Ingenieurwissenschaften und zugeordnete Tätigkeiten
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- 4.1 Biologische Materialschädigung und Referenzorganismen (11)
- 6.3 Strukturanalytik (11)
- 8.5 Röntgenbildgebung (11)
The exploration of metal phosphonates chemistry has gained great interest during the last decades, because of their structural diversity. Transition metal phosphonates are promising candidates for an application as electrocatalysts in oxygen evolution reactions (OER).
Here, we present the in situ investigation of mechanochemical syntheses of different manganese phosphonates by synchrotron X-ray diffraction. Nitrilotri(methylenephosphonic acid) and N,N-Bis(phosphonomethyl)glycine were chosen as ligands. The liquid-assisted milling process can be divided into three steps, including an amorphous stage. One of the products has not been obtained by classical solution chemistry before.
These metal phosphonates and/or their derivatives are considered to be active in electrochemical energy conversion. The verification of their applicability is one of the topics of our resent research.
Mechanochemistry is a versatile approach for green and fast synthesis of pure substances. By milling the reactants, various organic, inorganic, and metal-organic compounds can be obtained in high yields. Although mechanochemistry is widely used, the underlying mechanisms are not fully understood making mechanochemical reactions difficult to predict. Metal phosphonates are metal-organic compounds accessible by grinding. Because of their structural diversity, the exploration of the chemistry of metal phosphonates has gained considerable interest during the last decades. Transition metal phosphonates are promising candidates for an application as electrocatalysts in oxygen evolution reaction (OER). Here, we present the in situ investigation of the mechanochemical synthesis of a manganese(II)-phosphonate by synchrotron X-ray diffraction and thermography. The product has not been obtained by classical solution chemistry before and its crystal structure was determined from PXRD data. The milling process can be divided into different steps, with the product crystallization corresponding with the highest temperature rise. The activity of this metal phosphonate towards OER was measured and is presented here.
Mechanochemistry is a versatile approach for green and fast synthesis of pure substances. The exploration of the chemistry of metal phosphonates has gained considerable interest during the last decades due to their structural diversity. We synthesized manganese phosphonates in milling reactions. The mechanochemical reactions were investigated in situ to reveal the underlying mechanisms.
Additive manufacturing (AM) offers a range of novel applications. However, the manufacturing process is complex and the production of defect-free parts with a high reliability is still a challenge. Thermography is a valuable tool for process surveillance, especially in metal AM processes. The high process temperatures allow one to use cameras usually operating in the visible spectral range. Here, we compare the results of first measurements during the manufacturing process of a commercial laser metal deposition (LMD) setup using a MWIR camera with those from a VIS high-speed camera with band pass filter in the NIR range.
Additive manufacturing (AM) opens the route to a range of novel applications.However, the complexity of the manufacturing process poses a challenge for the production of defect-free parts with a high reliability. Since process dynamics and resulting microstructures of AM parts are strongly influenced by the involved temperature fields, thermography is a valuable tool for process surveillance. The high process temperatures in metal AM processes allow one to use cameras usually operating in the visible spectral range to detect the thermally emitted radiation from the process. In our work, we compare the results of first measurements during the manufacturing processes of a commercial laser metal deposition (LMD) setup and a laser beam melting (LBM) setup using a MWIR camera with those from a VIS high-speed camera with band pass filter in the NIR range.
Microbiologically influenced corrosion (MIC) is the deterioration of metals due to the metabolic activities of microorganisms. Microorganisms can take electrons directly from the metal surface (EMIC) thereby causing corrosion. Well known culprits of EMIC are: sulfate-reducing bacteria (SRB), acetogens and methanogens.
Our aims
- Develop a novel flow system to study MIC by methanogens to mimic industrial Environments
- Investigate the inhibitory concentrations of biocides targeting SRB on corrosive methanogenic strains
- Investigate the inhibitory effects of corrosion inhibitors on methanogens
- Compare the inhibitory concentrations to SRB
Electrochemical study of polyaniline/silicon dioxide containing coatings in geothermal solution
(2018)
Polyaniline/Silicon Dioxide containing coatings were electrochemically investigated in a saline geothermal solution.
With the increase of exposure time, impedance values of coated specimens decreased at low frequency, which could be caused by the decrease of pore resistance due to electrolyte or water uptake.
Coating system needs further optimization work.
One of the biggest problems in high-voltage silicone rubber insulation cable accessories is the damage on electrical treeing, initiated by partial discharges. The electrical treeing starts at unavoidable imperfections inside the material or at interfaces. The damage is usually irreversible and leads around the starting points to a partial destruction of the material. To prolong the lifetime and thereby to increase the assurance of the structural component commonly, for mechanical improvement constituted filler is modified to obtain a self-healing silicone rubber. Damage mechanism is analysed to address the filler to the damage mode.
THz and mid IR spectroscopy of high-molecular PE (HMW) and ultra high-molecular PE (UHMW) reveals modifications of the molecular structure. Characteristic absorption bands are changed if the two materials are exposed by -Co60 radiation up to 600 kGy and subsequently stored at an annealing temperature of 398 K until for 729 days. UHMW-PE and HMW-PE behave differently during the ageing process because of their molecular weight and inherent structure distinctions. The spectroscopic data offer characteristic absorption bands, which have been used to describe the complete ageing process in more detail. For instance, the integral absorption in the B1u THz-region can be used to describe quantitatively the reduction of crystallinity. The formation of trans vinylene unsaturation and the decay of vinyl during ageing can be observed in detail in the mid IR range.
UCST-type thermoresponsive polymers (i.e. that phase separate from solution upon cooling) present a tremendous potential not only in aqueous media with applications in the field of drug delivery, diagnostic and microfluidic applications, but also in water/alcohol mixtures, where they can be used for instance in sensing systems for alcohol-soluble drugs. However, only a few thermoresponsive polymers have been reported that present an UCST in a relevant temperature range and “green” solvents such as water or ethanol.
In this context, acrylamide-based monomers can be very useful building blocks for designing novel non-ionic UCST-type polymers because of their hydrophilic nature (with the appropriate side chain) and propensity to form hydrogen bonds. We will present our latest results on the UCST-type thermoresponsive behaviour of acrylamide- and/or 2,6-diaminopyridine-based homopolymers and copolymers in water or water/alcohol mixtures, and give some insights about the rational design of UCST polymers relying on H-bonding.
Sintered bioactive glass scaffolds of defined shape and porosity, e.g. made via additive manufacturing, must provide sufficient bioactivity and sinterability. As higher bioactivity is often linked to high corrosion and crystallization tendency, a certain compromise between sintering ability and bioactivity is therefore required. Groh et al. developed a fluoride-containing bioactive glass (F3), which allows fiber drawing and shows a bioactivity well comparable to that of Bioglass®45S5.
To study whether and to what extent the sinterability of F3 glass powder is controlled by particle size, coarse and fine F3 glass powders (300-310µm and 0-32µm) were prepared by crushing, sieving and milling. Sintering, degassing and phase transformation during heating were studied with heating microscopy, vacuum hot extraction (VHE), DTA, XRD, and SEM.
For the coarse glass powder, sintering proceeds slowly and is limited by surface crystallization of primary Na2CaSi2O6 crystals. Although the crystallization onset of Na2CaSi2O6 is shifted to lower temperature, full densification is attained for the fine powder. This finding indicate that certain porosity might be tuned via particle size variation. Above 900°C, intensive foaming is evident for the fine powder. VHE studies revealed that carbon species are the main foaming source.
Influence of deposition hatch length on residual stress in selective laser melted Inconel 718
(2018)
The present study aims to evaluate the bulk residual stresses in SLM parts by using neutron diffraction measurements performed at E3 line -BER II neutron reactor- of Helmholtz-Zentrum für Materialien und Energie (HZB) Berlin. Together with microstructure characterization and distortion measurements, it is possible to describe the stress state throughout the whole sample. The sample was measured in as-build condition (on a build plate) and after releasing from the build plate. The used material is the nickel based superalloy 718. This alloy is widely used in aerospace and chemical industries due to its superior corrosion and heat resistant properties.
Obtained results indicated different residual stress states for each of the transversal, longitudinal and normal component. The normal and transversal component exhibits a rather compressive behavior while the longitudinal was tensile in the center part of the sample and became compressive towards the tip. As expected, the absolute values of all stress components decreased after releasing the sample from the building plate. A surface scan utilizing a coordinate-measuring machine (CMM) allowed us to present top surface distortion before and after releasing. The top surface showed a distortion around ±80µm after releasing. Microstructure evolution in the scanning-building cross-section is largely dominated by columnar grains. In addition, many small random orientated grains are prominent in the regions of a laser overlap during SLM.
In summary, for the sample of superalloy 718 manufactured by SLM, a small distortion occurred when removing the sample from the build plate whereby the residual stress state decreases. Moreover, the observed columnar grains in the building direction could give a reason for the lowest stress values in that normal direction. However, the most important parameter controlling the residual stresses is the temperature gradient. Hence, future investigations are planned for a different scan strategy to distribute the laser impact in a more homogenous manner.
A numerical pre-study has shown that cracks in a flat sample featuring a drilled hole can be classified into one of three crack shape classes based on the combined evaluation of various types of test data.
During the last years, there has been a rapid rise in the use of nanomaterials in consumer products. Especially silver nanoparticles are frequently used because of their well-known optical and antimicrobial properties. However, the toxicological studies focusing on silver nanoparticles are controversial, either claiming or denying a specific nano-efffect. To contribute to localizing nanoparticles in toxicological studies and to investigate the interaction of particles with cells, a fluorescent marker is often used to monitor their transport and possible degradation. A major problem, in this context is the issue of binding stability of a fluorescent marker which is attached to the particle.
In order to overcome this problem we provide an investigation of the binding properties of fluorescence-labeled BSA to small silver nanoparticles. Therefore, we synthesized small silver nanoparticles which are stabilized by poly(acrylic acid). The particles are available as reference candidate material and were thoroughly characterized in an earlier study. The ligand was exchanged by fluorescence marked albumin (BSA-FITC). The adsorption of the ligands was monitored by dynamic light scattering (DLS). To verify that the observed effects on the hydrodynamic radius originate from the successful ligand exchange and not from agglomeration or aggregation we used small angle X-ray scattering (SAXS). The fluorescent particles were characterized by UV/Vis and fluorescence spectroscopy. Afterwards, desorption of the ligand BSA-FITC was monitored by fluorescence spectroscopy and the uptake of particles in different in vitro models was studied.
The particles are spherical and show no sign of aggregation after successful ligand exchange. The fluorescence intensity is quenched significantly by the presence of the silver cores as expected, but the remaining fluorescence intensity was high enough to use these particles in biological investigations. Half-life of fluorescence labeling on the particle was 21 d in a highly concentrated solution of non-labeled BSA. Thus, a very high dilution and long incubation times are needed to remove BSA-FITC from the particles. Finally, the fluorescence-labeled silver nanoparticles were used for uptake studies in human liver and intestinal cells, showing a high uptake for HepG2 liver cells and almost no uptake in differentiated intestinal Caco-2 cells. In conclusion, we showed production of fluorescence-marked silver nanoparticles. The fluorescence marker is strongly adsorbed to the silver surface which is crucial for future investigations in biological matrices. This is necessary for a successful investigation of the toxicological potential of silver nanoparticles.
An increase in the thermal diffusivity of Fe2TiO5 is observed after only three cycles of measurement. X-ray refraction shows an increase in the mean specific surface. A segregation of Ca- and F-rich nanocrystals at grain boundaries is also observed by SEM and STEM-EDX. This emphasizes the importance of precursor purity and the influence of redistribution of impurities on thermoelectric properties.
The quenching and partitioning (Q&P) heat treatment enables a higher deformability of high strength martensitic steels. The Q&P heat treatment was applied on the martensitic stainless steel 1.4034 (X46Cr13) to study the influence of partitioning time. Therefore, extensive characterizations of the mechanical properties, focussing on the materials behaviour under different mechanical load scenarios, were performed. A comprehensive analysis of the microstructural evolution was per-formed for different heat treatment and mechanical loading states. A complete solution of chromium carbides was detected to be a first requirement for successful Q&P heat treatment. The comparison of common quenching and tempering with the Q&P heat treatment verifies the extensively enhanced materials strength whereat the formability is still acceptable. The microstructural reason was detected to be an increasing aus-tenite fraction due to austenite reversion at subgrain boundaries of martensite besides the stabilising of retained austenite. Further a distinctive strength differential effect was observed.
There is a need for an assessment of the emission properties of volatile organic compounds (VOCs) from consumer products. A method comparison was carried out to evaluate adapted and cost-effective procedures for such items. Smaller and automated emission chambers de-picted similar kinetics compared to a 203 L standard chamber. Toy samples made of PVC (Polyvinyl chloride) emitted more VOCs compared to other tested polymeric products. The emissions from 2 selected samples were studied to allow an evaluation of the resulting room concentration and external exposure of a child. Obtained concentrations were not of concern.
Two metal matrix composites, both consisting of a near-eutectic cast AlSi12CuMgNi alloy, one reinforced with 15%vol. Al2O3 short fibers and the other with 7%vol. Al2O3 short fibers + 15%vol. SiC particles were studied. Distribution, orientation, and volume fraction of the different phases was determined by means of synchrotron computed tomography. The load partitioning between phases was investigated by in-situ neutron diffraction compression tests. The internal damage of the eutectic Si phase and Al2O3 fibers after ex-situ compression tests was directly observed in CT reconstructed volumes. Significant debonding between Al-matrix and SiC particles was found. Those observations allowed rationalizing the load transfer among the constituent phases of two different composites. Finally, based on the Maxwell scheme, a micro-mechanical model was utilized for the composite with one and two ceramic reinforcements. The model rationalizes the experimental data, and predicts the evolution of principal stresses in each phase.
The fundamental impact of sulfur and water on corrosion rates and potential failure of the exposed material is well known. However, the access to the related corrosion mechanism causing material degradation is often a problem to solve. This study investigates the effect of SO2 and water vapor in the initial stages of corrosion of an Fe9Cr0.5Mn model alloy at 650 °C in situ. The analysis was carried out under laboratory conditions using energy-dispersive X-ray diffraction (EDXRD).
Die Probenpräparation ist ein Teil im Prozess der Baustoffuntersuchung und muss dementsprechend sorgfältig geplant werden. Die Probenpräparation ist letztendlich der Grundstein für alle folgenden Untersuchungen, somit wirken sich alle hier getroffenen Entscheidungen direkt auf die Qualität der Ergebnisse aus.
In well-annealed thin polymer films, with non-repulsive polymer/substrate interactions, an irreversibly adsorbed layer is expected to form. These adsorbed layers have shown great potential for technological applications. However, their growth kinetics and molecular dynamics are still not fully understood. This is partially due to the hard accessibility of these layers in thin films. Here, the irreversibly adsorbed layers of homopolymer thin films are revealed by solvent-leaching experiments. First, the growth kinetics of these layers is investigated as a function of annealing times and original film thickness. The thickness, topography and quality of the adsorbed layer is controlled with Atomic Force Microscopy (AFM). Secondly, the molecular mobility of the adsorbed layer is investigated with Broadband Dielectric Spectroscopy (BDS). A recently developed nanostructured capacitor is employed to measure the adsorbed layers with a free surface layer. The results are quantitatively compared and discussed with respect to recently published work.
Mechanochemistry is known for short reaction times, nearly quantitative conversions, and decreasing amount of solvents. Among organic syntheses, the Knoevenagel condensation is an important C-C bond forming reaction. We investigated the reaction of benzaldehyde derivates (nitro- and fluoro-derivates) with malononitrile syntheses by a combination of different in situ investigation techniques.
Mechanochemistry is widely applicable for the synthesis of inorganic, metal-organic, and organic compounds. It is known for short reaction times, nearly quantitative conversions, and decreasing amount of solvents, which opens the field to more environmentally friendly syntheses routes. Among organic syntheses, the Knoevenagel condensation is an important C-C bond forming reaction leading to α,β-unsaturated compounds. To gain more information on the underlying processes, we investigated the syntheses by a combination of different in situ investigation techniques, including synchrotron X-ray diffraction, Raman spectroscopy and thermography. This combination provides information on the structural changes and temperature influences during milling. Benzaldehyde derivates (nitro- and fluoro-derivates) reacted with malononitrile to the respective benzylidenemalononitriles. The in situ investigations show direct and quantitative conversions. In the case of the fluorinated benzaldehyde derivates we showed the possibility of using liquid substrates in mechanochemical organic synthesis. Surprisingly, after crystallization from a viscous state, the material was suitable for single-crystal X-ray analysis.
In this contribution we describe an in-situ study of the crystallization of simvastatin in three solvents. The studies were carried out by solvent evaporation at the µSpot beamline using acoustically levitated solution droplets in combination with simultaneous X-ray diffraction, Raman spectroscopy, and imaging analysis.
Ellipsometry is well known as a highly sensitive and reproducible surface analysis technique. However, in a context of metrological applications, the most important property of a measurement process is accuracy, relying on statistical precision, (reproducibility) and trueness (in an absolute sense versus a given standard). The latter is much more difficult to achieve. In this presentation, we discuss the possibility of establishing ellipsometry in a diverse metrological landscape by means of defining standard procedures and best practice methodologies for the measurement and for calibration purposes. The most important task of this approach is to determine the model-inherent uncertainty, originating from parameter coupling. We achieve this by means of sensitivity analysis of the parameters resulting from the fit process. We discuss the definition of reference materials by which accuracy can be made available for ellipsometry, passed along between ellipsometry laboratories and for other measurement techniques. The determination of uncertainty is presented in this work for a number of examples involving difficult analysis models employed for samples from different production environments. We present a standardization initiative with the goal to disseminate this work into an international standard alongside an inter-laboratory study comparing the results for complex samples gained by laboratories with different instrumentation. We also present the results gained within EURAMET projects focused on the metrology of materials with strong non-idealities used in photovoltaics and other energy technology.
Colloidal semiconductor nanoparticles with a spherical core and an elongated shell form bright emitters with a high absorption cross section. They show great potential for a multitude of optoelectronic applications such as LEDs or photovoltaic cells and can be used as gain material or as markers for bio imaging. For most of these applications high fluorescence quantum yields are a figure of merit for the emitter quality. In this work we investigate how the ensemble quantum yield is affected by the properties of the individual particles. In particular, we prove the role of non-emitting particles as well as the role of blinking. Using a combination of AFM and spatially resolved photoluminescence spectroscopy we measured hundreds of individual CdSe/CdS dot/rod particles of different shell lengths exciting with two different excitation wavelengths for shell or core excitation, respectively.
Phage display is used to find specific target binding peptides for polypropylene (PP) surfaces. PP is one of the most commonly used plastics in the world. Millions of tons are produced every year. PP binders are of particular interest because so far gluing or printing on PP is challenging due to its low surface energy. A phage display protocol for PP was developed followed by Next Generation DNA Sequencing of the whole phage library. Data analysis of millions of sequences yields promising peptide candidates which were synthesized as PEG conjugates. Fluorescence-based adsorption-elution-experiments show high adsorption on PP for several sequences.
Polynuclear aluminium species (Al13 keggin cluster) find application in different areas like water purification [1], contaminant transport [2], and as pilling clays with high specific surface areas[3], due to their strong binding ability to aggregates and high positive charge.
In the present contribution, we report on the in situ investigation of the Al13 sulfate synthesis by synchrotron wide-angle X-ray scattering (WAXS). Al13 cluster were crystallized by precipitating hydrolyzed aluminum solutions by the addition of sodium sulfate. The measurements were performed using a custom-made acoustic levitator as sample holder. The study provides information about the intermediates during the crystallization process. From the data, a mechanism was derived indicating the influence of the crystallization process.
We present the synthesis of four mesoporous templated iron oxides: Ferrihydrite, Hematite, Maghemite, Magnetite/Maghemite and the influence of water on the crystallization mechanism and the kinetics. The absence of water stabilize the ferrihydrite structure. By monitoring the dissolution in situ by using a QCMB and ex situ microscopy we got details in the dissolution mechanism of ferrihydrite.
The influence of isothermal ageing on microstructure, sensitisation and pitting corrosion resistance of the lean duplex stainless steel (LDSS) X2CrNiN23-4 was investigated with various electrochemical methods. The aging at 600 °C (from 0.1 h up to 20 h) lead to the formation of precipitations at the ferrite-ferrite (α/α) and ferrite-austenite (α/γ) grain boundaries, inducing sensitisation due to chromium depletion. The degree of sensitisation was evaluated with the double loop electrochemical potentiokinetic reactivation method (DL-EPR) according to ASTM G108 and correlated with critical pitting potentials (Epit) as well as critical pitting temperature (CPT) measured in an electrolyte according to ASTM G48 using electrochemical noise. Up to an ageing time of 1 h, the sensitisation did rise significantly, stabilising at a nearly constant level with a slight drop at 20 h. This behaviour correlated perfectly with the potentiodynamically determined pitting potentials Epit and sensitisation. The CPT showed a higher sensitivity at short ageing times compared to the DL-EPR and Epit. Finally, the KorroPad method was applied to visualise the sensitisation induced reduction of pitting corrosion resistance. The “KorroPad” is an agar-based gel-electrolyte containing 0.1 mol/l sodium chloride (NaCl) and 0.1 mol/l potassium ferricyanide III (K3[Fe(CN)6]), invented at the Federal Institute of Materials Research and Testing in Berlin (Germany) to detect surfaces of stainless steel prone to pitting corrosion. The standard configuration of the KorroPad showed no differentiation for the various aging conditions. Increasing the concentration of both NaCl and potassium ferrocyanide III to 0.5 M shifts the detection limit of the KorroPad method to stainless steels with higher corrosion resistance, producing the same trends detected by standard electrochemical pitting corrosion values (Epit, CPT) and sensitisation (DL-EPR). By that, the KorroPad method was successfully adjusted to the lean-duplex stainless steel X2CrNiN23-4, enabling short-time testing to detect sensitization.
The copper alloyed stainless steel 1.4542 (X5CrNiCuNb16-4) is used in different areas due to its good mechanical properties and corrosion resistance. Strength and corrosion resistance can be adjusted by the heat treatment, which is of importance for the application of this alloy. The mechanical properties (strength and hardness) are attributed to the dispersive precipitation of the copper rich ε–Phase. The additional precipitation of chromi-um carbides can reduce the corrosion resistance. Different ageing states were produced to investigate the precipitation behaviour with various methods. Furthermore, the influence of cold-rolling on the precipitation behaviour was studied in comparison to a solution annealed state without deformation. The microstructure was studied by SEM and the variations of hardness and magnetic proportion were characterised. The electrochemical potentiodynamic reactivation (EPR) was used to determine the corrosion resistance and detect chromium depletion in all heat-treated states. The results show that a work hard-ening accelerates the precipitation rate, while ageing at 600 °C reduces the corrosion resistance due to chromium depletion.
The copper alloyed stainless steel 1.4542 (X5CrNiCuNb16-4) is used in different areas due to its good mechanical properties and corrosion resistance. Strength and corrosion re-sistance can be adjusted by the heat treatment, which is of importance for the application of this alloy. The mechanical properties (strength and hardness) are attributed to the dispersive precipitation of the copper rich ε–Phase. The additional precipitation of chromium carbides can reduce the corrosion resistance. Different ageing states were produced to investigate the precipitation behaviour with various methods. Furthermore, the influence of cold-rolling on the precipitation behaviour was studied in comparison to a solution annealed state without deformation. The microstructure was studied by SEM and the variations of hardness and magnetic proportion were characterised. The electrochemical potentiodynamic reactivation (EPR) was used to determine the corrosion resistance and detect chromium depletion in all heat-treated states. The results show that a work hardening accelerates the precipitation rate, while ageing at 600 °C reduces the corrosion re-sistance due to chromium depletion.
Compact nuclear magnetic resonance (NMR) instruments make NMR spectroscopy and relaxometry accessible in industrial and harsh environments for reaction characterization and process control. Robust field integration of NMR systems have to face explosion protection or integration into process control systems with short set-up times. This paves the way for industrial automation in real process environments.
The design of failsafe, temperature and pressure resistant flow through cells along with their NMR-specific requirements is an essential cornerstone to enter industrial production plants and fulfill explosion safety requirements. Additionally, if fast reactions are monitored, suitable mixing devices need to be placed in close vicinity to the measuring volume to mix the reactants properly.
NMR-specific requirements aim at full quantitative pre-magnetization and acquisition with maximum sensitivity while reducing sample transfer times and dwell-times. All parameters are individually dependent on the applied NMR instrument.
Luckily, an increasing number of applications are reported together with an increasing variety of commercial equipment. However, these contributions have to be reviewed thoroughly.
The performance of sample flow cells commonly used in online analytics and especially for low-field NMR spectroscopy was experimentally and theoretically investigated by 1H-NMR experiments and numerical simulations. Especially, the applicability of 3D printed zirconium dioxide for innovative flow cell designs was of interest. Here, we demonstrate and discuss an automated test method to determine the critical parameters of flow through cells for quantitative online NMR spectroscopy. The setup is based on randomized setpoints of flow rates in order to reduce temperature related effects. Five flow cells and tubing were assessed and compared for high-field as well as low-field NMR spectrometers.
Statistical analysis of Vickers induced subcritical crack growth in soda-lime silicate glasses
(2018)
Studies on Vickers induced subcritical crack growth are controversially discussed since the stresses that drive the crack growth are distributed three dimensionally within the material and cannot be retraced by available methods. Hence, empirical approaches are used to calculate mechanical material parameters such as the stress intensity factor KI. However, the results of these approaches show large deviations from those measured by standardized techniques such as double cantilever beam (DCB) or double cleavage drilled compression (DCDC). Yet, small specimen sizes and low specimen quantities can prevent the execution of DCB and DCDC measurements. Here we present an approach that is based on a statistical analysis of Vickers induced radial cracks. For this purpose more than 150 single radial cracks were analyzed. The cracks were generated in a commercial soda-lime silicate glass. The experiments were performed in a glovebox purged with dry nitrogen gas to minimize the influence of atmospheric water on crack growth. The temporally resolved evolution of the radial cracks was monitored in-situ using an inverted microscope equipped with a camera system directly below the Vickers indenter. An automated image analysis software was used to determine the crack length over time. The data show that the crack propagation and thereby the crack velocities are not uniformly but statistically distributed. These findings allow, using the statistical mean value of the distributions in combination with DCB data, a precise formulation of KI for each measured crack length.
The presence of water in the surrounding atmosphere of a propagating crack has a major influence on the subcritical crack growth. While these external phenomena are well understood, there is still a lack of knowledge on the influence of structurally bound water on crack propagation. Thus, our recent study aims on the analysis of crack propagation in water bearing soda-lime silicate glasses with up to 8 wt.% water. The samples were synthesized in an internally heated pressure vessel at 0.5 GPa. Since this preparation route limits the sample sizes, standard test geometries allowing for the determination of stress intensity factors, such as double cantilever beam, are not feasible. Thus, radial cracks in the hydrous glasses were initiated by Vickers indentation and crack growth was simultaneously captured with a camera system. An automated image analysis algorithm was used for the analysis of the crack length of each single video frame. To minimize influences by atmospheric water, all experiments were conducted in a glovebox purged with dry N2. About 150 cracks per glass composition were analyzed to provide statistical significance of the Vickers-induced SCCG. The results show that structurally bound water has a major influence on SCCG by means of crack lengths, growth rates and time of crack initiation.
Cancer is a leading cause of death worldwide, and its early detection and resultant treatment contributes significantly to patient recovery and survival. Detection is currently based on magnetic resonance imaging and computed tomography, methods that are expensive, while processing of the results is time consuming. There is a need for low-cost cancer-detection techniques that give conclusive results in the shortest time possible. Molecularly imprinted polymers (MIPs) targeting tumor markers on cancerous cells may provide a cheaper solution for cancer detection. Thin MIP layers immobilized on particle platforms are known to give faster response times and increased selectivity in comparison to bulk MIPs. It has been reported that a fluorescent monomer can be incorporated into the MIP layer, allowing for faster detection of the target group, thus significantly shortening the turn-around time for biopsies.
Changes in sialylation patterns of cell surface glycoproteins indicate malignancy. Here, we present the development of MIPs that target sialic acid-terminated glycoproteins (SA MIPs), prepared as a thin layer on a silica nanoparticle platform. A fluorescent monomer is incorporated into the MIP layer, and upon binding of the target group to the specific binding pockets in the MIP, the fluorescence signal is enhanced. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) are used for structural characterization. To validate the specificity, fluorescence changes of MIPs in the presence and absence of template are compared to their corresponding non-imprinted polymer particles (NIP). Initial binding experiments with tumor cells using fluorescence microscopy demonstrate that the presented technique shows promise as a cheaper alternative to current detection methods, while allowing for relatively shorter analysis of biopsy results.
Microbiologically influence corrosion (MIC) has become a big concern due the increased usage of different metals by our society. Microorganisms can use metal as an electron donor, causing unpredictable but serious damages. Nowadays it is known that besides sulfate reducing bacteria (SRB), other microorganisms including acetogens, iron oxidizers and methanogens can also induce MIC. Current studies related to methanogen-induced MIC (MI-MIC) mainly focused on environmental isolates from the oil and gas industry (e.g. Methanococcus maripaludis) with industrial materials e.g. iron. However, MI-MIC can occur in many other environments as well, including the oral cavity. Methanobrevibacter oralis is a methanogen isolated from the human oral cavity and was found more frequently in patients suffering from peri-implantitis/periodontitis. Titanium-implants removed from those patients have also showed clear signs of corrosion. The aim of our study is to establish and analyze corrosion potentials of dental metals (e.g. titanium) by oral methanogens. Periodontal pockets samples from patients suffering from periodontitis/peri-implantitis were taken for methanogenic and SRB enrichments. Stainless steel, pure titanium or Ti-6Al-4V alloy was used for corrosion studies. Corrosion rates and methane production were measured using weight-loss method and gas chromatography, respectively. Metal surfaces were visualized with scanning electron microscopy. Microbial communities in the dental pockets of healthy people and patients will be compared using 16S rRNA amplicon sequencing. Overall, this is the first study investigating the susceptibility of different dental implant materials to corrosion using human-related Archaea. The outcomes of this study can be further explored for a variety of clinical applications.
The Ni-Cr-Mo-W alloy is characterized by the excellent high-temperature corrosion resistance, good strength and ability to work in aggressive environments. To protect the surface of the substrate 13CrMo4-5 steel against aggressive environments the Inconel 686 as clad layer was used. The corrosion process was performed in oxidizing mixture of gases like O2, COx, SOx. The second part of corrosion Experiment concerned the corrosion test of the coating in reducing atmosphere of the specified gases with ashes, which contained e.g. Na, Cl, Ca, Si, C, Fe, Al.
Microbiologically influenced corrosion (MIC) is the deterioration of metals due to the metabolic activities of microorganisms. Microorganisms can take electrons directly from the metal surface (EMIC) thereby causing corrosion. Well known culprits of EMIC are: sulfate-reducing bacteria (SRB), acetogens and methanogens.
Microbially influenced corrosion (MIC) of iron is usually attributed to sulfate-reducing microorganisms (SRM) which act upon the metal by the reactiveness of hydrogen sulfide, and by withdrawal of the available electrons (Fe → Fe²⁺ + 2e⁻ ; E° = 0.47 V) in electrical contact through surface attachment. Also methanogenic archaea are supposed to cause MIC. Because they do not produce hydrogen sulfide, withdrawal of electrons may be their main corrosive mechanism; however, mechanistic details and kinetics of the overall process are poorly understood. Precipitation of siderite (4Fe + 5HCO₃⁻ + 5H⁺ → 4FeCO₃ + CH₄ + 3H₂O) can lead to an insulating layer on the metal surface and lower the corrosion rate. Still, the extent of FeCO₃ precipitation may be significantly influenced by environmental conditions such as pH and advective processes.
To investigate the corrosive potential of methanogens, we studied strains isolated from marine sediments (Methanococcus maripaludis 14266, 2067, Methanobacterium-affiliated strain IM1), crude oil tanks (Methanococcus maripaludis Mic1c10, KA1) and the oral cavity (Methanobrevibacter oralis) in a closed (batch) culture, and in a sand-packed flow-through cell with pH control and simulation of a fluctuating environment. Results indicate that the rates of iron corrosion due to coupled methanogenesis (up to 0.3 mm/yr) are comparable to that caused by SRM. Surface analyses of the metal showed severe pitting. Such knowledge and deeper understanding also from an electrokinetic point of view may not only provide further models in microbial electrophysiology, but also contribute to mitigation strategies in MIC.
Microbially influenced corrosion (MIC) of iron is usually attributed to sulfate-reducing microorganisms (SRM) which act upon the metal by the reactiveness of hydrogen sulfide, and by withdrawal of the available electrons in electrical contact with the metal. Methanogenic archaea can also cause MIC by directly withdrawing electrons from the iron surface for methanogenesis. However, the mechanistic details and kinetics of the overall process are poorly understood. Precipitation of siderite, a by-product of methanogenesis, (4Fe + 5HCO3 + 5H+ 4FeCO3 + CH4 + 3H2O) can lead to an insulating layer on the metal surface and lower the corrosion rate. Still, the extent of FeCO3 precipitation may be significantly influenced by environmental conditions such as pH and advective processes.
Microbially influenced corrosion (MIC) of iron is usually attributed to sulfate-reducing microorganisms (SRM) which act upon the metal by the reactiveness of hydrogen sulfide, and by withdrawal of the available electrons in electrical contact with the metal. Methanogenic archaea are supposed to cause MIC. Because they do not produce hydrogen sulfide, withdrawal of electrons may be their main corrosive mechanism; however, mechanistic details and kinetics of the overall process are poorly understood. Precipitation of siderite (4Fe + 5HCO3 + 5H+ 4FeCO3 + CH4 + 3H2O) can lead to an insulating layer on the metal surface and lower the corrosion rate. Still, the extent of FeCO3 precipitation may be significantly influenced by environmental conditions such as pH and advective processes.
Microbially influenced corrosion (MIC) of iron is usually attributed to sulfate-reducing microorganisms (SRM) which act upon the metal by the reactiveness of hydrogen sulfide, and by withdrawal of the available electrons in electrical contact with the metal. Methanogenic archaea are supposed to cause MIC. Because they do not produce hydrogen sulfide, withdrawal of electrons may be their main corrosive mechanism; however, mechanistic details and kinetics of the overall process are poorly understood. Precipitation of siderite (4Fe + 5HCO3 + 5H+ 4FeCO3 + CH4 + 3H2O) can lead to an insulating layer on the metal surface and lower the corrosion rate. Still, the extent of FeCO3 precipitation may be significantly influenced by environmental conditions such as pH and advective processes.