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Eingeladener Vortrag
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In the presentation different zinc coatings are presented and investigated. Their naturally formed protective layers are electrochemically characterized and corrosion relevant values are determined by using a gel pad based on polysaccharide. The corrosion relevant values allow the differentiation of various zinc coating systems and can describe the current protective effect provided by the coating. It is shown that gel-type electrolytes influence protective layers and coatings considerably less than corresponding bulk electrolytes. From the results it is evident that gel-type electrolytes represent a viable and promising field in corrosion research.zeige mehr
Deuterium permeation and cracking in duplex steels as viewed by ToF-SIMS and HR-SEM with data fusion
(2016)
Better understanding of hydrogen assisted degradation and trapping mecha-nisms requires sufficient imaging techniques for respective hydrogen-microstructure interaction studies, in particular with multi-phase metallic micro-structures [1]. The present work is focusing on the elucidation of deuterium be-havior in two austenitic-ferritic duplex stainless steels (DSS) under the assumption that deuterium behaves in many ways similarly to hydrogen [2]. For case studies standard 2205 and lean 2101 DSSs were chosen due to the extensive use of these steels in industry [3]. The analyses were conducted by using a novel in-situ permeation and Time-of-Flight secondary ion mass spectrometry (ToF-SIMS) imaging technique or by ex-situ ToF-SIMS imaging following electrochemical charging experiments. Another pioneering procedure was data fusion (including chemometry) of results of powerful laterally resolved chemical analysis and high resolution structural characterization techniques .
Results for the ex-situ observations showed a different influence of deuterium loading on the two steel grades as well as different damage mechanisms in each phase. Formation of sub-surface blisters between the ferrite and austenite were obtained in both the standard and the lean DSS. In both steels, an increased deuterium concentration was observed around deformed regions such as cracks, confirming that they originate from the presence of deuterium [4]. The formation of parallel cracks was obtained only in the austenite within the standard duplex whereas in the lean duplex the highest intensity of deuterium was obtained in the austenite along the ferrite-austenite interphase.
In comparison, application of the novel in-situ permeation technique enabled to register and record the deuterium permeation through the material and the respective saturation sequence of the two phases as well as the interfaces. Faster diffusion of the deuterium was observed in the ferrite and a direct proof for deuterium enrichment at the austenite-ferrite interface has been given [1]. The integration of the specified techniques gives a better insight into the processes leading to hydrogen induced failure. These two experimental techniques provide very valuable tools for elucidation of respective metallurgical failure mechanisms that can be used for the validation of respective numerical models for hydrogen assisted cracking (HAC).
The chemical industry has expressed great interest in using polyethylene terephthalate (PET) as material for packagings for the transport of dangerous goods. Due to the high strength and stiffness of PET, the wall thickness and weight of packagings can be reduced. This is a relevant cost factor. PET is a semi-crystalline thermoplast which is produced by polycondensation of terephthalic acid and ethylene glycol.
According to the European dangerous goods regulations RID and ADR, samples of PET design types of packagings for dangerous goods must be pre-stored with the original filling good for six months at 23°C, before the design type tests can be carried out. For packagings made of polyethylene (PE) tests to prove the stress cracking resistance by using laboratory methods are possible to reduce time and costs. Therefore, standard liquids, simulating the different types of damaging effects on PE are defined in RID and ADR. However, there is no information and research available about the damaging mechanisms on PET in comparison to PE, especially regarding to stress cracking resistance and test methods.
The aim of this work is to compare the stress cracking resistance of PE and PET with the Full Notch Creep Test (FNCT), which was developed by chemical industry and is described in the standards EN ISO 16101 and EN 15507. It was investigated whether testing specimens made of PE and PET with a full coplanar notch around the middle of the specimens show weakening after the impact of a tensile force in a wetting solution (Lutensol® FSA 10) at 50°C in a test device on the basis of the FNCT.
The test results confirmed the suitability of the method for eight PE grades. Unfortunately, this method couldn’t be used for PET because the specimens broke during notching. In addition the molding of the sheets and the following temper process for twelve hours are very time-consuming, and the specimens broke during notching due to the high brittleness of PET.
Another possibility to provide evidence of stress cracking resistance of PE packagings is laid down in BAM’s Dangerous Goods Rule BAM-GGR 015. This test was carried out with PE and PET bottles to compare both materials. Therefore 1l test bottles were filled with a 5% wetting solution and mounted with a clamping tool for 28 days at 40°C. Tensile test specimens were cut out afterwards from the middle of the bottles in the deformed areas. Tensile strength and breaking elongation of PE specimens were determined in comparison to the PET specimens. The tensile properties of the PET specimens couldn’t be determined due to the strength and the stiffness of the material.
In conclusion the only way to provide information about the stress cracking resistance of PET was to perform stacking tests. 1l bottles made of PE and PET were filled with a 5% wetting solution and stored with a stacking load for 28 days at 40°C according to EN ISO 16495. Design types of PE and PET both passed the stacking tests.
Hydrogen-assisted cracking (HAC) represents a significant failure risk for (high strength) creep resistant low-alloyed steel components in fossil-fired power plant applications at temperatures of up to and above 200 °C. This particularly applies to respective start-up and shut-down processes associated with alternating service-conditions in terms of load flexible power plants. For quantitative determination of localized crack critical hydrogen concentrations, the temperature dependent hydrogen diffusion coefficients have to be determined as exactly as possible.
However, available literature provides a wide range of hydrogen diffusion coefficients for low alloyed steels with similar microstructures. Additionally, the available diffusion data seem not to be very reliable and their scatter increases with decreasing temperature. One reason is that the experimental boundary conditions can have a major impact on the determination of respective effective diffusion coefficients. Hence, the scope of this study is to evaluate the influence of the experimental boundary conditions on the derived diffusion coefficients. In addition, different methods for calculating diffusion coefficients are discussed. To elucidate such influences and to draw a line to practical application, the diffusion and trapping behavior in the creep resistant steel 7CrMoVTiB10 10 has been studied.
For such purpose, hydrogen charged specimens were isothermally degassed at different temperatures using carrier gas hot extraction (CGHE). Based on experimental data, a numerical model has been developed by which the hydrogen transport behavior and the respective hydrogen distribution during CGHE can be assessed.
It is demonstrated that the specimen heating rate has a large influence on the calculated diffusion coefficients under assumption of isothermal degassing which elsewhere has been underestimated in the assessment of diffusion data in creep-resistant steels. The numerical results suggest that calculation methods for diffusion coefficients are limited if compared to experimental results. It also turned out that the sample preparation time before CGHE can enormously influence determined diffusion coefficients. Consequently, non-homogeneous hydrogen concentration profiles have to be anticipated in the simulations to arrive at characteristic effusion curves consistent to respective CGHE experiments. In turn, validated diffusion coefficients are now available for the low-alloyed Cr-Mo-V steel, which can be helpful to calculate appropriate hydrogen removal heat treatment procedures.
A test campaign was launched to determine the mechanical properties of the HL-LHC 11 T Nb3Sn magnet components in order to accurately model the mechanical properties in Finite Element simulations that predict the stress and strain distribution in These magnets. Static and dynamic test methods have been applied for determining elastic materials behavior, and highly accurate Young’s moduli are obtained with the dynamic methods resonance and impulse excitation. These non-destructive methods also enable temperature dependent modulus measurements during in situ heat cycles.
Hydrogen-assisted cracking (HAC) represents a significant failure risk for (high strength) creep resistant low-alloyed steel components in fossil-fired power plant applications at temperatures of up to and above 200 °C. This particularly applies to respective start-up and shut-down processes associated with alternating service-conditions in terms of load flexible power plants. For quantitative determination of localized crack critical hydrogen concentrations, the temperature dependent hydrogen diffusion coefficients have to be determined as exactly as possible.
However, available literature provides a wide range of hydrogen diffusion coefficients for low alloyed steels with similar microstructures. Additionally, the available diffusion data seem not to be very reliable and their scatter increases with decreasing temperature. One reason is that the experimental boundary conditions can have a major impact on the determination of respective effective diffusion coefficients. Hence, the scope of this study is to evaluate the influence of the experimental boundary conditions on the derived diffusion coefficients. In addition, different methods for calculating diffusion coefficients are discussed. To elucidate such influences and to draw a line to practical application, the diffusion and trapping behavior in the creep resistant steel 7CrMoVTiB10 10 has been studied.
For such purpose, hydrogen charged specimens were isothermally degassed at different temperatures using carrier gas hot extraction (CGHE). Based on experimental data, a numerical model has been developed by which the hydrogen transport behavior and the respective hydrogen distribution during CGHE can be assessed.
It is demonstrated that the specimen heating rate has a large influence on the calculated diffusion coefficients under assumption of isothermal degassing which elsewhere has been underestimated in the assessment of diffusion data in creep-resistant steels. The numerical results suggest that calculation methods for diffusion coefficients are limited if compared to experimental results. It also turned out that the sample preparation time before CGHE can enormously influence determined diffusion coefficients. Consequently, non-homogeneous hydrogen concentration profiles have to be anticipated in the simulations to arrive at characteristic effusion curves consistent to respective CGHE experiments. In turn, validated diffusion coefficients are now available for the low-alloyed Cr-Mo-V steel which might be helpful to calculate appropriate hydrogen removal heat treatment procedures, for instance.
Modeling of Hydrogen-Assisted Cracking (HAC) in Duplex Stainless Steels (DSS):
- Hydrogen causes significant degradation in DSS and consequently HAC
- Mechanisms of HAC have not been fully understood in two-phase microstructures
- Mesoscale numerical modeling for HAC in DSS was created, coupled to the macroscale, enabling simulation of HAC in both phases independent from predefined crack paths
Renewable resources become more and more relevant to maintain energy demands for an increasing global population. Biosynthetic fuels like biodiesel might replace conventional petrochemical fuels, such as diesel. However, more research is needed to characterize the interaction between the different fuels and the polymeric material, especially with respect to ageing and degradation.
The poster will present several interaction and degradation phenomena of high density polyethylene (PE-HD) induced by diesel and biodiesel 1-3. Also the possible influence of microbial growth (fungi and bacteria) is considered. The chosen PE-HDs are typical thermoplastic resins for container and storage tank applications. Degradation of PE-HD will be investigated by changes of the mechanical properties – with main emphasis on the Charpy impact strength 2. Furthermore, with alternating sorption and desorption cycles in combination with oven ageing the co-oxidation 3 of PE-HD in contact with biodiesel will be addressed.
The widespread use of antibiotics in livestock farming leads to trace residues in food products and wastewater, potentially entailing antimicrobial resistance in food-borne pathogens. The determination of antibiotics in aqueous environments and foodstuff is thus of major concern.
Analytical assays based on molecularly imprinted polymers (MIPs) have emerged as a valuable tool in this field due to the low production costs, stability, format adaptability and the possibility to imprint and thus their ability to recognize a wide variety of target analytes. With regard to optical sensing technologies, however, MIPs have only been used in considerably few applications, especially in fluorescence sensors. This limitation is basically due to the fact that the incorporation of a fluorescently responding moiety into a polymer matrix is challenging. One way to overcome this limitation is to use tailor-made fluorescent indicator monomers for direct transfer of the binding event into an optical signal. If such a monomer is integrated into a thin MIP-shell on microspheres such core/shell particles can be readily used in advanced multiplexing sensory fiber-optic microarrays.
Here, we propose such a fiber-optic microarray based on fluorescent MIP microspheres for antibiotics. The binding behavior and the selectivity of a microarray using these MIP were examined and compared with a non-imprinted polymer (NIP) control, employing the target molecules and other structurally closely related antibiotics.
Metal reducing bacteria (MRB) are able to utilize various materials such as iron, uranium and manganese as well as many organic compounds as electron acceptors. This process leads to the conversion of Fe(III) containing passive film species to soluble Fe(II) oxides and hydroxides. The reduction process triggers the acceleration of general and local corrosion processes. Electron transfer mechanisms are not yet fully understood. In literature it has been controversially discussed to which extend secreted electron shuttles contribute to the extracellular electron transfer (EET).
To understand the chemical and electrochemical interaction mechanisms of MRB with steel surfaces this project combines a variety of in-situ techniques. The changes in oxide chemistry on Fe/steel surfaces in the presence of biomolecules and MRB are under investigation using a newly designed electrochemical cell for in situ XANES (x-ray absorption near edge structure) spectroscopy. Electrochemical quartz crystal microbalance (eQCM) studies support the spectroscopic investigations to gain information about the kinetics of attachment processes and changes in biofilm viscosity. The biofilm structure and composition as well as cell viability are investigated by complementary ex situ spectroscopic and microscopic analysis.
Combining spectroscopic techniques and eQCM data with electrochemical measurements, biological processes and the resulting degradation of steel surfaces can be observed in a non-destructive manner. Selecting model systems and a defined biological medium allows the determination of individual effects of diverse surface and environmental parameters. The fundamental understanding of bacterial attachment mechanisms and initial steps of biofilm formation will contribute to the development of new antifouling strategies.
In recent years, upconversion nanocrystals (UCNC) have shown great promise for biological and medical applications, mainly because of their excitation in the NIR region, which provides minimum fluorescence background and a rather deep penetration into biological samples, as opposed to excitation in the visible or UV region. Moreover, they show a multitude of characteristic narrow emission bands as basis for ratiometric measurements. Commonly, Yb is the sensitizer of choice, because of a comparatively high absorption cross section, simple energy scheme, and rather efficient energy transfer to the activator, mostly Er, Tm or Ho. A main disadvantage of the use of Yb as sensitizer for biological and medical applications is its absorption band at 976 nm and hence the use of an excitation wavelength at which water has a non-negligible absorption. This can lead to significant sample heating, especially at long illumination times or high excitation power densities, and thus, tissue damage or even cell death. A possible solution is the tri-doping of UCNC with Nd as sensitizer, which can be excited efficiently at around 800 nm, where water absorption is at minimum.
The use of Nd as a sensitizer and Yb as a bridge between Nd and the activator Er in NaYF₄ nanocrystals is a relatively new way to overcome the problems of heating of samples in an aqueous environment. Disadvantages can arise from the tri-doping, which can favor non-radiative relaxation due to the more complicated excitation process compared to e.g., simple Yb,Er-doped UCNC, which might lower the upconversion quantum yields in these tri-doped systems. In order to quantify clear advantages, NaYF₄:Yb,Er,Nd nanoparticles were synthesized and spectroscopically studied using an 8 W 804 nm laser diode and a custom-designed Edinburgh instruments FSP980 spectrometer. Wavelength-dependent studies of the emission intensities and the decay kinetics of these tri-doped UCNC at different excitation power densities and excitation pulse widths revealed the clear advantages of preventing water absorption on measurable luminescence signals.
We were able to show the influence of pulse width and excitation power density on the luminescence intensities and decay kinetics lifetimes at different emission wavelengths. Additionally, we can clearly discern power density-dependent and independent peaks in the emission spectra. In summary, we demonstrate that the tri-doping of NaYF₄:Yb,Er,Nd nanoparticles is a very promising approach to render UCNC more efficient and to make them better suitable for biological and medical applications requiring measurements in aqueous environment.
Silicon surface passivation with atomic layer deposited (ALD) thin films has gained more and more interest in the PV community in recent years. With ALD good film quality, accurate thickness control and conformity are reached. Furthermore, ALD is capable of coating difficult substrates such as nanostructured surfaces with the same accuracy as flat surfaces. A variety of materials such as Al2O3, TiO2 and HfO2 demonstrate good surface passivation quality both for front and rear surface of silicon solar cells. In addition of providing good surface passivation, thin films with high refractive index e.g. HfO2, TiO2 and AlN can act simultaneously as antireflection coatings when applied on the front surface of the device. Hence, ALD thin films can reduce both electrical and reflective losses in solar cells.
Thorough investigation of the optical properties of these layers is crucial for several reasons related to their production and use. Optical measurements provide a fast, easy, non-destructive, and in situ capable approach to quality assurance for photovoltaic devices. As the function of the final device is optical, optimisation of the device performance relies strongly on the knowledge of the wide-range dielectric function of the thin layers. In this contribution, we determined the optical constants of ALD generated layers of AlN, Al2O3, TiO2, and HfO2 in a wide spectral range covering the near ultraviolet and the mid-infrared regions by means of spectroscopic ellipsometry. By combining data from a UV-Vis-NIR ellipsometer (Woollam M2000DI) and an FTIR ellipsometer (Sentech Sendira), we can determine the optical constants alongside with the layer thicknesses from one large set of spectroscopic measurements. We consider this a contribution to the metrological treatment of stratified and structured thin films in the optical range by polarisation-sensitive measurement methods.
By means of an effective medium (EMA) based approach, it is possible to use spectroscopic ellipsometry to determine the mixing ratios between air and material in porous dielectrics and calculate a quantitative value of the porosity for these materials. As this method is model-based, it is very difficult to provide a quantitative measure for the accuracy of porosity values determined by this method. Valuable additional information can often be obtained by combining ellipsometry with other complementary methods. In the present study, the ellipsometry results were validated by Electron Probe Microanalysis (EPMA) with the option of layer analysis (by the socalled “STRATAGem” approach), gravimetry, and electron microscopy. We analysed porous TiO2 thin layers synthesised by means of a template synthesis approach (evaporation induced self assembly).
Ellipsometry measurements on porous samples are difficult to analyse due to the complexity of the models necessary. Often it is difficult to decide if the measured data contains enough information to successfully determine the target quantities (mixing ratio, dielectric function of the matrix material). One method to decrease the complexity of the fit and therefore use the measurement data most efficiently is a multi-sample analysis. In the present case, multi-sample analysis was used for determining the porosity factors of the individual layers while using one common set of dielectric function values for the matrix in all cases.
While the results of the fit analysis in this case can be used to show the feasibility and also the limitations of the multi-method approach, the porosity values themselves show a promising agreement between the independent methods. It can therefore be concluded that determining porosity values with ellipsometry is in accordance to other methods to the level of accuracy provided by the complementary methodologies.
Microbial induced corrosion (MIC) is a crucial problem in many technical plants as well as fuel tanks, leading to considerable damage and huge financial losses. Successful prevention of MIC requires the localization of first signs of corrosion as well as the identification of factors influencing the corrosion process.1 Hence, there is a growing need for sensitive and preferably inexpensive tools that enable the early detection of MIC. Of high importance are methods, which provide spatially and time-resolved information and allow the study of changes on metal surfaces as prerequisites for a more detailed analysis of ongoing corrosion processes at a MIC-affected site.2 In this respect, also the determination of corrosion rates can be of interest for the possible prevention of MIC.
In respect of modern approaches in material sciences and highly increased requirements on materials on safety relevant components, quality management and non-destructive testing reclaims a steadily increased meaning. The destructive meaning of measuring the degree of purity is defined in DIN EN 10247 through metallurgical investigations, especially microsections. For and comparable, but non-destructive testing due ultrasonic testing, the material the SEP 1927 is a well-defined industry standard. A novel and alternative way of reference block construction was focused by this work. The proposed amendments, regarding the manufactoring and machining, are less time and cost consuming. Verified by measurements the presented reference block fits the same acoustical characteristics and the requirements of the guideline.
Volatile organic compounds (VOC) are ubiquitous in the indoor air, since they emit from materials used indoors. Investigations of these materials are mostly carried out in test chambers under controlled climatic conditions. Quality control of these test chamber measurements is important but there is a lack of commercially available homogenous reference materials. The approach of this study is to dope a supporting material with VOCs, which are then reproducibly released in measurable chamber air concentrations between 30 to 300 µg m ³. From several tested supporting materials vacuum grease (APIEZON M) was selected because of its very low own emissions. First tests were conducted with styrene. For the estimation of the initial emission and the emission over time FEM (finite element methods) modelling was used. Based on this, five samples with a surface of 7 cm2 and a thickness of 12 mm with a content of 1 ‰ styrene were investigated at (23 ± 2) °C and (50 ± 5) % relative humidity in the µ-chamber (3 samples) and 24 L test chambers (2 samples) for 28 days. Air samples were taken after 24 hours, 3, 7, 14, 21 and 28 days on Tenax TA® sorption tubes and analyzed by TD-GC-MS. The area specific emission rate (SERa) was calculated to compare the results from both chamber types. After 24 hours SERa was between 0.8 0.9 µg cm 2 h 1 (3800 4000 µg m 3) for the µ-chamber samples and between 0.9 1.1 µg cm 2 h 1 (300-370 µg m 3) for the 24 L test chamber samples. After 28 days the SERa was at 0.2 µg cm 2 h 1 for all samples. The relative standard deviation of the SERa was between 1 26 %. These results show the applicability of vacuum grease as supporting material and the favored starting concentration range could be achieved in the 24 L test chambers.
In situ investigations using PXRD coupled with Raman spectroscopy permit the evaluation of the formation pathways of milling reactions. The liquid-assisted grinding cocrystallisation of theophylline with benzamide leading to polymorphic compounds was investigated. The dipole moment of the solvent used in the synthesis determines the structure of the polymorphic product. A detailed investigation allows determining the kinetically and thermodynamically favored product. In situ observations of the formation pathway during the grinding process of both polymorphs show that the thermodynamically favored cocrystal is formed in a two-step mechanism with the kinetic cocrystal as intermediate. The evaluation of the mechanochemical formation pathways reveals the importance of in situ investigations for an in depth understanding of mechanochemical synthesis mechanisms. Our study demonstrates that the choice of the solvent in the LAG synthesis is decisive for the controlled formation of a desired polymorphic final product.
X-ray powder diffraction (XRD) patterns of the high-temperature (HT) cristobalite form of SiO2 and its isoelectronic AlPO4 analogue are essentially influenced by the dynamic disorder of these crystal structures. The nature of this disorder and of the phase transition between the α- and β-form has been the subject of intensive research during the last four decades [1]. By 1989 it became possible to stabilize the HT-form of cristobalite SiO2 at room temperature in laboratory and engineering ceramic industries by applying solid solution forming techniques [2]. However, for the HT-form of cristobalite AlPO4 nothing similar has been known until 2014 when it was discovered that nanocrystalline and stacking-disordered β-cristobalite AlPO4 is the major component of the fly ash of a large incineration facility operated by the waste water treatment authorities of Frankfurt/M. [3]. Previous comprehensive investigations of this fly ash failed to interpret its complex XRD pattern – presumably mainly due to the lack of a matching experimental digital pattern in the Powder Diffraction Database. The present paper reports on a synthesis route that facilitates the crystallization of nanocrystalline and stacking-disordered β-cristobalite AlPO4 that is free of crystalline impurity phases and long-term stable at ambient. Its room temperature XRD pattern is presented with parameters traced back to certified reference materials.
[1] Yuan F. and Huang L., Phys. Rev, B, 2012, 85, 134114. [2] Perrotta J.A., Grubbs D.K., Martin E.S., Dando N.R., McKinstry H.A. and Huang C.-Y., J. Am. Ceram. Soc., 1989, 72, 441. [3] Peplinski B., Adam C., Adamczyk B., Müller R., Michaelis M., Krahl Th. and Emmerling F., Powder Diffraction Journal, 2015, 30, 2, Supp. 1, S31.
Characterization of silver nanoparticles in cell culture medium containing fetal bovine serum
(2016)
Nanoparticles are being increasingly used in consumer products worldwide, and their toxicological effects are currently being intensely debated. In vitro tests play a significant role in nanoparticle risk assessment, but reliable particle characterization in the cell culture medium with added fetal bovine serum (CCM) used in these tests is not available. As a step toward filling this gap, we report on silver ion release by silver nanoparticles, and changes in the particle radii and in their protein corona when incubated in CCM. Particles of a certified reference material (CRM), p1, and particles of a commercial silver nanoparticle material, p2, were investigated. The colloidal stability of p1 is provided by the surfactants polyethylene glycole-25 glyceryl trioleate and polyethylene glycole-20 sorbitan monolaurate, whereas p2 is stabilized by polyvinylpyrrolidone (PVP). Dialysis of p1 and p2 reveal that their silver ion release rates in CCM are much larger than in water. Particle characterization was performed with asymmetrical flow field-flow fractionation (FFF), small-angle X-ray scattering (SAXS), dynamic light scattering (DLS) and electron microscopy. p1 and p2 have similar hydrodynamic radii of 15 nm and 16 nm, respectively. The silver core radii are 9.2 and 10.2 nm. Gel electrophoresis and subsequent peptide identification reveal that albumin is the main corona component of p1 and p2 after incubation in CCM, which consists of Dulbeccos Modified Eagle Medium with 10% fetal bovine serum added.
Advanced methods for 3D green density characterization like computed tomography and 3D FE sinter modeling can be utilized for increasing the reliability of sintered components. The experimental in situ observation of sin-tering, however, is currently restricted to silhouette methods, i.e. heating microscopy. For complex shaped sam-ples, in situ shape screening during shrinkage would allow better validation of 3D sinter simulation models. Further, by revealing temporary sinter warpage, 3D high-temperature shape screening would allow to locate potential defects of complex sintered components. Against this background, BAM developed a testing device for in situ 3D high-temperature shape screening for ceramic and glass-ceramic tapes up to 1000°C [1-3]. Current work is focused on dropping this restriction in sample shape and temperature. The poster illustrates the current state of this work and possible applications of the method e.g. in detecting sinter warpage of metallized glass-ceramic LTCC tapes.
In the course of miniaturizing modern technology down to the molecular scale, much remain unknown about the materials behavior and the deviations from the bulk that might arises from confinement effects. Here, a combination of nano-sized relaxation spectroscopies (Broadband dielectric spectroscopy (BDS) and Specific heat spectroscopy (SHS); employing AC nanochip calorimetry) were utilized to investigate the glassy dynamics of ultra-thin films of Poly (vinyl methyl ether) (PVME) and of blends PVME / Polystyrene (PS) 50:50 wt-%,, which are miscible in bulk (thicknesses: ca. 8 nm – 160 nm, film thickness was controlled by ellipsometry, film topography by AFM). Both methods are sensitive to different probes; where SHS senses entropy fluctuations while BDS measures dipole fluctuations. For BDS measurements, a recently developed nano-structured electrode sample arrangement is employed, where ultra-thin films are spin-coated on an ultra-flat highly conductive silicon wafer, sandwiched between a wafer with nanostructured SiO2 nano-spacers with heights between 35 nm and 70 nm. For PVME films, two thickness independent processes were observed and interpreted to be the α-processes of a bulk-like layer and a process due to an absorbed layer to the substrate. This adsorbed layer further undergoes a confinement effect that results in the localization of the segmental dynamics, which results in an Arrhenius-like temperature dependence. A detailed analysis of the dielectric strengths of both processes reveals that the thickness of the adsorbed layer decreases with increasing temperature, while that of the bulk-like layer increases. For the blend system, by measuring the dynamic Tg in dependence of the film thickness, SHS showed that the Tg of the whole film was strongly influenced by a nanometer-thick surface layer at the polymer/air interface due to a self-assembling process. The dynamic Tg obtained from the SHS measurements decreased with decreasing film thickness. On the other hand, BDS measurements showed a completely different behavior. At high temperatures, the temperature dependence of the relaxation times of the films follows that of bulk-like PS/PVME; obeying the VFT-law. With decreasing temperature, the temperature dependence deviates from the VFT to an Arrhenius law; where the apparent activation energy decreases with decreasing film thickness. This is the first example where confinement induced changes were observed by BDS for ultra-thin films. All results were analyzed in detail in a comprehensive discussion.
Successful implementation of an optical polarimetry measurement setup. Due to wall anchoring interactions HAT6 embedded in an untreated alumina membrane exhibits a radial orientation for pore sizes in between 30 nm and 80 nm. Embedded in large membranes, pore size of 180 nm, HAT6 forms the favored hexagonal columnar phase along the pore axis.
In the last years, secondary low-energy electrons (LEE) emerged as important, if not predominant, reductive pathway in ionizing damage of biomolecules. These electrons are created in copious amount as result of inelastic scattering of high energy radiation at water. Until now, all experiments the quantification of the effects of LEEs on the biomolecular damage was either performed in vacuum with LEE sources or with DNA on surfaces in humid atmosphere.
We present a new experimental setup to irradiate biomolecules with electrons under physiological conditions. In combination with monte carlo simulations this setup makes it possible to determine microdosimetric quantities for biomolecules in liquid environment under electron irradiation.
This opens up new possibilities in radiation research to access the LEE damage under well defined physiological condition, for more complex systems, such as DNA-Protein complexes and even living cells.
Time-resolved studies on the formation of maghemite nanoparticles combining fast-XANES and SAXS
(2016)
Iron oxide nanoparticles find application in different areas like sensing, magnetic storage media, and biomedicine, due to their magnetic properties and environment-friendliness.
In the present contribution, we report on the in situ investigation of an iron oxide nanoparticle synthesis by coupled X-ray absorption near-edge structure (XANES) and small-angle X-ray scattering (SAXS). The combination provides simultaneously information about the size of particles (SAXS) and on the oxidation state and the local structure of the iron atoms (XANES). The co-precipitation synthesis was exemplary studied, using a stabilization agent to decelerate the fast precipitation of the iron oxides. This allows to detect intermediates in situ. The measurements were performed using a custom-made acoustic levitator as sample holder. From the data, a mechanism was derived indicating different phases of particle Formation and oxidation state changes.
The ability to penetrate dielectric materials makes T-rays attractive to reveal discontinuities in polymer and ceramic materials. Changes of travelling time (ToF) and pulse shape due to the interactions of THz pulses with the dielectric material and its inherent discontinuities can be observed. A tomogram of the object under the test can be reconstructed from time of flight diffraction (ToFD) scans if a synthetic focusing aperture (SAFT) algorithm is applied.
Ceramic components with complex shape cannot be produced frequently by usual ceramic forming and sintering processes. Therefore, numerous joining methods were developed and introduced in industrial scale. Nowadays, multi-stage Mo-Mn-process and active brazing are preferentially used, if temperature-stable and gastight joints are required. Unfortunately, both processes involve cost-intensive thermal processes: hydrogenous atmosphere is essential for metallization in Mo-Mn-process and active brazing takes place under vacuum. Thermal processes can be drastically simplified by using Reactive Air Brazing (RAB). Joining under air atmosphere is an interesting alternative, especially to join oxide ceramic components among themselves. So far, main disadvantage of RAB is low strength of join connections.
Aim of this investigation was the development of high-strength, thermal shock resistant and gastight ceramic-ceramic joints by RAB. Therefore,
- commercial, silver and copper oxide containing RAB soldering composition was modified by addition of ceramic particles with low thermal expansion coefficients (TEC). Hence, thermal misfit between TEC of solder and ceramic components was significantly reduced.
- RAB soldering paste was replaced with newly developed RAB composite tapes, produced by ceramic “doctor blade” technology. Thereby, improved potential exist to tailor the brazing layer relating to composition, thickness and thickness uniformity.
Gastight alumina-alumina, alumina-zirconia and zirconia-zirconia joints with strongly improved strength were produced by novel composite tapes. No strength degradation of joints was observed after thermal cycling up to 700°C.
The wetting behavior of material surfaces can be controlled by surface structures. We functionalized inorganic material surfaces, such as steel, titanium alloy and silicon, to modify the wetting behavior using ultrashort laser pulses (fs- to ps-range). The laser processing was performed by scanning the laser beam across the surface of initially polished flat sample material. A combined experimental and theoretical study of the laser processing parameters (peak fluence, scan velocity, line overlap) allowed the identification of different regimes associated with characteristic surface morphologies (laser-induced periodic surface structures, grooves, micro cones, dimples, etc.). Analyses of the surface using optical as well as scanning electron microscopy allowed the identification of morphologies providing the optimum similarity to the natural skin of lizards. For mimicking skin structures of moisture-harvesting lizards towards an optimization of the surface wetting behavior, additionally, a two-step laser processing strategy was established for realizing hierarchical micro- and nanostructures. In this approach, a laser-generated regular array of small dimples was superimposed (step 2) to the micron-scaled capillaries processed before (step 1). Optical focus variation imaging measurements finally revealed the three dimensional topography of the laser processed surfaces derived from lizard skin structures. The functionality of these surfaces was analyzed in view of wetting properties.
Large area periodic surface structures were generated on steel surfaces using 30-fs laser pulses at 790 nm wavelength. Two types of steel exhibiting a different corrosion resistance were used, i.e. a plain structural steel (corrodible) and a stainless steel (resistant to corrosion). Homogeneous fields of laser-induced periodic surface structures (LIPSS) were realized utilizing laser fluences close to the ablation threshold while scanning the sample under the focused laser beam in a multi-pulse regime. The nanostructures were characterized with optical and scanning electron microscopy. For each type of steel, more than ten dentical samples were laser-processed.
These samples were subjected to microbial adhesion tests, investigating bacterial adhesion behavior on the laser structures in comparison to polished reference surfaces. Short term experiments (<24h) were carried out to determine initial biofilm development. E. coli as a typical bacterium representing pathogenic bacteria and Shewanella putrefaciens as metal corrosive bacterium were used for biofilm development analyses. Bacterial cell adhesion was determined microscopically after DAPI cell staining (DNA staining). Comparison of the coverage areas between nanostructured and polished surfaces revealed differences in cell adhesion behavior and biofilm structure.
Laser-induced periodic surface structures (LIPSS) were generated on titanium nitride (TiN) hardcoating surfaces (deposited on metallic substrates) upon irradiation with multiple linearly polarized femtosecond laser pulses in air (30 fs duration, 790 nm wavelength, 1 kHz pulse repetition rate). The conditions were optimized in a sample-scanning geometry for the processing of large surface areas (5 mm x 5 mm) covered homogeneously by nanostructures with sub-wavelength periods ranging between ~200 nm and 700 nm. For these nanostructures the coefficient of friction was characterized under reciprocating sliding condition against a ball of hardened steel at 1 Hz using different lubricants (regime of mixed friction). After 1000 cycles, the corresponding wear tracks were characterized by optical and scanning electron microscopy. High-resolution energy dispersive X-ray analyzes (EDX) allowed the visualization of chemical alterations within the wear tracks. For specific conditions, the nanostructures endured the tribological treatment. Our experiments provide a qualification of the tribological performance of the fs-LIPSS on TiN surfaces.
Laser-induced periodic surface structures (LIPSS, ripples) were generated on steel and titanium surfaces upon irradiation with multiple linear polarized femtosecond laser pulses (pulse duration 30 fs, central wavelength 790 nm). The experimental conditions (laser fluence, spatial spot overlap) were optimized in a sample-scanning geometry for the processing of large surface areas covered homogeneously by the nanostructures. The irradiated surface regions were subjected to optical microscopy (OM), white light interference microscopy (WLIM) and scanning electron microscopy (SEM) revealing sub-wavelength spatial periods. The nanostructured surfaces were tribologically tested under reciprocal sliding conditions against a sphere of hardened 100Cr6 steel at 1 Hz using paraffin oil and engine oil as lubricants. After 1000 sliding cycles at a load of 1.0 N, the corresponding wear tracks were characterized by OM and SEM. For specific conditions the laser-generated nanostructures endured the tribological treatment. Simultaneously, a significant reduction of the friction coefficient was observed in the laser-irradiated (LIPSS-covered) areas when compared to the non-irradiated surface, indicating the potential benefit of laser surface structuring for tribological applications.
For the characterization of disperse and porous solids, usually single gas adsorption(GA) is employed. In the case of liquid adsorption (LA), the extraction of information on solids immediately becomes a more sophisticated matter since information on geometric as well energetic parameters of the solids is both superposed by liquid-mixture effects and displayed in excess terms. We have to ask if reliable solid parameters can be also obtained from LA isotherms. The enlarged data bank of gas and liquid adsorption measurements enables us to change systematically solid parameters (e.g., the pore width of MCM-41, the pore entrances of SBA-16, chemical heterogeneity) and to study in this way the influence of solid parameters on LA.
Ionic Liquids (ILs) are employed in various fields, for example, reaction engineering (reactions with gases, such as hydroformylation (CO, H2), hydrogenation (H2), oxidation (O2)) or separation technology (separations of gases, reactants, and high-volatility reaction products). For the basic engineering of such processes, knowledge of phase equilibria, particularly of mixtures, over a broad (p,T) range is mandatory. This contribution reports on recent experimental results from our laboratory: – for the simultaneous solubility of a binary gas mixture in a pure ionic liquid – for the solubility of a single gas in a binary liquid solvent mixture.
The term „Alternative Solvents“ often refers to ionic liquids (ILs), mainly to distinguish these substances from traditional (i.e., molecular) solvents.
In applications, any „alternative“ is required to perform better than something that is proven and tested.
To bring ILs into practical use, availability and costs are the fundamental points to be addressed.
There are two ways to proceed:
▬ tailoring a molecule, implanting the expected characteristics
advantage: optimization of the targeted performance possible
risks: outcome not always foreseeable, costly and time-intensive (“trial and error“)
▬ to target on mixtures of well-characterized ILs with molecular solvents
advantage: substance characteristics are known, less costly, less time-consuming,
mixture composition another tunable parameter
risks: the same but with less impact
For the basic engineering of technical processes, knowledge of phase equilibria, particularly of
mixtures, over a broad (p,T) range is mandatory.
This contribution reports on recent experimental results from our laboratory:
▬ the solubility of CO2 in a mixture of water and [bmim][CH3SO4]
▬ the solubility of CO2 in a mixture of methanol and [bmim][PF6]
While polymorphism is a common phenomenon in the crystallization processes of organic compounds, polyamorphism has gained importance only recently. Using sophisticated sample environments and applying in situ scattering methods and vibrational spectroscopy, the complete crystallization process of organic compounds from solution can be traced and characterized. Diffuse scattering from amorphous intermediates can be investigated by analyzing the atomic pair Distribution function (PDF) to gain further insights into molecular pre-orientation. The crystallization behavior of Paracetamol was studied exemplarily under defined, surface-free conditions. Based on the choice of the solvent, the formation of different polymorphs is promoted. The thermodynamically stable form I and the metastable orthorhombic form II could be isolated in pure form directly from solution. For both polymorphs, the crystallization from solution proceeds via a distinct amorphous precursor phase. PDF analyses of these different amorphous states indicate a specific pre-orientation of the analyte molecules introduced by the solvent. The resulting crystalline polymorph is already imprinted in these proto-crystalline precursors. Direct experimental evidence for the polyamorphism of paracetamol is provided.
One-part-geopolymers, produced by addition of water to a mixture of solid silica and sodium alumi-nate, are a less exhaustively studied approach to form geopolymeric binders. Depending on the silica source, the reaction products show significant amounts of zeolite Na-A besides amorphous compounds. Previously, 29Si MAS NMR has been used to analyze the chemical structure of such one-part geopolymers, having crystalline structures and amorphous phases (Q2, Q3, Q4).
In this work, pure zeolites and three different one-part-geopolymers cured for 1 day were investigated by 29Si-27Al TRAPDOR NMR. It was used to identify aluminum phases in overlapping silicon sites. Zeolites Na-X (Si/Al=1.4) and Na-Y (Si/Al=2.7) served as model systems to measure the TRAPDOR effect of the structural units Q4(mAl). Both materials show several Q4(mAl) signals, which are all separated by their chemical shifts. The more aluminum surrounds the silicon tetrahedron the higher are the normalized TRAPDOR difference signals (S0/∆S). The intensity ratios between Q4(mAl) to Q4({m-1}Al) of these signals is fixed but vary slightly between both zeolites. These results are transferred to the complex geopolymer structure.
Mechanochemistry is increasingly used for synthesizing various materials including cocrystals and metal organic compounds. Although this synthesis approach offers a fast and pure synthesis in high yields there is a lack in understanding the mechanisms of milling reactions. The driving forces triggering the formation of cocrystals under milling conditions were investigated using a set of multi-component competitive milling reactions. In these reactions, different active pharmaceutical ingredients were ground together with a further compound acting as coformer. The study was based on new cocrystals including the coformer anthranilic acid. The results of the competitive milling reactions indicate that the formation of cocrystals driven by intermolecular recognition are influenced and inhibited by kinetic aspects including the formation of intermediates and the stability of the reactants.
Ultrasonic echo testing has become a common method in civil engineering for the investigation of concrete structures. The detection of inhomogeneities, reinforcing elements and the geometry of the object is required for quality assurance and Inspection. This assessment depends on the quality of ultrasonic images which can be improved by using Reverse Time Migration (RTM) rather than the standard method, Synthetic Aperture Focusing Technique (SAFT). Although RTM provides a better mapping of circular objects and (dipping) reflectors, the image is corrupted by migration noise. To suppress the image noise, we have tested various filter methods in the spatial domain, frequency domain as well as in the curvelet domain on ultrasonic RTM images. We found that either a spatial edge detection filter in combination with a lowpass filter (Laplacian of Gaussian filter) or two lowpass filter with different filter parameters (Difference of Gaussian filter) removed artefacts. An additional smoothing was obtained by applying the first generation curvelet transform after downsampling the image matrix and adding Gaussian noise. The proposed filter scheme is able to suppress RTM noise and enhance the image quality such that the objective interpretation of ultrasonic images for Quality assessment of concrete specimen is simplified.
One of the alternative renewable fuels is biomass but it is a difficult fuel because of its diversity and complexity. It can contain high percentages of K and Cl responsible for corrosion together with sand that have additionally an abrasive effect during combustion. Because of permanently extending the surface reaction due to abrasion the corrosion of the materials increases. In particular in power plants, the superheater tubes are exposed to a corrosive abrasive attack that is one of the main sources of concern. The development of new alloys for multilayer surface, which combines corrosive and abrasive resistance is therefore of high importance. Those new technical approaches must be at the same time cost-effective to be an alternative to conventional materials. The aim of the presented investigation methods is to test and develop suitable alloys for coatings for the super heater tubes of biomass power plants. First results of abrasion investigations show improved abrasion resistance compared to the multi-component reference material Alloy 625.
The integration of finite element method (FEM) into the least-squares adjustment presented in is further extended for a joint evaluation of an elastostatic model and displacement field measurement. For linear solids which obey the Hooke's law, the material parameters determination from measurements is being examined.
Hard materials consist of a hard phase embedded in a metallic binder. In order to achieve high toughness and strength, it is necessary to have a perfect mixing of hard phase and binder, which is mainly achieved by ball milling. Niobium carbide (NbC) has a high potential to substitute tungsten carbide as hard material.
The publication presents the development of stable homogeneous and de-agglomerated NbC-dispersions. To prevent agglomeration of the powder, stable suspensions were achieved by surface treatments with the dispersants (PD and HD), which resulted in a charge reversal from a negative to a positive zeta potential. This surface-modified powder guaranteed a stable re-dispersion in the binder suspension. Nickel powder was added as metallic binder. This suspension was suited for 3D-printing. The green samples could be sintered in vacuum or Argon atmosphere.
Microbial induced corrosion (MIC) is a crucial problem in many technical plants as well as fuel tanks, leading to considerable damage and huge financial losses. Successful prevention of MIC requires the localization of first signs of corrosion as well as the identification of factors influencing the corrosion process. In this respect, also the determination of corrosion rates can be of interest for the possible prevention of MIC. Hence, there is a growing need for sensitive and preferably inexpensive tools that enable the early detection of MIC. Of special interest are methods, which provide spatially and time-resolved information and allow the study of changes on metal surfaces as prerequisites for a more detailed analysis of ongoing corrosion processes at a MIC-affected site.
Biofilm formation can lead to changes in pH, oxygen and chloride concentration as well as to the release of certain metal ions like Fe(II) and Mn(II) depending on the type of metal surface involved. Hence, optical methods enabling the detection of these analytes at very low concentration and monitoring of their changes can be used for MIC detection. Here, we propose to utilize polymeric nanosensors for MIC detection via the determination of the local pH value changes in different biofilms. Such nanosensors are known to have several advantages in imaging applications such as intracellular pH measurements including the ease of doping or labeling with a multitude of analyte-responsive and inert dye molecules for the realization of a high analyte sensitivity and ratiometric sensing. Moreover, they can be surface functionalized with target-specific ligands e.g., lectins, for the specific binding to the outer surface of certain types of bacteria. In this respect, different polymer architectures will be studied to identify an optimal candidate in terms of imaging performance in conjunction with several classes of pH-responsive fluorescent dyes like cyanines, aza-BODIPYs, and xanthenes, utilizing different mechanism of signal generation such as photo-induced electron transfer or protonation-induced changes in the spectral position of absorption and emission spectra.
Current pollen screening information networks are based on time-consuming, microscopic determination of the genus-specific pollen morphology. Additionally, the given information relies on prediction of plant growth, wind direction and seasonal information.
Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) was introduced for rapid analysis of complex biological samples. MALDI-TOF provides the possibility to measure species-specific mass peak patterns of pollen and offers a powerful tool for investigation of taxonomic relations.
Our objective is to develop a fast, reliable, routine method for detecting single pollen grains in pollen mixtures. The obtained spectra are analyzed by multivariate statistics.