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The interest in porous anodic aluminum oxide (AAO) has been rapidly growing due to its numerous applications in separation, catalysis, energy generation and storage, electronics, and sensors. From the scientific point of view, AAO is a topical interest in soft matter fields. Spatial confinement of soft matter in nanoporous media influences its structure, thermodynamics, and mobility. Embedding polymers and liquid crystals into nanopores of AAO results in a 2D nanoconfinement of these materials. This confinement affects their properties, compared to the bulk, such as phase transition temperatures and enthalpies, molecular mobility, and architecture of the crystallization. On the other hand, discotic liquid crystals (DLCs) are a promising class of soft matter for electronic applications. This is due to their ability to organize and stack themselves into columns in a hexagonal columnar mesophase, a mesophase in between the plastic crystalline and isotropic phase, driven by the overlap of the π orbitals of their aromatic core. This leads to a high charge-carrier mobility along the column axis. Further, these columns could then be considered as “molecular nanowires”. In this study, 2,3,6,7,10,11 hexakis[hexyloxy] triphenylene (HAT6), a triphenylene based DLC, was confined into nanoporous AAO membranes. The structure, dynamics and the phase behavior of the confined HAT6 were investigated by broadband dielectric spectroscopy (BDS) and differential scanning calorimetry (DSC). HAT6 was embedded into nanoporous AAO membranes by melt infiltration in the isotropic phase under argon atmosphere. The membranes have parallel aligned cylindrical nanopores, with pore diameter of 10, 20, 25, 40, 80, 120 and 180 nm. The filling degree for each sample was checked by thermogravimetric analysis (TGA) in order to ensure complete filling. Bulk HAT6 forms a hexagonal columnar phase; in between the isotropic phase above 371 K and the plastic crystalline phase below 340 K. Unlike the bulk, the confined HAT6 split the plastic crystalline-to-hexagonal columnar phase transition in two, which might be interpret as two different phase structures; close to the wall and at the pore center. Moreover, the isotropic-to-columnar transition of the confined HAT6 shifted, with decreasing pore diameter, to lower temperatures. Furthermore, pore surfaces of a series of membranes were chemically modified, resulting in a more hydrophobic pore surface than the unmodified ones. HAT6 was embedded into the modified membranes by the same aforementioned preparation. The influence of the changed host-guest-interaction, on the structure, dynamics, and the phase behavior of HAT6 confined in the modified membranes, was also investigated by BDS and DSC.
Upconversion nanoparticles are characterized by their ability to convert low energy near-infrared excitation in high energy emissions in the visible range. This is enabled by sequential absorption of two or more photons via energy transfer from the sensitizer lanthanide ion Yb3+ to an activator lanthanide ion, e.g. Er3+. Yb3+ sensitation has the advantage of 980 nm excitation achieved by commercial available low power cw laser modules.
Nevertheless, for some applications, especially in aqueous media, which is predominantely in bioanalytical applications, there is the drawback of a local Absorption maximum of water at this wavelength. Sample heating can occur, and excitation power density is strongly distance dependent.
To overcome this issue, the idea is to shift the excitation wavelength to 808 nm. This can be achieved by a tandem-excitation using Nd3+ and Yb3+ ions. Nd3+ gets excited by 808 nm irradiation and transfers the energy to Yb3+, which triggers the upconversion emission of the Er3+ ions. Therefore, it is mandatory to separate Nd3+ and Er3+ by core-shell architecture for reducing the energy backtransfer from Er3+ to Nd3+.
To further enhance the upconversion luminescence an additional inert shell formed by the host material NaYF4 reduces the quenching effects caused by surface defects and dangling bonds.
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.
Chemical admixtures like superplasticizers or stabilizing agents are of ever increasing importance for modern concrete technology. Although such admixtures have meanwhile become common practice in many applications of concrete technology, the understanding of these highly complex systems is still limited and the relevant parameters, which predominantly control the interaction between the superplasticizer and the cement components, have not been identified yet.
Optical methods have been successfully used for the analysis and monitoring of the interactions between a broad variety of nanoscale and molecular systems like nanoparticles of various chemical composition and different types of organic ligands or biomolecules. This encouraged us to assess the potential of these methods, and particularly reflectance and fluorescence measurements, for the study of the interactions that occur at the interface between particle or hydrate surfaces and the fluid phase at a very early stage of concrete formation. Special emphasis is dedicated to search for and identify differences between commonly used superplasticizers.
Here, we focus on hydration effects using commercial comb shape polycarboxylate ethers (PCEs) with different charge densities, which are known to allow a very low water/cement ratio (w/c of 0.20 or less) while maintaining good workability. Based upon changes of the intensity of the reflectance and fluorescence signal and spectral effects of a dye, acting as optical reporter, a model for the interactions of dye, PCE molecules and cement nanoparticles in the very first phase of cement hydration is derived
The results are based on data1. Figure 3 displays temperatures of the tank wall and of the gas phase over testing time. It can be seen that a complete coating strongly delayed the heating of tank wall and gas phase, whereas the partly coated tanks only had a minor influence on temperature development. There was no significant difference between a half coated and a thirdly coated tank measurable. Figure 4 shows the internal pressure of tanks over testing time. Only the fully coated tank enabled a low pressure over 90 min testing time. Hence, a complete coating is necessary to guarantee the fire safety of hazmat tanks and a partly coating is not sufficient.
Spray drying based granulation processes aim for flowable granules neither containing voids nor hard shells thus leading to a homogenous microstructure in the green and sinter bodies without strength reducing large pores. The increase of the specific surface area due to the utilization of finer powders as raw materials makes the production of granules of demanded quality more sophisticated. Innovations regarding additives as well as process engineering are therefore required.
While conventional spray granulation processes of ceramic materials are based on rotational, one stream or two stream nozzles for nebulization, the investigations in the ZIM project concentrate on the applicability of an ultra sound atomizer unit. A spray dryer comprised of the aforementioned ultra sound atomization unit implemented in a commercial spray dryer (Niro, Denmark) was used as test system. Potential advantages of the ultra sound nebulization are investigated for model systems of alumina, zirconia and a ZTA composite while focusing on solids content, yield, pressability and granule properties (size, size distribution, flowability, shape and microstructure) as well as the final sinter body properties (density, microstructure and flexural strength).
First ultra sound spray drying experiments yielded granules with excellent processability. Spray drying of identical slurries, as before tested and optimized for a two stream nozzle atomization process, resulted in a more suitable size distribution for dry pressing (less particles below 20 µm) and a higher yield. Furthermore, sinter bodies produced of ultra sound granules seem to have less large pores and a more homogenous microstructure
Additive manufacturing (3D printing) of ceramics and other materials offers significant advantages compared to conventional production processes for several applications. While ceramics have been extensively investigated in this regard, additive manufacturing of geopolymers have received much less attention to date. In the present contribution we study a ‘standard’ metakaolin-based geopolymer, a fly ash-based geopolymer and a silica-based one-part geopolymer regarding their suitability for additive manufacturing via selective laser curing. Model geometries such as bars and cuboids could be produced by this route. After selective laser curing the specimens were additionally cured at 80 °C for 24 h. The specimens were studied by means of scanning electron microscopy (SEM) and powder X-ray diffraction (XRD). SEM showed that the precursors in all geopolymers had reacted partially and geopolymeric gel had formed. XRD confirmed these results and additionally revealed that the crystalline byproducts (zeolites) in the one-part geopolymer differed from the byproducts observed in conventionally produced samples. This indicates that also the geopolymerization reactions differ between the two synthesis routes. The mechanical strength after selective laser curing and 80 °C-curing appeared to be highest for the metakaolin-based geopolymer. However, SEM also showed that a significant volume of macropores remained in most regions of all specimens, while some regions in the metakaolin-based geopolymer appeared to be significantly denser. These preliminary results demonstrate that selective laser curing offers potential for the production of geopolymers, but more research has to be undertaken to optimize the process.
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. In this study the influence of microbial growth on biodiesel and diesel on the storage tank systems were investigated. Polymeric fuel storage tanks for diesel and biodiesel provide suitable environmental conditions for a broad spectrum of fungi and various bacteria, including cyanobacteria and aerobic heterotrophic, and even anaerobic, fermentative Bacteria. However, the questions whether and how ageing of the materials is affected by biofouling processes have not been answered so far. Therefore, a model system for biofilm formation was established to study the initial attachment phase of bacteria in dependency of ageing, quality and surface modification of thermoplastic polymers used for storage tank systems. The microbial survey is closely connected with a detailed characterization of the material’s properties and its ageing processes.
A widely applied plastic used for fuel storage tanks is high-density polyethylene (PE-HD), which is available with various additives to increase UV-light stability and even for the storage of biodiesel. These materials were aged under UV-light and temperature using a defined climate chamber set-up. Further, the repeated filling of fuels was mimicked for such storage tanks, as this has an important impact on the life-cycle length for the storage Container. The aged polymers showed a significant change in the material’s characteristics, including surface characteristics (e.g. hydrophobicity) and carbonyl groups. The effect of the changed material properties on the biofilm formation are studied using bacterial isolates, previously obtained from a “dieselpest”, and as a model-reference E. coli. The unaged polymers showed already some significant differences for the initial attachment of E. coli K12. Polyethylene with additives was colonized faster than the reference material (without additives) although the final biofilm coverage was not impaired. Likewise, the settlement of a kerosene-isolated Bacillus species on the unaged materials independently of additives was only minor interfered.
In future, our results should give stakeholders in industry and public authorities a better estimation of the life-cycle security for fuel storage tank systems and on the fuel quality. Further, our results could help to test and develop new materials or additives to prevent biofouling processes.
Polynuclear aluminium species (Al13 keggin cluster) find application in different areas like water purification, contaminant transport, and as pilling clays with high specific surface areas, 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 report on the in situ investigation of the Al13 sulfate synthesis by WAXS. Al13 sulfates were crystallized by precipitating hydrolyzed aluminum solutions by the addition of sodium sulfate. The measurements were performed using an acoustic levitator. The study provides information about the intermediates during the crystallization process.
Selective Electron Beam Melting (SEBM) is a promising powder bed Additive Manufacturing (AM) technique for near net-shape manufacturing of high-value titanium components. However, as with every emerging technique, the manufacturing processes can still be greatly improved and optimised. In particular, the links between AM settings and the resulting sample porosity is of great interest, as the fatigue life of SEBM parts is currently dominated by the presence of porosity. In this study, the size, volume fraction, and spatial distribution of the pores in model samples have been characterised in 3D, using X-ray Computed Tomography (CT), and correlated to the SEBM process variables. A strong relationship was found with the different beam strategies used to contour, and infill by hatching, a part section. The majority of pores were found to be small spherical gas pores, concentrated in the infill hatched region. Rarer irregular shaped pores were mostly located in the contour region and have been attributed to a lack of fusion between powder particles.
Additive Manufacturing by Selective Laser Melting (SLM) offers ample scope for producing geometrically complex parts as compared to the traditional subtractive manufacturing strategies. However, the residual stresses (RS) developed during the processing can reduce the load bearing capacity as well as induce unwanted distortion, limiting the application of SLM parts. In the present work, residual stresses in additivly manufactured IN718 part were analised by means of neutron diffraction and synchrotron X-ray diffraction.
In this study a metal-matrix-composite with aluminum matrix and Al2O3 particles was investigated with x-ray refraction topography and in-situ tensile loading. It could be observed that after reaching a certain load the specific surface increased steadily. However, the classical radiographs taken for comparison show no damage in the sample.
We investigated the efficiency of phase gratings, i.e., the visibility upon variation of different parameters. Rotating around an axis parallel to the grid lines of the phase grating changes the grating’s shape and thereby the initial distribution of phase shifts. This yields high visibilities for shorter propagation distances than derived from box shapes. Tilting the grating in the scattering plane allows continuous tuning of the grating’s height that corresponds to an ideal phase shift for a particular photon energy. This opens the way for tuning the design energy suitable for the material under investigation. Our study included simulations for monochromatic sources with the sampling procedure for rectangular and triangular phase gratings.
Elastic wave propagation of ultrasound in bituminous road surfaces – simulations and measurements
(2015)
Maintenance costs of road infrastructure are increasing steadily. Adverse environmental impacts on infrastructure get more and more important as well. Therefore, it is important to determine how limited financial resources can be directed with an optimum pay-out. The present study takes first steps towards the usage of low-frequency ultrasound as a tool to evaluate the road condition.
We investigated the efficiency of phase gratings, i.e., the visibility upon variation of different parameters. Rotating around an axis parallel to the grid lines of the phase grating changes the grating’s shape and thereby the initial distribution of phase shifts. This yields high visibilities for shorter propagation distances than derived from box shapes. Tilting the grating in the scattering plane allows continuous tuning of the grating’s height that corresponds to an ideal phase shift for a particular photon energy. This opens the way for tuning the design energy suitable for the material under investigation. Our study included simulations for monochromatic sources with the sampling procedure for rectangular and triangular phase gratings.
We report on the in situ investigation of mechanochemical syntheses of metal phosphonates. The metal phosphonates are formed in milling reactions starting from a metal acetate and a phosphonic acid. The conversions are observed by synchrotron PXRD and Raman spectroscopy to shed light on the reaction mechanisms including possible intermediates.
We present an in situ investigation of the mechanochemical formation of cocrystals using synchrotron XRD and Raman spectroscopy. This combination allows to study milling processes on the level of the molecular and crystalline structure thus obtaining reliable data for mechanistic studies. Thereby, mechanochemical syntheses can be optimized to isolate new crystal structures.
Characterization of residual stress state by neutron diffraction and residual magnetic field mapping
(2016)
Based on the residual stress characterization of tungsten inert gas welded S235JRC+C plates by means of neutron diffraction, the evaluation of residual stress with high spatial resolution GMR (giant magneto resistance) sensors is discussed. The experiments performed indicate a correlation of residual stress changes and local residual magnetic stray fields.
Additive Manufacturing (AM) by Selective Laser Melting (SLM) offers ample scope for producing geometrically complex parts as compared to the traditional subtractive manufacturing strategies. However, the residual stresses developed during the processing can reduce the load bearing capacity as well as induce unwanted distortion, limiting the application of SLM parts.
IN718 manufactured by SLM process can show high tensile residual stresses in the surface as high as the yield strength of the wrought alloy. On the other hand, residual stresses in the bulk Show considerably lower stress values, even in compression, indicating a stress re-distribution during deposition of the SLM layers.
Selective Laser Melting (SLM) technique allows to produce parts with complex geometry. Due to the rapid solidification and heat gradient during production, SLM results in presence of residual stress. The present study shows the influence of manufacturing parameters on surface residual stress of Ti-6Al-4V SLM parts. High tensile stresses in the front surface are found. Heat Treatment conditions relax residual stresses almost to zero. High scanning speed during manufacturing results in higher tensile stresses in the surface.
Were prepared four unsubstituted Pc - C60 fullerene systems, using two different synthetic strategies, via Prato (1,3 - dipolar cycloaddition) or Bingel reactions. The precursor Pcs 1 and 2 were successfully synthesized by cyclotetramerization reaction between TBDPS - protected and unsubstituted phthalonitriles. The surface studies are currently ongoing.
Ethylene-propylenene-diene copolymer rubbers (EPDM) are used in a wide range of sealing applications e.g. in automotive industry or in containers for dangerous goods. Investigations with regard to the ageing behavior and lifetime prediction of commercial EPDM rubber seals consisting of 48 % polypropylene (PP) and 4.1 % of 5-ethylidene-2-norbornene (ENB) were conducted [1]. However, structural parameters (monomer ratio, diene type, curing agent etc.) and additives (filler, plasticizer etc.) are known to affect the ageing behavior of rubber compounds [2, 3]. The aim of the current study was to elucidate the influence of each component on the overall deterioration of material properties after thermal ageing. Therefore, different EPDM mixtures were prepared at BAM, the reference being an EPDM with 48 % PP and 4.1 % ENB reinforced with Sillitin. Five more formulations were prepared in order to assess the effect of (i) filler type (carbon black or sillitin), (ii) curing agent (sulfur or peroxide), (iii) plasticizer, (iv) ethylene-propylene ratio and (v) ENB content. Initially, the properties of the unaged materials were investigated by tensile testing, hardness and density measurements, TGA, DSC and DMA. Sulfur vulcanization resulted in higher elongation at break due to the flexibility of the sulfidic crosslinks. Carbon black resulted in better reinforcement compared to Sillitin. A higher ethylene and ENB content lead to higher hardness due to higher crystallinity and higher crosslink density, respectively.
Thermal ageing for up to 30 days (with 10 days intervals) took place in circulating hot air ovens at 125 °C. Pronounced crosslinking was found to take place in all peroxide-cured materials, as the unreacted double bonds of the ENB units acted as starting points for oxidation and crosslinking. Increasing the ethylene content resulted in an increase in the ageing resistance of EPDM. This improvement was attributed to the higher crystallinity that inhibits oxygen diffusion and to the smaller number of chain scissions which occur in the PP units. Although significant loss of the plasticizer was observed, the remaining plasticizer adequately improved the tensile properties of the material. The filler type did not significantly affect the ageing behavior of EPDM. Finally, the lower thermal stability of the sulfidic crosslinks resulted in desulfurization and, thus, in an increase in the crosslinking density.
To sum up, it has been shown that the monomer composition, curing agent and additives used in EPDM formulations greatly influence the properties and ageing resistance of these materials.
Application of 4Q-BSE detector and dedicated software enables 3D surface measurements of fracture samples in SEM. 3D surface measurement is independent from magnification and material invariant. Quantitative height measurements require careful detector adjustment and system calibration. Live 3D view allows a fast assessment of topographical features. In addition to SE and BSE imaging, 3D surface data help to analyse and interpret fracture samples.
Pressurisation of full-containment pressure vessels in fire is known to be driven by thermal stratification. The predominant mode of heat transfer to the contents (convection from the shell to the liquid phase) results in formation of „hot“ boundary layers. Sub-cooled boiling may also be present. The warm layer rises to the surface through buoyancy and bubble flow, increasing the surface of the liquid above that of the bulk temperature, and hence driving a pressure rise.
For reliable prediction of the complex effects governing vessel pressurization a three-dimensional numerical model is required. Work is being undertaken on such a model by other institutions in cooperation with this project.
The arrangement of the measuring sensors allowed the
capture of air flow induced temperatures and material
temperatures on various points of the cylinder body. Four
significant temperature levels could be observed: Inside the cylinder (far from the wall, close to the wall), inside the aluminium liner and outer surface. Figure 5 shows the temperature distribution after a regular filling process with a filling time of ten minutes. The temperature sensors T1 - T9 are marked with different colors. The corresponding measurement points are shown in Figure 4. Due to the high thermal conductivity of the aluminum liner the induced temperature peaks are quickly derived. A flow-induced exceeding of the maximum approval temperature is not expected. Regarding the safety assessement the results show that the pressure and temperature profilesmustbe taken into account.
A new tank design for Hazmat
(2016)
Initial studies have shown pre-deformed honeycomb structure
pressure vessels to have comparable burst pressure to straight steel vessels.
It was shown that honeycomp structured tanks have a higher energy absorption than straight steel tanks.
Future studies will investigate optimization of the deformed plate, to determine if increased payloads or a reduced wall thickness can be achieved.
Mg-Y,RE-Zn systems present second phases with high thermal stability, promoting the increase of strength and creep resistance at high temperatures.
Mg and its alloys have a potential application as biomaterials due to their biocompatibility and degradation behaviour. The dominant corrosion mechanism in those alloys is the microgalvanic corrosion through coupling of the more noble second phases with the Mg matrix, and therefore a low concentration of those was sought.
In order to reduce CO2 emissions fossil fuelled power stations with high combustion efficiency are being developed. The increase of the operating temperature, a common way to improve combustion efficiency, leads to enhanced corrosion of heat exchange steel tubes in the power plants. Within the framework of the European project “Production of Coatings for New Efficient and Clean Coal Power Plant Materials” (POEMA)", high temperature corrosion protection coatings are now under investigation.
Thin porous sol-gel alumina films are promising candidate coating materials. Coatings were prepared by applying boehmite sols on grinded steel P92 and subsequent heat treatments at temperatures up to 650 °C. Thus a porous layer of worm-like particles was formed consisting of nano-crystallites and amorphous alumina. A dense interface with satisfying adhesion resulted from diffusion of chromium and iron ions out of the steel into the porous coating. However, the film locally exhibited some cracks caused by steep edges in the grinded steel surface. An appropriate substrate pretreatment should avoid this problem.
The protection of the steel relies on the barrier function of the alumina coating and the formation of a dense chromia layer at the steel surface.
As subcritical crack growth (SCCG) can reduce tensile strength of glasses by many orders of magnitude, the potential for improvement of fatigue behaviour is most intriguing in developing ultra-strong glasses. An essential bottleneck is the basic understanding of the numerous interplaying pressure-, temperature- and water-affected relaxation phenomena at the crack tip and related toughening strategies. Therefore, the present project aims to advance the basic understanding of structural relaxation effects and local properties caused by increased water concentration and tensile stresses at the crack tip as they are a key for structural toughening designs to develop SCCG-free glasses and glass surfaces.
Our first studies give clear evidence that glass structure and dynamics is strongly modified upon hydration of glasses. These changes are highly related to the nature of network formers but are affected as well by the counter ions (network modifier). Results of the 1st project part suggest that structural relaxation below glass transition temperature, i.e. overlapping of short-range (beta) and long-range (alpha) interactions can contribute to SCCG in water-free environments and that structurally dissolved water in the glasses can have decisive impact on this effect.
In the 2nd project stage specific glasses compositions will be investigated to gain an improved understanding on the relation of sub-Tg relaxation and inert SCCG as well as to shed light to the related effects of dissolved water and its speciation. These glasses cover a broader range of different glass topologies and binding partners, whereby the coupling of alpha and beta relaxations is varied systematically by alkali-, alkaline earth ions and water species concentrations. Preparation of hydrous glasses (up to 8 wt% water) will be performed by high pressure syntheses. Structure will be resolved by NMR, Raman and IR spectroscopy while structural relaxation is accessed in the temperature and frequency domain using dynamic mechanical spectroscopy and ultrasonic damping. We will focus on measurements of inert SCCG (region III) conducting experiments in vacuum and dry gas atmospheres using indentation techniques and stressing of glass specimens in DCB geometry.
Experimental data on SCCG will be provided to SPP groups, which deals with fatigue in metallic glasses and vice versa we will test theoretical predictions of ab-initio simulations of partner within SPP 1594 in order to quantify the effect of water on the crack tip. In summa topological factors controlling the subcritical crack growth with respect to water will be identified from which structural toughening designs for highly fatigue resistant-glasses can be derived.
We investigated the efficiency of phase gratings, i.e., the visibility upon variation of different parameters. Rotating around an axis parallel to the grid lines of the phase grating changes the grating’s shape and thereby the initial distribution of phase shifts. This yields high visibilities for shorter propagation distances than derived from box shapes. Tilting the grating in the scattering plane allows continuous tuning of the grating’s height that corresponds to an ideal phase shift for a particular photon energy. This opens the way for tuning the design energy suitable for the material under investigation
Optimizing the performance of phase gratings for better visibility in Talbot- Lau interferometry
(2015)
We investigated the efficiency of phase gratings, i.e., the visibility upon variation of different parameters. Rotating around an axis parallel to the grid lines of the phase grating changes the grating’s shape and thereby the initial distribution of phase shifts. This yields high visibilities for shorter propagation distances than derived from box shapes. Tilting the grating in the scattering plane allows continuous tuning of the grating’s height that corresponds to an ideal phase shift for a particular photon energy. This opens the way for tuning the design energy suitable for the material under investigation. Our study included simulations for monochromatic sources with the sampling procedure.
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 sintering, however, is currently restricted to silhouette methods, i.e. heating microscopy. For complex shaped samples, in situ shape screening during shrinkage would allow much better validation of 3D sinter simulation models. Further, by revealing temporary sinter warpage, 3D high-temperature shape screening allows 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.
Bioglass® 45S5 is mainly used clinically as powders, granules or pastes instead of sintered compacts. This is due to the inherent problem of crystallization during the sintering, which results in poor mechanical properties and reduced bioactivity. Recently, new bioactive glasses with improved crystallization stability have been developed as promising candidates for manufacturing of sintered powder compacts for bone regeneration, which combine improved sintering behavior with bioactivity. Compared with the well-known Bioglass® 45S5 (SiO2-P2O5-CaO-Na2O) the calcium/alkali oxide ratio was increased, sodium oxide was partially replaced by potassium oxide and up to 3 mol% calcium fluoride were added, in order to stabilize the glass against crystallization. The aim of this study was to investigate the sintering and crystallization behavior of these new bioactive glasses.
Sintering and crystallization were characterized by heating microscopy, XRD, FTIR, SEM, and DTA. The results show that a sintered density of 88-99 % is achieved in contrast to only 57-67% for Bioglass® 45S5. In addition, FTIR and XRD analyses show that Bioglass® 45S5 crystallized during sintering while for the new glasses no crystalline phases are detected. The thermal properties of all glasses were studied by DTA measurements, and the influence of grain size was characterized. These studies showed that full densification can be attained for particle size < 32 µm, whereas coarser particles progressively increase residual porosity. Observed foaming phenomena, are strongly retarded by crystallization of beta-HAp.
Bioglass® 45S5 is mainly used clinically as powders, granules or pastes instead of sintered compacts. This is due to the inherent problem of crystallization during sintering. Recently, new bioactive glasses with improved crys-tallization stability have been developed as promising candidates for manufacturing of sintered powder compacts for bone regeneration, which combine improved sintering behavior with bioactivity. Compared with the well-known Bioglass® 45S5 (SiO2-P2O5-CaO-Na2O) the calcium/alkali oxide ratio was increased, sodium oxide was partially replaced by potassium oxide and up to 3 mol% calcium fluoride were added, in order to stabilize the glass against crystallization. Sintering and crystallization were characterized by heating microscopy, XRD, FTIR, SEM, and DTA. The results show that a sintered density of 88-99 % is achieved in contrast to only 57-67% for Bioglass® 45S5. Whereas Bioglass® 45S5 powder compacts crystallize during sintering, for the new glasses no crystalline phases were detected. Additionally the influence of grain size was characterized. These studies showed that full densification can be attained for particle size < 32 µm, whereas coarser particles pro-gressively increase residual porosity. Observed foaming phenomena, are strongly retarded by crystallization.
Nowadays, the use of bioactive glasses is established for bone regeneration; however glasses are used mostly as powders, granules or in a paste. Sintered scaffolds are not used clinically, because of the in inherent problem of crystallization during the sintering process, resulting in poor mechanical properties and reduced bioactivity. The aim of this study was therefore to design new bioactive glasses, which combine improved processing and sintering with bioactivity.
Compared with the well-known Bioglass® 45S5 (SiO2-P2O5-CaO-Na2O) the calcium/alkalioxide ratio was increased, sodiumoxide was partially replaced by potassiumoxide and up to 8 mol% calciumflorid were added, in order to stabilize the glass against crystallization.
The sintering behavior of the new glasses was characterized by heating microscopy and compared to Bioglass® 45S5. The results showed that the new glasses achieved a sintered density of 88-99 % in contrast to only 57-67% for Bioglass® 45S5. In addition FTIR and XRD analyses showed that Bioglass® 45S5 crystallized during sintering while for the new glasses no crystalline phases were detected. The thermal properties of all glasses were studied by DTA and DSC measures, and the influence of grain size and heating rate were characterized. These studies showed a shift of start and end temperature of sintering process as well as the final density. The structure of sintered specimens during and after sintering was examined using light and electron microscopy (REM).
Bioglass® 45S5 is mainly used clinically as powders, granules or pastes instead of sintered compacts. This is due to the inherent problem of crystallization during the sintering, which results in poor mechanical properties and reduced bioactivity. Recently, new bioactive glasses with improved crystallization stability have been developed as promising candidates for manufacturing of sintered powder compacts for bone regeneration, which combine improved sintering behavior with bioactivity. Compared with the well-known Bioglass® 45S5 (SiO2-P2O5-CaO-Na2O) the calcium/alkali oxide ratio was increased, sodium oxide was partially replaced by potassium oxide and up to 3 mol% calcium fluoride were added, in order to stabilize the glass against crystallization. The aim of this study was to investigate the sintering and crystallization behavior of these new bioactive glasses.
Sintering and crystallization were characterized by heating microscopy, XRD, FTIR, SEM, and DTA. The results show that a sintered density of 88-99 % is achieved in contrast to only 57-67% for Bioglass® 45S5. In addition, FTIR and XRD analyses show that Bioglass® 45S5 crystallized during sintering while for the new glasses no crystalline phases are detected. The thermal properties of all glasses were studied by DTA measurements, and the influence of grain size was characterized. These studies showed that full densification can be attained for particle size < 32 µm, whereas coarser particles progressively increase residual porosity. Observed foaming phenomena, are strongly retarded by crystallization of beta-HAp.
To better understand the mechanism of hydrogen assisted cracking (HAC), it is important to investigate the 3D structure of the cracks non-destructively. Since, cracks introduced by HAC are usually very small, conventional x-ray imaging methods often lack the required spatial resolution.
However, the detection of those cracks can be enhanced by taking advantage of refraction at interfaces within the sample.
To image this refractive deflection we employ analyser based imaging (ABI). In this work we aim at proving the enhanced crack detection of ABI by investigating an alluminum alloy weld.
Ferritic steels with Cr-contents up to 13 wt. % are used as heat exchanger or boiler tube materials in combustion based power plants. These materials are subject to aggressive corrosion caused by the reaction of the steel with highly corrosive gases under high temperatures up to 650°C. The early stages of corrosion and sulfidation especially and the influence of the Cr-content in the alloy are thereby not understood but of fundamental interest.
Our work shows corrosion mechanisms and presents corrosion models for Fe and different Fe-Cr-alloys under pure SO2 und SO2+O2 atmospheres for different time scales. Modell alloys of high purity are used to focus on the reaction of the intended elements: Fe, Cr, S, and O. Long-time experiments (≥12h) took place in tube furnaces and short-time experiments (≥5min) in a special designed light furnace. Heating and cooling took place under inert atmosphere. The reactive gases were added not until the experimental temperature was reached. Samples were analyzed using high resolution synchrotron X-ray diffraction using a micro focus setup and electron microscopy including FIB.
Many earlier studies on corrosion and sulfidation on iron based alloys show a higher corrosion rate and material loss when sulfur was present in the atmosphere. In contrast, later studies propose an inhibiting effect of sulfur containing atmospheres. On the one side, most likely due to the formation of a protective layer of Mx(SO4)y -phases at the scale-gas interface. On the other side, a very recent study proposes the theory that MxSy-phases limit the further diffusion of elements. Up to now, no Mx(SO4)y –phases were detected in our samples, but sulfide phases nucleated within the oxide phases. For pure Fe our samples show FeS at the scale-metal interface working as a diffusion barrier for Fe-Cations from the base material in to the oxide scale. The above lying spalled off oxide-sulfide scale shows a wide area of small voids and accumulations of FeS-Crystals at the bottom. Under the main oxide scale a second generation of oxide-sulfide scale starts to form. For the Fe-Cr-alloys the inner oxide scale only shows FeS- and CrS-phases surrounded by hollow space. The here presented study will explain and discuss a new growth model for the shown phenomenon.
The role of metal reducing bacteria (MRB) in corrosion is being controversially discussed in the literature. They can utilize metals including iron, uranium and manganese as well as many organic compounds as electron acceptors. The reduction of Fe(III) compounds to soluble Fe(II) species leads to the destruction of passive films on steel, resulting in acceleration of general and local corrosion processes. Recent research shows that the secretion of electron shuttles like riboflavins also contribute to the extracellular electron transfer (EET).
The aim of this project is to understand the chemical and electrochemical interaction mechanisms of MRB with steel surfaces by means of combined in situ techniques. An electrochemical XANES (x-ray absorption near edge spectroscopy) cell has been designed to study the changes of passive film chemistry in the presence of biomolecules and MRB. Electrochemical quartz crystal microbalance (eQCM) is used for studying the kinetics of bacterial cell attachment and diffusion of biomolecules in model biofilms. In situ investigations are complemented by ex situ spectroscopic and microscopic analysis to investigate the biofilm structure, composition and cell viability.
Via the combination of electrochemical methods with spectroscopic techniques and QCM we are able to follow biological processes and resulting degradation of steel surfaces in a non-destructive manner. The selection of model systems and a defined biological medium allows the identification of the effects of individual 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.
The optical properties of semiconductor nanocrystals (SCNCs) depend on constituent material, particle size, and surface chemistry, with the size of the photoluminescence (PL) quantum yield (QY) and the PL decay kinetics being largely controlled by the number of dangling bonds, which have to be properly passivated for high quality materials. Hence, PL measurements can provide insight not only in SCNC photophysics, yet can be also used for quality control of SCNC synthesis and surface modification. In this respect, steady state and time-resolved fluorometry and confocal microscopy with time correlated single photon counting were used to study the PL properties of core-shell CdSe SCNCs with different shells and surface chemistries on ensemble and single particle level, thereby focusing on a correlation of ensemble PL QY and PL decay kinetics with particle brightness, PL time traces, and the On-time fraction of single SCNCs. Additionally, confocal PL images were correlated with AFM measurements in order to derive the amount of absorbing, yet non-emissive ”dark” SCNCs, the presence of which resulting in an underestimation of ensemble PL quantum yields. The results of this study can help to identify synthetic routes and surface modifications, which minimize the fraction of dark SCNCs.
The optical properties of semiconductor nanocrystals (SCNC) are controlled by constituent material, particle size, and surface chemistry, specifically the number of dangling bonds favoring nonradiative deactivation, and hence also by particle synthesis. In this respect, the fluorescence properties of coreshell CdSe SCNCs with different shells and surface chemistries were studied on ensemble and single particle level, using steady state and timeresolved fluorometry and confocal microscopy with time correlated single photon counting detection. Special emphasis was dedicated to correlate ensemble photoluminescence (PL) quantum yields and decay kinetics with particle brightness, PL time traces, and the Ontime fraction of the single SCNCs. Additionally, the confocal PL images were correlated with AFM measurements in order to derive the amount of absorbing, yet nonemisssive ”dark” SCNCs, the presence of which leading to an underestimation of ensemble PL quantum yields. The results of this study can help to identify synthetic routes and surface modifications minimizing the fraction of dark SCNC, thereby closing the gap to the ultimate goal of colloidally and photochemically stable SCNCs with a PL quantum yield of close to unity.
Maintaining a consistent product quality is critical for the thin film industry. Therefore, the development of highly accurate protocols able to detect variations and nonidealities in manufactured thin film devices is essential and helps improve production quality and decrease manufacturing costs. The present work will discuss the accuracy and reproducibility in the determination of the thickness of thin films relevant for optoelectronic industry using spectroscopic ellipsometry, starting with the importance of set-up calibration, the need for very well defined calibration standards suitable for real devices and not least, the importance of accurate data analysis. As ellipsometry is an indirect method and theoretical modelling is needed to obtain the desired information regarding the investigated samples (e.g. thickness, roughness, optical constants), the model uncertainty has to be discussed and taken into account. If for ideal samples consisting of single layers with well-known optical constants the determination of thickness and roughness is straight forward and pretty accurate, for real samples, more complex theoretical models are needed and extracting accurate information regarding the samples can be very challenging. With careful calibration and a multidisciplinary approach, a combined measurement methodology can be developed enabling reliability, comparability, and accuracy. For production-relevant operation, maintaining the ease of use and scalability of ellipsometry as a technique can also be retained.
In the present study, internal damage to an AlSi12CuMgNi alloy reinforced with planar random Al2O3 short fibres was investigated after compression testing. Due to the alloy composition, this composite contains a second reinforcement phase in the form of eutectic Si, which builds interpenetrated networks in the volume and increases the creep resistance and load-bearing capacity of the material. Materials with their fibre plane parallel and transversal to the load direction were characterized in order to investigate the dependence of load partition and damage on fibre plane orientation. In-situ compression testing during neutron diffraction measurements showed that internal damage is strongly influenced by the load partition between matrix and reinforcement. Moreover, micro-computed tomography was performed in the same material after ex-situ compression for damage analysis. In the case of a fibre plane perpendicular to the applied load, breakage and interconnected cracks appeared in a significantly higher volume fraction than with a fibre plane parallel to load.
Two polyethylene types with ultra high (UHMWPE) and high molecular weight (HMWPE), which are used as neutron radiation shielding materials in storage casks for radioactive waste, were subjected to gamma irradiation doses up to 600 kGy and subsequent thermal ageing at 125 °C for up to one year. One material was a medical grade UHMWPE and the other a HMWPE containing an antioxidant. Degradation effects in the materials were characterized using colorimetry, UV-Vis spectroscopy, MIR and FTIR measurements, DSC and, in the case of HMWPE, insoluble content determination. Both materials exhibited a yellowing upon irradiation. The discoloration of UHMWPE disappeared again after thermal ageing, which is why it was attributed to annealable color centers in the form of free radicals entrapped in the crystalline regions of the polymer that recombine during thermal ageing. Furthermore, oxidation species were observed with MIR and FTIR spectroscopy. For HMWPE, the yellowing occurred during both irradiation and thermal ageing and was correlated to antioxidant decomposition. Additionally, black spots were observed after thermal ageing of HMWPE that were attributed to reaction products of antioxidant derivatives and catalyst residues. While only little evidence of oxidation species was found in the light material parts, oxidation is expected to concentrate in the black spots as the catalyst residue promotes hydroperoxide decomposition and thus radical formation that initiate polymer oxidation
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.
Polymers are favorable materials for gas separation membranes. In general, gas transport experiments are performed with films in the range of 100 µm thickness. However, in large-scale processes very thin selective polymer layers in the range of 100 nm to 1 µm are used. Moreover, it was shown that thin films behave different compared to thick films with respect to gas transport properties and physical aging as well. Thus, for fundamental research it is important to realize gas transport experiments with thin films. The Quartz Crystal Microbalance (QCM) is a very sensitive method to detect mass changes in the range of nanograms. Therefore, this method enables sorption experiments with thin films or layers attached to the QCM crystal (100 nm up to 1 µm). Here, we present the experimental set-up for using the QCM technique for characterizing the gas sorption behavior of thin polymer films in a temperature controlled pressurized environment (up to 50 bar) - also quartz crystals and crystal holders were optimized. The study aims for the characterization of long-term behavior and physical aging of high-performance polymers for gas separation membranes - such as polyimides and polymers of intrinsic microporosity (PIMs) and respective nanocomposites. Especially the differences of the behavior of thin films compared to films with thicknesses up to 100 µm as well as nanofiller induced-effects are adressed.
Low-alloyed CrMoV steels, such as T24, are widely used for welded components in fossil power stations due to their excellent creep-strength. Spectacular failure cases in the recent years exhibited severe cracking in T24 welds. The results showed that hydrogen-assisted cracking (HAC) occurring up to 200 degree Celsius cannot be excluded. Hence, a basic understanding is necessary on how hydrogen affects the material properties of welded microstructures. In this regard, each weld microstructure (HAZ and weld metal) has influence on the HAC susceptibility and respective hydrogen diffusion. Thus, the present contribution summarizes different results obtained from experiments with grades T24 (CrMoV alloy) and T22 (CrMo) and thermally simulated HAZ. Tensile tests were conducted with hydrogen charged specimens and compared to hydrogen-assisted stress corrosion cracking results obtained from slow strain rate tests (SSRT) up to 200 degree Celsius. Electrochemical permeation and degassing experiments were performed to identify a particular weld microstructure influence on hydrogen diffusion and trapping (especially in the HAZ). The results showed that T24 base material has improved resistance to hydrogen-assisted degradation/cracking. In contrast, the as-welded HAZ had remarkably increased susceptibility (tesnile tests at hydrogen concentration of 1 to 2 ppm). SSRT experiments confirmed this at elevated temperatures for both the T24 and the T22. Hence, the evaluation of a particular degradation of the mechanical properties should be performed independently for each weld microstructure. In addition, the HAZ showed decreased diffusion coefficients (at room temperature) of approximately one magnitude compared to the base materials. Trapped hydrogen was determined in the T24 at temperatures up to 120 degree Celsius compared to 75 degree Celsius in the T22. This has to be considered in case of changing operational temperatures, e.g. in the case of start-up and shutdown processes of boiler components.
Since geothermal wells are a feasible energy source to replace fossil fuel supply, many technologies have been developed to take advantage of geothermal energy. Nevertheless, service conditions in geothermal facilities are due to the chemical composition of hydrothermal fluids and temperatures, in many cases, extreme in terms of corrosion.
Therefore, materials selection based on preliminary material qualification is essential to guarantee a secure and reliable operation of the facilities. The corrosion behavior of different high-alloyed metals including Duplex and austenitic stainless steels as well as a nickel alloy have been evaluated in artificial geothermal fluids simulating the conditions in some locations with geothermal potential in Germany as well as two sites in Indonesia. The suitability of carbon steel 25CrMo4, stainless steels X2CrNiMo17-12-2, X2CrNiMo-22-5, X2CrNiMoCuWN25-7-4 and super austenitic steel X1CrNiMoCu32-28-7 in these geothermal fluids obtained by electrochemical measurements and exposure tests is limited. The nickel alloy NiCr23Mo16Al shows an excellent corrosion resistance against pitting corrosion. Excluding its high cost, it is a very good alternative to be used in the construction of geothermal facilities having highly saline brines. Stainless and Duplex steels exhibit a limited corrosion resistance concerning pitting and crevice corrosion. Beside of the higher alloyed materials, also the lowalloyed steel 25CrMo4 could be employed as a constructional material for the geothermal power plant in stagnant highly acidic non Saline environments, as long as the wall thickness of the material vs. corrosion rate is taken into account.
The formation of biofilms on different materials provokes high costs in industrial processes, as well as in medical applications. Therefore, the interest in development of new materials with improved surfaces to reduce bacterial colonization rises. In order to evaluate the quality and safety of these new materials, it is highly important to ensure world-wide comparable tests that are relying on statistical evidence. The only way to reach this statistical safety is through a high-throughput Screening under standardized test conditions.
We developed a flow through system for cultivation of biofilm-forming bacteria under controlled conditions with a total capacity for testing up to 32 samples in parallel. Quantification of the surface colonization was done by staining the bacterial cells with a fluorescence marker, followed by epifluorescence microscopy. More than 100 images of each sample were automatically taken and the surface coverage was estimated with the free open source software gmic (http://gmic.eu), followed by a precise statistical evaluation. Overview images of all gathered pictures of the whole material coupon were generated to illuminate the colonization characteristics of the selected bacteria on certain materials.
With this method, differences in bacterial colonization on different materials can be quantified in a statistically validated manner. The innovative and solid test procedure will support the design of improved materials for medical and industrial applications such as implants, ship hulls, pipelines, heat exchangers, aquaculture equipments, photovoltaic-panels and fundaments of wind power plants.
The Full-Notch Creep Test (FNCT) is widely used to characterize the slow crack growth (SCG) behavior of polyolefin materials in “inert” media as well as effects of environmental stress cracking (ESC) in which the medium has decisive influence on damage mechanism and time to failure tf*. Usually the FNCT is applied as a standardized testing method (ISO 16770) using a few universal liquid media, such as solutions of Arkopal N 100 (detergent).
Selected relevant PE-HD materials are investigated also in real media and influences of temperature and geometry of specimen and notch are explicitly addressed. The investigations comprise also the ESC behavior of PE-HD in media that are sorbed to a significant extent – such as Diesel and Biodiesel – based on comparison with samples previously saturated with those media.
Due to their chemical structure, a rigid disk-like aromatic core and flexible alkyl chains attached to the core, discotic liquid crystals (DLCs) can organize and stack themselves into columns in a hexagonal columnar mesophase, a mesophase in between the plastic crystalline and isotropicphase. The overlap of the π orbitals of the aromatic core in the hexagonal columnar mesophase leads to a high charge-carrier mobilitie along the column axis – these columns can be considered as “moleculer nanowires” making liquid crystals a promising class of materials for electronic applications. Previous studies on DLCs showed that the phase behavior of DLCs is susceptible to nano confinement. Here in this study, the thermotropic collective orientational order of 2,3,6,7,10,11 hexakis[hexyloxy] triphenylene (HAT6), a triphenylene based DLC, and the effects of nano confinment on of its phase behavior were investigated by broadband dielectric spectroscopy (BDS) and differential scanning calorimetry (DSC). HAT6 was embedded into nanoporous anodic aluminum oxide membranes by melt infiltration in the isotropic phase under argon atmosphere. The filled membranes have the thickness of 80 µm and the diameter of 15mm and parallel aligned tubular nanopores having the pore diameters of 25, 40, 80 and 180 nm. The filling degree for each sample was checked by thermogravimetric analysis (TGA) in order to ensure complete filling. The bulk HAT6 forms, a hexagonal columnar phase between the isotropic phase above 371 K, and the plastic crystalline phase below 340 K. Unlike the bulk, the confined HAT6 forms two peaks in the heat flow during the plastic crystalline-to-hexagonal columnar phase transition, which might be the evidence of two different phase structures close to the wall and in the pore center. Moreover, the isotropic-to-columnar transition of the confined HAT6 shifts with decreasing pore diameter to lower temperatures.
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 sintering, however, is currently restricted to silhouette methods, i.e. heating microscopy. For complex shaped samples, in situ shape screening during shrinkage would allow much 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. 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 times of the energy revolution, the need for energy efficient separation processes promotes the advancement of new high performance materials for use as highly selective separation membranes. Most promising materials in this field, especially for gas separation, are polymers with intrinsic microporosity (PIMs) which were firstly introduced by Budd and McKeown. In this study the permeability of PIM-1 was increased by 439 % by formation of nanocomposites with only 1 wt% of polyhedral oligomeric phenethyl-silsesquioxane (PhE-POSS) within the polymer matrix. As the CO2/CH4 selectivity is fully retained, this leads to a shift in the Robeson plot towards the upper bound. The Robeson plot describes the current state of the art trade-off relation between selectivity and permeability of all known membrane polymers. As molecular mobility is a key factor for gas transport as well as the often observed physical aging of such polymers, our study also includes for the first time, molecular dynamics and conductivity of pure PIM-1 and PIM-1 nanocomposites as investigated by broadband dielectric spectroscopy (BDS).
Mechanical characterization of high-density polyethylene in contact with diesel and biodiesel fuels
(2016)
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 polymeric materials widely used in the fuel infrastructure as well as for automotive parts. Especially changes in the structural properties and mechanical behavior of the polyethylene (PE-HD) have to be addressed.
The presented work comprises the direct interaction of high density polyethylene (PE-HD) with diesel and biodiesel, resulting in swelling and plasticization. Also long-term degradation phenomena will be discussed.
The chosen PE-HD types are typical thermoplastic resins for container and storage tank applications. The impact of diesel and biodiesel in PE-HD is investigated by changes in the mechanical properties with emphasis on the Charpy impact strength. Furthermore, structural and dynamic influences on the polymeric material induced by diesel and biodiesel are proven in Dynamic Mechanical Analysis (DMA). Both methods, Charpy impact strength and DMA, reveal softening effects due to the migration of diesel and biodiesel into the amorphous regions of PE-HD.
Since biodiesel is more prone to oxidative degradation compared to diesel, the fuel/air/polymer-interaction is studied for partly immersed tensile test specimens. Main focus of the evaluation is the co-oxidation. Here, the accelerated deterioration of PE caused by the sorption of the facile oxidation of biodiesel into the solid polymer might be a major degradation mechanism in this context.
Characterization of statistical EO-PO copolymers containing different end groups by UPLC/ESI-MS
(2016)
Commercial statistical ethylene oxide (EO) and propylene oxide (PO) copolymers of different monomer compositions and different average molar masses were studied by liquid chromatography under critical conditions (LCCC). Theoretical predictions of the existence of a critical adsorption point (CPA) for statistical copolymers with a given chemical and sequence distribution, could be studied and confirmed. An improved way to determine these critical conditions in a copolymer, alongside the inevitable chemical composition distribution (CCD), with the aid of mass spectrometric detection is described. Shift of the critical eluent composition with the monomer composition of the polymers could be observed. Due to the relatively low average molecular weight, broad molecular weight distribution (MWD) and the presumed existence of different end group functionalities as well as sequence distribution, gradient separation only by CCD was not possible. Therefore isocratic separations at the CPA of definite CCD’s were applied. Although the various present distributions partly superimposed the separation process the goal of separation by end group functionality could still be achieved on the basis of the additional dimension of ESI-MS. The existence of HO-H besides the desired AllylO-H end group functionalities could be confirmed and their amount could be estimated.
Materials that respond to the environment by changing their properties are critical for developing
autonomously adaptive systems. However, to reversibly influence a material's inherent characteristics, such as its ability to self-heal, from distance without continuously expending energy, remains a challenging task. Herein, we report on the modul at ion of imine exchange kinetics by light, manifested in a remote controllable dynamic covalent polymer network. Simple mixing of a commercially available amino-functionalized polysiloxane with small amounts of a photoswitchable diarylethene cross-linker, carrying two aldehyde groups, yields a rubbery material. Its viscoelastic and self-healing properties can be reversibly tuned with everyday light sources, such as sunlight. Our two-component system offers the unique advantage that self-healing takes place continuously without any additives at ambient conditions and is neither dependent on continuous illumination nor does it require recent damage. Overall, our approach allows for the local amplification of intrinsic material properties in a permanent yet reversible fashion. The availability of the inexpensive sta1ting materials on a multi-gram scale, the easy synthesis of the polymer network, and its convenient handling paired with high versatility make our Approach highly applicable to create custom-tailored adaptive materials.
Healable materials are able to repair inflicted damages, herin often applied: dynamic covalent polymer networks. We have shown in this study that light of different colors shift the Diels-Alder and retro Diels-Alder crosslinking and decrosslinking equilibrium. This effect was utilized for self-healing of a polymer film. Small-angle X-ray scattering was used to quantifiy the polymeric mesh size on a nanoscale.
Calcium cobaltite is a promising p-type oxide thermoelectric material for high temperature applications due to its high figure of merit between 600 °C and 900 °C in air. The solid-state-reaction is well known for large scale powder synthesis of functional materials. As a high temperature process, the powder synthesis consumes a lot of energy. In different studies, different synthesis conditions were used for the preparation of calcium cobaltite powder. This study showed that a higher energy input (elevated temperatures, longer dwell times, or repeated calcinations) during powder synthesis does not increase but decrease the Seebeck coefficient and the electrical conductivity. The same correlation was determined for the densification. As a higher energy input leads to a larger grain size and therefore to a reduced sinter activity, it can be concluded that the thermoelectric properties are correlated with the sinter activity of the powder. These results can be used to minimize the energy demand for the powder synthesis of Ca₃Co₄ O₉.
Multilayer carbon nanomembrances (CNMs) could pave the way for a new ultrathin functional conductive coatings with tunable electrical, optical, and chemical properties. Due to their molecular thickness, they can also be regarded as “interfaces without bulk” separating regions of different gaseous, liquid, or solid components and controlling the materials exchange between them, making them optimal materials for membranes applications. Furthermore, their physical and chemical properties depend strongly on their structure, molecular composition, and the surroundings of either sides, thus allowing for tailored properties. Here, nanolayers of Aromatic p-terphenylthiol (TPT) self-assembled into 2D carbon monolayers (thickness - 1.6 nm) were synthesized and further crosslinked by ion bombardment, forming CNMs. Here, though a recently developed multilayer nanosheets routine, stacks of 5, 10, 15 and 20 TPT sheets where transferred on top of each other forming a multilayered CNMs. However, this transfer routine could introduce some intrinsic defects to the sheets, which would alter the molecular composition and / or structure, thus consequently the CNMs properties. Therefore, it is essential to characterize defects in “pure” TPT nanomembranes, before tailoring the molecular compositions, e.g. adding functional groups. For this reason, broadband dielectric spectroscopy (BDS) was utilized to characterize any defects that could be rasied during preparation. Due the structure of pure TPT membranes, no dipole moment should exsist. However, the presence of other elements, e.g. water or sulphur, would result in a dipole moment that could be probed by BDS.
As a main result, for all different stacked-layer numbers, a clear relaxation process is seen, which moves to higher frequencies with increasing the temperature. The temperature dependence of the relaxation rate of this process is independent of film thickness and can be well described by a common VFT function, hence a corporative motion. This relaxation process was assigned to intrinisic defects in the membranes, introduced during preparation, which was further confimed by a detailed anaylsis of the dielectric strength. This is the first BDS measurment on TPT CNMs.
Many engineering structures are made of composite materials or metal foam. To simulate the deformational behaviour of these structures often requires a high number of discretisation elements. This in turn yields a very large system of linear
equations that are extremely time and memory consuming or practically impossible to solve. It is therefore desirable to find an approach to overcome this obstacle.
Many engineering structures are made of composite materials or metal foam. To simulate the deformational behaviour of these structures often requires a high number of discretisation elements. This in turn yields a very large system of linear equations that are extremely time and memory consuming or practically impossible to solve. It is therefore desirable to find an approach to overcome this obstacle.
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.