performance steels offer competitive wear performance and better friction behaviour than the case-hardened 20MnCr5.
2. pre-conditioning led to COF reductions to under 7/10 and wear coefficient reductions to an astonishing 1/10 of the original values for the untreated steels under mixed/boundary lubrication.
3. the observed improvements to friction behaviour and wear performance are indicative of
a technically simple, cost- and energy-efficient pre-conditioning strategy that may prove