Ingenieurwissenschaften und zugeordnete Tätigkeiten
Filtern
Erscheinungsjahr
Dokumenttyp
- Zeitschriftenartikel (1904)
- Beitrag zu einem Tagungsband (72)
- Beitrag zu einem Sammelband (11)
- Buchkapitel (9)
- Posterpräsentation (1)
- Forschungsbericht (1)
Sprache
- Englisch (1959)
- Deutsch (30)
- Mehrsprachig (8)
- Russisch (1)
Referierte Publikation
- ja (1998) (entfernen)
Schlagworte
- Additive manufacturing (74)
- Mechanochemistry (63)
- Quantum yield (62)
- SAXS (61)
- Fluorescence (58)
- Nanoparticles (48)
- Nanoparticle (46)
- Microstructure (45)
- Lifetime (41)
- MALDI-TOF MS (40)
Organisationseinheit der BAM
- 6 Materialchemie (576)
- 5 Werkstofftechnik (299)
- 9 Komponentensicherheit (297)
- 6.3 Strukturanalytik (240)
- 8 Zerstörungsfreie Prüfung (202)
- 1 Analytische Chemie; Referenzmaterialien (179)
- 7 Bauwerkssicherheit (139)
- 8.5 Röntgenbildgebung (134)
- 6.1 Oberflächen- und Dünnschichtanalyse (115)
- 5.1 Mikrostruktur Design und Degradation (114)
Paper des Monats
- ja (40)
Die in zunehmenden Maße Mitte der 80er Jahre einsetzende Substitution von metallischen Materialien z. B. durch hochleistungsfähige polymere Werkstoffe und Verbundwerkstoffe wurde u. a. von der DGM zum Anlass genommen, ihre zukünftigen Aufgaben neu zu definieren und gleichzeitig mit der Gründung des Fachausschusses "Gefüge und Eigenschaften von Polymerwerkstoffen" dieser neuen Entwicklung in der Materialkunde auf dem Gebiet der Kunststoffe und ihrer Anwendungen Rechnung zu tragen.
Characterization of the fcc/bcc orientation relationship by EBSD using pole figures and variants
(2004)
The orientation relationship (OR) between fcc and bcc lattices are described by crystallographic fundamentals using the example of Kurdjumov-Sachs (K-S) and Nishiyama-Wassermann (N-W). Complete pole figures containing all variants will be used to distinguish even between slightly different ORs. EBSD on iron meteorites and duplex steel has been used to analyse a large number of crystal orientations with regard to a high statistical significance and a high probability to capture all variants in a single measurement. It is shown that the use of fixed OR models like K-S, N-W, Bain, Pitsch, or Greninger-Troiano does not satisfacturally reflect the observed experimental pole distributions. It is not convenient to use high-indexed lattice planes and directions to describe the small deviations from the given models. The Euler subspace representation offers a readily comprehensible tool to get an idea about the characteristic of the experimentally detected OR.
ür die Berücksichtigung mechanischer Belastungen unterhalb der Streckgrenze ist im Rahmen einer zuverlässigen Bauteilauslegung die Kenntnis der elastischen Konstanten von besonderer Bedeutung. Für die experimentelle Bestimmung des Elastizitätsmoduls wurde eine Vielzahl von Verfahren entwickelt, die zum Teil werkstoffspezifisch Eingang in die Normung gefunden haben.
Prinzipiell können diese Verfahren in zwei Gruppen unterteilt werden: die statischen und die dynamischen Prüfverfahren. Die statischen Verfahren beruhen auf der direkten Messung des Spannungs-Dehnungs-Zusammenhangs während einer mechanischen Belastung im elastischen Verformungsbereich (Zug, Biegung, Druck). Die dynamischen Verfahren basieren auf der Schwingungsanregung eines Prüfkörpers und der Analyse der resultierenden Schwingungen (Resonanzmethode oder Impulsanregungsmethode) oder auf der Messung der Ultraschallausbreitungsgeschwindigkeit.
Stellvertretend für die dynamischen Verfahren wird im ersten Teil dieses Beitrages die Resonanzmethode vorgestellt. Der zweite Teil dieses Beitrages fasst die werkstoffabhängigen Ergebnisse der E-Modulbestimmung mit statischen Verfahren im Zug- und Biegeversuch zusammen.
For the safety and cost efficiency of welded high-strength steel structures, precise knowledge of the level and distribution of welding- and cooling-specific stresses and residual stresses is essential, since they exert a decisive influence on strength, crack resistance, and finally on the bearable service load. This paper presents innovative filler materials, of which the phase transformation temperature was deliberately adjusted via the chemical composition. The transformation behaviour of these martensitic Low Transformation Temperature (LTT-) filler materials shows direct effects on the local residual stresses in the weld and the HAZ. These effects can purposefully be exploited to counteract the thermally induced shrinkage of the material and to produce significant compressive residual stresses in the weld. Comparative welding experiments were carried out on 690 MPa high-strength base materials using various LTT-filler materials. High energy synchrotron radiation was used for residual stress measurement. Particularly the use of high energy synchrotron radiation makes it possible to detect the residual stress condition fast without destruction of material. Thereby, residual stress depth gradients can be determined simultaneously without removing material. In steel, gradients of up to 150 µm can be resolved in such a way. Furthermore, the application of high energy radiation permits determination of residual stresses of any available residual austenite contents. Results show significant dependence of transformation temperatures on the resulting residual stress level and distribution.
Cold cracking resistance is a relevant evaluation criterion for welded joints and affected by residual stresses which result from the welding procedure. Compressive residual stresses can thereby have a positive influence on preventing cracking. A unique possibility of generating compressive residual stresses already during the welding procedure is offered by the so-called Low Transformation Temperature (LTT) filler wires. Compared to conventional wires, these materials show decreased phase transformation temperatures which can work against the cooling-specific contraction. In consequence, distinct compressive residual stresses can be observed within the weld and adjacent areas. The strength of these fillers makes them potentially applicable to high-strength steel welding. Investigations were carried out to determine the phase transformation behaviour of different LTT-filler materials. Transformation temperatures were identified using Single Sensor Differential Thermal Analysis (SS-DTA). Additionally Synchrotron radiation was used to measure the transformation kinetics of all involved crystalline phases during heating and cooling of a simulated weld thermal cycle.
Bisphenol A polycarbonate/acrylonitrile–butadiene–styrene (PC/ABS) with and without bisphenol A bis(diphenyl phosphate) (BDP) and 5 wt.% zinc borate (Znb) were investigated. The pyrolysis was studied by thermogravimetry (TG), TG-FTIR and NMR, the fire behaviour with a cone calorimeter applying different heat fluxes, LOI and UL 94. Fire residues were examined with NMR. BDP affects the decomposition of PC/ABS and acts as a flame retardant in the gas and condensed phases. The addition of Znb results in an additional hydrolysis of PC. The fire behaviour is similar to PC/ABS, aside from a slightly increased LOI and a reduced peak heat release rate, both caused by borates improving the barrier properties of the char. In PC/ABS + BDP + Znb, the addition of Znb yields a borate network and amorphous phosphates. Znb also reacts with BDP to form alpha-zinc phosphate and borophosphates that suppress the original flame retardancy mechanisms of BDP. The inorganic–organic residue formed provides more effective flame retardancy, in particular at low irradiation in the cone calorimeter, and a clear synergy in LOI, whereas for more developed fires BDP + Znb become less effective than BDP in PC/ABS with respect to the total heat evolved.
Die Analytik von Phthalaten (DMP bis DEHP) in der Luft ist mit thermischer Desorption unter Verwendung von Quarzwolle als Adsorbens erfolgreich realisierbar. Dies wurde durch eine Methodenvalidierung bestätigt. Es wurden sowohl Messungen im Innenraum als auch in Emissionskammern vorgenommen. In den Emissionskammermessungen wurden mögliche Senkeneffekte der Kammeroberfläche (Glas) untersucht. Unter Zuhilfenahme der idealen Abklingkurve wird bestätigt, dass diese Oberfläche eine Senke darstellt.
Phosphorus-based flame retardancy mechanisms - Old hat or a starting point for future development?
(2010)
Different kinds of additive and reactive flame retardants containing phosphorus are increasingly successful as halogen-free alternatives for various polymeric materials and applications. Phosphorus can act in the condensed phase by enhancing charring, yielding intumescence, or through inorganic glass formation; and in the gas phase through flame inhibition. Occurrence and efficiency depend, not only on the flame retardant itself, but also on its interaction with pyrolysing polymeric material and additives. Flame retardancy is sensitive to modification of the flame retardant, the use of synergists/adjuvants, and changes to the polymeric material. A detailed understanding facilitates the launch of tailored and targeted development.
Structural changes in the condensed phase of bisphenol A polycarbonate (containing 0.45 wt% poly (tetrafluoroethylene))/silicone acrylate rubber/bisphenol A bis(diphenyl-phosphate) (PC/SiR/BDP) and PC/SiR/BDP/zinc borate (PC/SiR/BDP/ZnB) during thermal treatment in nitrogen atmosphere and in fire residues were investigated by solid-state NMR. H-1, B-11, C-13 and P-31 NMR experiments using direct excitation with a single pulse and H-1-P-31 cross-polarization (CP) were carried out including 31P(1 H) and C-13{P-31}double-resonance techniques (REDOR: Rotational Echo Double Resonance) on a series of heat-treated samples (580 K-850 K). Because many amorphous phases occur in the solid residues, and solid-state NMR spectroscopy addresses the most important sites carbon, phosphorus and boron, this paper is the key analytical approach for understanding the pyrolysis and flame retarding phenomenon in the condensed phase of PC/SiR/BDP and PC/SiR/BDP/ZnB.
For the system PC/SiR/BDP it is shown that (i) at temperatures around 750-770 K (main decomposition step) carbonaceous charring of PC occurs and arylphosphate structures are still present, reacted in part with the decomposing PC; (ii) for higher temperatures from 770 K the phosphorus remaining in the solid phase increasingly converts to amorphous phosphonates and inorganic orthophosphates with a minor amount of crystalline orthophosphates; and (iii) H-1-P-31{H-1} CP REDOR and H-1-C-13{P-31} CP REDOR NMR experiments suggest that the phosphates and phosphonates are bound via oxygen to aromatic carbons, indicating the interaction with the carbonaceous char.
When ZnB is added to the system PC/SiR/BDP, (i) ZnB leads to a slightly enhanced PC decomposition for temperatures below 750 K; (ii) alpha-Zn-3(PO4)(2) and borophosphate (BPO4) are formed in small amounts at high temperatures suggesting a reaction between BDP and ZnB during thermal decomposition; and (iii) most of the borate remains in the solid residues, forming an amorphous pure borate network, with the BO3/BO4 ratio increasing with higher temperatures.
The NMR data of thermal and fire residues are highly correlated, underlining the importance of this work for understanding the pyrolysis and flame retardancy mechanisms in the condensed phase during the burning of the PC/SiR blends. (C) 2010 Elsevier Ltd. All rights reserved.
The pyrolysis and fire behavior of halogen-free flame-retarded DGEBA/DMC, RTM6 and their corresponding 60 vol.-% carbon fibers (CF) composites were investigated. A novel phosphorous compound (DOPI) was used. Its action is dependent on the epoxy matrix. DGEBA/DMC and DOPI decompose independently of each other. Only flame inhibition occurs in the gas phase. RTM6 shows flame inhibition and a condensed phase interaction increasing charring. Both mechanisms decrease with increasing irradiance, whereas in RTM6-CF charring is suppressed at low ones. RTM6+DOPI shows a higher LOI (34.2%) than DGEBA/DMC+DOPI and a V-0 classification in UL 94. Adding CF only enhances the LOI, DOPI+CF leads to a superposition in LOI for DGEBA/DMC-CF+DOPI (31.8%, V-0) and a synergism for RTM6-CF+DOPI (47.7%, V-0).
Pyrolysis, flammability, fire behavior, melt viscosity, and gas diffusion of bisphenol A polycarbonate/acrylonitrile-butadiene-styrene (PC/ABS) were investigated, with bisphenol A bis(diphenyl phosphate) (BDP), with 10 wt.% talc and with BDP in combination with 5, 10 and 20 wt.% talc, respectively. Compared to PC/ABS, PC/ABS + BDP results in an increased decomposition temperature of PC, a higher char yield, a significantly increased LOI, a V-0 classification in UL 94, a reduced peak heat release rate (pHRR), and a reduced total heat release (THR) in the cone calorimeter. This efficient flame retardancy is due to mechanisms in both the gas and condensed phases. PC/ABS + 10 wt.% talc shows a decrease in the PC decomposition temperature. The fire behavior is improved in part compared to PC/ABS, with an increased LOI and reduced pHRR. PC/ABS + BDP + 10 wt.% talc shows a strong synergism in LOI, a V-0 classification, and a decrease in pHRR, whereas THR is slightly increased compared to PC/ABS + BDP. Talc decreases the gas diffusion and enhances the flow limit for low shear rates, both of which influence the pyrolysis and flammability results. Further, talc improves the protection properties of the fire residues. Nevertheless it also partly suppresses flame inhibition and the charring effect of BDP. The synergism between BDP and talc in LOI is obtained even for low talc loadings in PC/ABS + BDP + talc, whereas for higher loadings saturation is observed.
Downsizing (power-to-weight ratio) and higher speeds lead to a rise in Hertzian contact pressures in combination with an increase in surface or oil temperatures. Under such conditions, commonly used bearing steels, such as 100Cr6, reach their limits, creating a demand for alternative slip-rolling resistant steel alloys. The present work therefore compares the slip-rolling performance of various steel types with Maraging- and PM-type steel alloys such as e.g. CSS-42L™, ASP2012, BIMAX42+, in the Hertzian contact pressure range up to P0max of 4 GPa. Through-hardened 100Cr6H (AISI 52100), case-hardened 20MnCr5 (AISI 5120H) and nitrogen alloyed Croni-dur30 (AMS 5898) still compete in terms of slip-rolling and wear resistance and load carrying capacity, whereas Maraging- and PM-type steel alloys offer superior strength and toughness properties.
Several construction and building materials, including wood, glue and coatings, are possible sources of very volatile organic compounds (VVOCs) and volatile organic compounds (VOCs) like formic and acetic acid. Due to very high air tightness and very low air exchange rates in new buildings concentrations of these harmful substances can increase considerably. To minimize the risk, emissions from building products should be identified and quantified. With the common standard method, this means Tenax® sampling followed by thermal desorption and GC-MS analysis, these acids could not be detected sufficiently. The aim oft this study is the comparison of two different methods for the determination of acetic and formic acid. The sampling of method one, which is usually used for identification and quantification of VOCs, is done in accordance with ISO 16000-6 and ISO 16017-1 on Carbotrap® 202 multi-bed thermal desorption tube by subsequent identification and quantification with GC-MS. Method two is based on sampling on 2,4-dinitrophenylhydrazine (DNPH) cartridges, derivatisation, elution, identification and quantification of the derivatives with LC-MS/MS (liquid chromatography mass spectrometry/mass spectrometry).
The use of coconut fiber (CF) agricultural waste was considered as an environmentally friendly and inexpensive alternative in flame retarded biocomposites. To decrease the high content of aluminum trihydrate (ATH) required, the thermal decomposition (thermogravimetry), flammability [oxygen index (LOI) and UL 94 test] and fire behavior (cone calorimeter) of a combination of CF and ATH were investigated in a commercial blend of thermoplastic starch (TPS) and cellulose derivatives. CF induced some charring activity, slightly decreasing the fire load and burning propensity in cone calorimeter test. ATH decomposes endothermically into water and inorganic residue. Significant fuel dilution as well as a pronounced residual protection layer reduces the fire hazards. Replacing a part of ATH with coconut fibers resulted in improved flame retardancy in terms of ignition, reaction to small flame, and flame-spread characteristics [heat release rate (HRR), fire growth rate (FIGRA), etc.]. The observed ATH and CF synergy opens the door to significant reduction of the ATH contents and thus to interesting flame retarded biocomposites.
Effect of well dispersed amorphous silicon dioxide in flame retarded styrene butadiene rubber
(2013)
Spherically shaped amorphous silicon dioxide with broad size particle distribution was used in combination with aluminium trihydroxide (ATH) in styrene butadiene rubber composites. The pyrolysis, flammability, fire properties, flame spread and gas diffusion were investigated. The kind and amount of ATH, but in particular the fine silicon dioxide chosen as an additive, influenced the thermal decomposition and fire behaviour of styrene butadiene rubber composites. Gravimetric gas sorption measurements showed that the gas diffusion was systematically lower with silicon dioxide. The initial pyrolysis gas release was hindered, increasing the temperature at which decomposition begins as well as the ignition time in fire tests. During combustion, ATH and silicon dioxide accumulate on the surface of the specimen, forming a residual protective layer. A reduced peak heat release rate and fire spread were observed. The addition of a special kind of silicon dioxide is proposed to play a key role in optimising fire retardancy.
We use a dynamic scanning electron microscope (DySEM) to analyze the movement of oscillating micromechanical structures. A dynamic secondary electron (SE) signal is recorded and correlated to the oscillatory excitation of scanning force microscope (SFM) cantilever by means of lock-in amplifiers. We show, how the relative phase of the oscillations modulate the resulting real part and phase pictures of the DySEM mapping. This can be used to obtain information about the underlying oscillatory dynamics. We apply the theory to the case of a cantilever in oscillation, driven at different flexural and torsional resonance modes. This is an extension of a recent work (Schr¨oter et al 2012 Nanotechnology 23 435501), where we
reported on a general methodology to distinguish nonlinear features caused by the Imaging process from those caused by cantilever motion.
In welding experiments conducted on heavy wall pipes, the penetration mode (full or partial penetration) occurred to be a significant factor influencing appearance of solidification cracks. To explain the observed phenomena and support further optimization of manufacturing processes, a computational model was developed, which used a sophisticated strategy to model the material. High stresses emerged in the models in regions which showed cracking during experiments. In partial penetration welding, they were caused by the prevention of weld shrinkage due to the cold and strong material below the joint. Another identified factor having an influence on high stress localization is bulging of the weld.
Odour measurements become increasingly important in view of the assessment of indoor air quality and the emissions of building products. Hence they need to be implemented into evaluation schemes such as the AgBB scheme. While there are already standards like DIN ISO 16000-28 and VDI 4302 Part 1 specifying the procedure of odour measurements using a comparison scale, no final validation of the method has been carried out so far. Therefore, a round robin test was conducted in 2012 with 12 participating laboratories that mainly consisted of the following two parts: 1) testing of the available comparison scales with respect to their operational performance and 2) execution of an odour assessment of an acrylic sealant using emission test chambers. Part one included the measurement of the air flow rates and the provided concentrations of the reference substance (acetone). Part two was conducted to test the performance of the laboratories and the applicability of DIN ISO 16000-28 and supplementary VDI 4302 Part 1 by assessing the perceived intensity and the hedonic tone of the air samples. Moreover, samples for VOC analysis were taken from the air in the emission test chamber on the 7th day of testing to allow for quality control. Resulting from this round robin test main deficits were detected and suggestions for the improvement of the odour measurement procedure were made.
A method for the determination of very volatile organic compounds (VVOC) in air was developed and successfully tested for methanol and ethanol. Carbotrap300® (a multi-bed tube using Carbopack C®, Carbopack B® and Carbosive SIII®) was selected as sorption material for thermal desorption and tested for its suitability for emission test chamber measurements. The adsorption behaviour and the chromatographic results are influenced negatively by spiking aqueous solutions on the adsorption medium for calibration purposes. The latter effect can be reduced by blowing dry air across the adsorbent to remove the adsorbed water. Detection and quantification limits were determined for a GC-FID system and compared to GC-MS. The applicability of the method was tested with a methanol eliminating silane modified polymeric adhesive (SMP-adhesive for parquet) in an emission test chamber
Thermally reduced graphite oxide (TRGO), containing only four single carbon layers on average, was combined with ammonium polyphosphate (APP) and magnesium hydroxide (MH), respectively, in polypropylene (PP). The nanoparticle's influence on different flame-retarding systems and possible synergisms in pyrolysis, reaction to small flame, fire behavior and mechanical properties were determined. TRGO has a positive effect on the yield stress, which is decreased by both flame-retardants and acts as a synergist with regard to Young's modulus. The applicability and effects of TRGO as an adjuvant in combination with conventional flame-retardants depends strongly on the particular flame-retardancy mechanism. In the intumescent system, even small concentrations of TRGO change the viscosity of the pyrolysing melt crucially. In case of oxygen index (OI) and UL 94 test, the addition of increasing amounts of TRGO to PP/APP had a negative impact on the oxygen index and the UL 94 classification. Nevertheless, systems with only low amounts (≤1 wt%) of TRGO achieved V-0 classification in the UL 94 test and high oxygen indices (>31 vol%). TRGO strengthens the residue structure of MH and therefore functions as a strong synergist in terms of OI and UL 94 classification (from HB to V-0).
Nanotechnology is one of the key technologies of the 21st century. The exploitation of 'new' effects that arise from materials structured on the nano-scale has also been proposed successfully for flame retardancy of polymers since the end of the 90s. Of all of the approaches these include, at this time the use of nanocomposites offers the best potential for industrial application, also some other ideas are sketched, such as using electrospun nanofibers mats or layer-by-layer deposits as protection coatings, as well as sub-micrometer multilayer coatings as effective IR-mirrors. The general phenomena, inducing a flow limit in the pyrolysing melt and changing the fire residue, are identified in nanocomposites. Key experiments are performed such as quasi online investigation of the protection layer formation to understand what is going on in detail. The flame retardancy mechanisms are discussed and their impact on fire behaviour quantified. With the latter, the presentation pushes forward the state of the art. For instance, the heat shielding is experimentally quantified for a layered silicate epoxy resin nanocomposite proving that it is the only import mechanism controlling the reduction in peak heat release rate in the investigated system for different irradiations. The flame retardancy performance is assessed comprehensively illuminating not only the strengths but also the weak points of the concepts. Guidelines for materials development are deduced and discussed. Apart from inorganic fillers (layered silicate, boehmite, etc.) not only carbon nanoobjects such as multiwall carbon nanotubes, multilayer graphene and graphene are investigated, but also nanoparticles that are more reactive and harbor the potential for more beneficial interactions with the polymer matrix.
The most successful additive manufacturing (AM) technologies are based on the layer-by-layer deposition of a flowable powder. Although considered as the third industrial revolution, one factor still limiting these processes to become completely autonomous is the often necessary build-up of support structures. Besides the prevention of lateral shifts of the part during the deposition of layers, the support assures quality and stability to the built process. The loose powder itself surrounding the built object, or so-called powder-bed, does not provide this sustenance in most existent technology available. Here we present a simple but effective and economical method for stabilizing the powder-bed, preventing distortions in the geometry with no need for support structures. This effect, achieved by applying an air flow through the powder-bed, is enabling an entirely autonomous generation of parts and is a major contribution to all powder-based additive manufacturing technologies. Moreover, it makes powder-based AM independent of gravitational forces, which will facilitate crafting items in space from a variety of powdery materials.
-Background-
Laboratory leaching tests on treated wood were performed during a European robustness study in the framework of the validation of a tank leaching test procedure that has been proposed for construction products in order to determine the potential release of dangerous substances which can be transferred to soil and groundwater. The release of substances has to be determined also for materials treated with biocidal products according to the requirements of the European Biocidal Products Regulation. A similar leaching test procedure was already harmonised for treated wood for this purpose. Both test procedures were applied in parallel to wood treated with the same preservative to investigate whether the results of these tests can replace each other. Additional experiments were performed to further investigate unexpected effects of L/A ratio on leaching of copper and duration of storage of treated test specimens.
-Results-
Both procedures generate similar results concerning cumulative emissions of tebuconazole, copper, dissolved organic carbon and total nitrogen. The emission rates with time are in comparable ranges for both leaching protocols. Emissions of copper increased with decreasing L/A ratios. Strong correlation of copper concentrations and dissolved organic carbon as well as total nitrogen concentrations in eluates indicates that this observation is caused by co-elution of copper with organic substances. Duration of storage of treated test specimens affected emissions for the investigated wood preservative.
-Conclusions-
Based on these findings, results from both test procedures can be used to describe leaching characteristics and avoid double testing of treated wood to fulfil the requirements of the European regulations for either biocides or construction products. Leaching of substances from treated wood is a complex process that depends on its chemical composition and ageing processes.
CONRAD-2 is an imaging instrument using low-energy (cold) neutrons. The instrument is installed at the end of a curved neutron guide which avoids the direct line of sight towards the reactor core. This ensures a very low background of high-energy neutrons and. photons at the sample position. The cold neutron beam provides a wavelength range which is suitable for phase-and diffraction-contrast imaging such as grating interferometry and Bragg edge mapping. The instrument is well suited for high resolution imaging due to the high efficiency of the very thin scintillators that can be used for the detection of cold neutrons. An instrument upgrade was performed recently as a part of an upgrade program for the cold neutron instrumentation at HZB. The parameters of the instrument as well as some research highlights will be presented.
Many industrial processes are run at non-atmospheric conditions (elevated temperatures and pressures, other oxidizers than air). To judge whether and if yes to what extent explosive gas(vapor)/air mixtures will occur or may be generated during malfunction it is necessary to know the safety characteristic data at the respective conditions. Safety characteristic data like Explosion limits, are depending on pressure, temperature and the oxidizer. Most of the determination methods are standardized for ambient conditions.
In order to obtain determination methods for non-atmospheric conditions, particularly for higher initial pressures, reliable ignition criteria were investigated. Ignition tests at the explosion Limits were carried out for mixtures of methane, propane, n-butane, n-hexane, hydrogen, ammonia and acetone in air at initial pressures up to 20 bar. The tests have been evaluated according to different ignition criteria: visual flame propagation, temperature and pressure rising. It could be shown that flame propagation and occasionally self-sustained combustion for several seconds occurred together with remarkable temperature rise, although the pressure rise was below 3%. The results showed that the combination of a pressure rise criterion of 2% and a temperature rise criterion of 100 K seems to be a suitable ignition criterion for the determination of explosion limits and limiting oxidizer concentration at higher initial pressures and elevated temperatures. The tests were carried out within the framework of a R&D project founded by the German Ministry of Economics and Technology.
In this paper we present results of our recent efforts to understand the mechanical interface behaviour of single-walled carbon nanotubes (CNTs) embedded in metal matrices. We conducted experimental pull-out tests of CNTs embedded in Pd or Au and found Maximum forces in the range 10 - 102 nN. These values are in good agreement with forces obtained from molecular Dynamics simulations taking into account surface functional Groups (SFGs) covalently linked to the CNT material. The dominant failure mode in experiment is a CNT rupture, which can be explained with the presence of SFGs. To qualify the existence of SFGs on our used CNT material, we pursue investigations by means of fluorescence labeling of surface species in combination with Raman imaging. We also report of a tensile test system to perform pull-out tests inside a transmission electron microscope to obtain in situ images of CNT-metal interfaces under mechanical loads at the atomic scale.
Melt flow and dripping of the pyrolysing polymer melt can be both a benefit and a detriment during a fire. In several small-scale fire tests addressing the ignition of a defined specimen with a small ignition source, well-adjusted melt flow and dripping are usually beneficial to pass the test. The presence of flame retardants often changes the melt viscosity crucially. The influence of certain flame retardants on the dripping behaviour of four commercial polymers, poly(butylene terephthalate) (PBT), polypropylene (PP), polypropylene modified with ethylene-propylene rubber (PP-EP) and polyamide 6 (PA 6), is analysed based on an experimental monitoring of the mass loss due to melt dripping, drop size and drop temperature as a function of the furnace temperature applied to a rod-shaped specimen. Investigating the thermal transition (DSC), thermal and thermo-oxidative decomposition, as well as the viscosity of the polymer and collected drops completes the investigation. Different mechanisms of the flame retardants are associated with their influence on the dripping behaviour in the UL 94 test. Reduction in decomposition temperature and changed viscosity play a major role. A flow limit in flame-retarded PBT, enhanced decomposition of flame-retarded PP and PP-EP and the promotion of dripping in PA 6 are the salient features discussed.
A user-friendly open-source Monte Carlo regression package (McSAS) is presented, which structures the analysis of small-angle scattering (SAS) using uncorrelated shape-similar particles (or scattering contributions). The underdetermined problem is solvable, provided that sufficient external information is available. Based on this, the user picks a scatterer contribution model (or 'shape') from a comprehensive library and defines variation intervals of its model parameters. A multitude of scattering contribution models are included, including prolate and oblate nanoparticles, core-shell objects, several polymer models, and a model for densely packed spheres. Most importantly, the form-free Monte Carlo nature of McSAS means it is not necessary to provide further restrictions on the mathematical form of the parameter distribution; without prior knowledge, McSAS is able to extract complex multimodal or odd-shaped parameter distributions from SAS data. When provided with data on an absolute scale with reasonable uncertainty estimates, the software outputs model parameter distributions in absolute volume fraction, and provides the modes of the distribution (e.g. mean, variance etc.). In addition to facilitating the evaluation of (series of) SAS curves, McSAS also helps in assessing the significance of the results through the addition of uncertainty estimates to the result. The McSAS software can be integrated as part of an automated reduction and analysis procedure in laboratory instruments or at synchrotron beamlines.
SASfit: a tool for small-angle scattering data analysis using a library of analytical expressions
(2015)
SASfit is one of the mature programs for small-angle scattering data analysis and has been available for many years. This article describes the basic data processing and analysis workflow along with recent developments in the SASfit program package (version 0.94.6). They include (i) advanced algorithms for reduction of oversampled data sets, (ii) improved confidence assessment in the optimized model parameters and (iii) a flexible plug-in system for custom user-provided models. A scattering function of a mass fractal model of branched polymers in solution is provided as an example for implementing a plug-in. The new SASfit release is available for major platforms such as Windows, Linux and MacOS. To facilitate usage, it includes comprehensive indexed documentation as well as a web-based wiki for peer collaboration and online videos demonstrating basic usage. The use of SASfit is illustrated by interpretation of the small-angle X-ray scattering curves of monomodal gold nanoparticles (NIST reference material 8011) and bimodal silica nanoparticles (EU reference material ERM-FD-102).
Simple models describing the relationship between basic mechanical properties and the relative density of various types of porous metals (such as foams, sponges and lattice structures) are well established. Carefully evaluating these relationships experimentally is challenging, however, because of the stochastic structure of foams and the fact that it is difficult to systematically isolate density changes from variations in other factors, such as pore size and pore distribution. Here a new method for producing systematic sets of stochastic foams is employed based on electron beam melting (EBM) additive manufacturing (AM). To create idealised structures, structural blueprints were reverse-engineered by inverting X-ray computed tomographs of a randomly packed bed of glass beads. This three-dimensional structure was then modified by computer to create five foams of different relative density ρr, but otherwise consistent structure. Yield strength and Young’s modulus have been evaluated in compression tests and compared to existing models for foams. A power of 3 rather than a squared dependence of stiffness on relative density is found, which agrees with a recent model derived for replicated foams. A similar power of 3 relation was found for yield strength. Further analysis of the strength of nominally fully dense rods of different diameters built by EBM AM suggest that surface defects mean that the minimum size of features that can be created by EBM with similar strengths to machined samples is ∼1 mm.
Microorganisms accumulate molar concentrations of compatible solutes like ectoine to prevent proteins from denaturation. Direct structural or spectroscopic information on the mechanism and about the hydration shell around ectoine are scarce. We combined surface plasmon resonance (SPR), confocal Raman spectroscopy, molecular dynamics simulations, and density functional theory (DFT) calculations to study the local hydration shell around ectoine and its influence on the binding of a gene-S-protein (G5P) to a single-stranded DNA (dT(25)). Due to the very high hygroscopicity of ectoine, it was possible to analyze the highly stable hydration shell by confocal Raman spectroscopy. Corresponding molecular dynamics simulation results revealed a significant change of the water dielectric constant in the presence of a high molar ectoine concentration as compared to pure water. The SPR data showed that the amount of protein bound to DNA decreases in the presence of ectoine, and hence, the protein-DNA dissociation constant increases in a concentration-dependent manner. Concomitantly, the Raman spectra in terms of the amide I region revealed large changes in the protein secondary structure. Our results indicate that ectoine strongly affects the molecular recognition between the protein and the oligonudeotide, which has important consequences for osmotic regulation mechanisms.
A new method for sampling wear particles directly from the lubricant reservoir has been developed and applied successfully for analyzing wear particles by high-resolution scanning electron microscopy in transmission mode having coupled energy-dispersive X-ray spectroscopy. The lubricated tribological testing was carried out with fully formulated as well as with non-formulated synthetic base oil. It was possible to analyze individual particles with dimensions as small as about 5–30 nm which are likely the 'primary' wear particles. A majority of the particles, however, are agglomerated and, thus, lead to the formation of larger agglomerates of up to a few micrometers. Chemical analysis led to the conclusion that most of the observed particles generated in formulated oil, especially the larger ones, are composed of the additives of the lubricant oil. In non-formulated base oil, the primary particles are of similar dimensions but contain only iron, chromium and oxygen, but most likely stem from the mating materials. This finding points to the fact that the main wear mechanism under lubricated conditions with fully formulated oil is more like a continuous shearing process rather than a catastrophic failure with the generation of larger primary particles. When the oil is non-formulated, however, several wear mechanisms act simultaneously and the wear rate is increased significantly. Generated larger primary particles are milled down to the nanoscale. When the oil is fully formulated, wear mainly takes places at the additive layer or tribofilm; thus, the steel surface is protected.
Selective Electron Beam Melting (SEBM) is a promising powder bed Additive Manufacturing technique for near-net-shape manufacture of high-value titanium components. However without post-manufacture HIPing 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, and correlated to the process variables. The average volume fraction of the pores (b0.2%) was measured to be lower than that usually observed in competing processes, such as selective laser melting, but a strong relationship was found with the differentbeamstrategies 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; this was attributed to the lower energy density and less focused beam used in the infill strategy allowing less opportunity for gas bubbles to escape the melt pool. Overall, increasing the energy density or focus of the beam was found to correlate strongly to a reduction in the level of gas porosity. Rarer irregular shaped pores were mostly located in the contour region and have been attributed to a lack of fusion between powder particles.
The steel grade 20MnMoNi5-5 (according to German DIN standard or 16MND5 according to French AFNOR standard) is widely applied in (weld) fabrication of reactor pressure vessel components. Thus, a wide range of welding technologies (like submerged arc welding (SAW) or tungsten inert gas (TIG)) is used resulting in different heat affected zone (HAZ) microstructures. During weld fabrication, the weld joints may take up hydrogen. Especially, the HAZ shows an increased susceptibility for a degradation of the mechanical properties in presence of hydrogen. In addition, the hydrogen-assisted degradation of mechanical properties is influenced by three main local factors: hydrogen concentration, microstructure, and load condition. Hence, the base material (BM) and two different simulated non-tempered as-quenched HAZ microstructures were examined using hydrogen-free and hydrogen-charged tensile specimens. The results indicate that the effect of hydrogen on the degradation is significantly increased in case of the HAZ compared to the BM. In addition, hydrogen has remarkable effect in terms of reduction of ductility. It was ascertained that the degradation of the mechanical properties increases in the order of BM, bainitic HAZ, and the martensitic HAZ. Scanning electron microscope (SEM) investigation showed a distinct change of the fracture topography depended on the microstructure with increasing hydrogen concentration in case of the as-quenched HAZ microstructures.
In this paper, we identify the strategic motives of German manufacturing companies in the electrical engineering and machinery industry to be involved in standards development organizations. First, we present the general motives for the formation of strategic alliances and relate them to specific standardization motives. Then, we identify pursuing specific company interests, solving technical problems, knowledge seeking, influencing regulation, and facilitating market access as motives to standardize by means of factor analysis. In a second step, we test hypotheses on the relationship between the importance of strategic motives and firm level variables, e.g. R&D intensity, innovation activities, and firm size. The results reveal that firms in electric engineering and machinery have a particularly strong interest in ensuring industry-friendly design of regulations, which can be achieved by standards. Moreover, the results confirm that small firms also from these two sectors are active in standardization alliances to access knowledge from other involved stakeholders.
Recent developments in Förster resonance energy transfer (FRET) diagnostics using quantum dots
(2016)
The exceptional photophysical properties and the nanometric dimensions of colloidal semiconductor quantum dots (QD) have strongly attracted the bioanalytical community over the last approximately 20 y. In particular, the integration of QDs in the analysis of biological components and interactions, and the related diagnostics using Förster resonance energy transfer (FRET), have allowed researchers to significantly improve and diversify fluorescence-based biosensing. In this TRENDS article, we review some recent developments in QD-FRET biosensing that have implemented this technology in electronic consumer products, multiplexed analysis, and detection without light excitation for diagnostic applications. In selected examples of smartphone-based imaging, single- and multistep FRET, steady-state and time-resolved spectroscopy, and bio/chemiluminescence detection of QDs used as both FRET donors and acceptors, we highlight the advantages of QD-based FRET biosensing for multiplexed and sensitive diagnostics.
Nanoclays like laponites, which are commercially avaible in large quantities for a very moderate price, provide a facile solubilization strategy for hydrophobic dyes without the need for chemical functionalization and can act as a carrier for a high number of dye molecules. This does not require reactive dyes, amplifies fluorescence signals from individual emitters due to the high number of dyes molecules per laponite disk, and renders hydrophobic emitters applicable in aqueous environments. Aiming at the rational design of bright dye-loaded nanoclays as a new class of fluorescent reporters for bioanalysis and material sciences and the identification of dye structure−property relationships, we screened a series of commercial fluorescent dyes, differing in dye class, charge, and character of the optical transitions involved, and studied the changes of their optical properties caused by clay adsorption at different dye loading concentrations. Upon the basis of our dye loading density-dependent absorption and fluorescence measurements with S2105 and Lumogen F Yellow 083, we could identify two promising dye−nanoclay hybrid materials that reveal high fluorescence quantum yields of the nanoclay-adsorbed dyes of at least 0.20 and low dye self-quenching even at high dye-loading densities of up to 50 dye molecules per laponite platelet.
A series of Mg₁₋ₓZnₓTiO₃, x = 0–0.5 (MZT0–MZT0.5) ceramics was synthesised and characterised. The dielectric properties of the samples in the frequency range of
1 Hz – 7.7 GHz were explored using three different methods:
a contacting electrode method, a parallel-plate method and a perturbed resonator method. The electrical properties in the space charge and dipolar polarisation frequency ranges are discussed in relation to the phase composition and microstructure data. Differences in the zinc Substitution divided the dielectrics into two groups, namely MZT0-MZT0.2 and MZT0.3–MZT0.5, each with different amount of a main Mg₁₋ₓZnₓTiO₃ solid solution phase and a secondary solid solution phase. Zinc substitution promoted the density of the ceramics, improved the purity of the main phase and increased the permittivity for frequencies up to 10⁸ Hz, but reduced the permittivity in the microwave range. In the MZT0.3–MZT0.5 samples, for frequencies less than 1 MHz the quality (Q x ƒ) factors were lower and log σ ₐ.c, the AC conductivity, was higher than for the MZT0–MZT0.2 samples. Above 10 MHz, the (Q x ƒ) factors and log σ ₐ.c of the two groups were similar.
For pulse laser materials processing often optical step index and gradient index multimode fibers with core diameters ranging from 100 to 600 μm are used. The design of a high power fiber transmission system must take into account limitations resulting from both surface and volume damage effects. Especially, breakdown at the fiber end faces and self-focusing in the fiber volume critically influence the fiber performance. At least operation charts are desirable to select the appropriate fiber type for given laser parameters.
In industry-relevant studies the influence of fiber core diameter and end face preparation on laser-induced (surface) damage thresholds (LIDT) was investigated for frequently used all-silica fiber types (manufacturer LEONI). Experiments on preform material (initial fiber material) and compact specimens (models of the cladding and coating material) accompanied the tests performed in accordance with the relevant LIDT standards ISO 21254-1 and ISO 21254 2 for 1-on-1 and S-on-1 irradiation conditions, respectively. The relation beam diameter vs. LIDT was investigated for fused silica fibers. Additionally, laser-induced (bulk) damage thresholds of fused silica preform material F300 (manufacturer Heraeus) in dependence on external mechanical stress simulating fiber bending were measured. All experiments were performed with 10-ns laser pulses at 1064 and 532 nm wavelength with a Gaussian beam profile.
Column percolation tests may be suitable for prediction of chemical leaching from soil and soil materials. However, compared with batch leaching tests, they are time-consuming. It is therefore important to investigate ways to shorten the tests without affecting the quality of results. In this study, we evaluate the feasibility of decreasing testing time by increasing flow rate and decreasing equilibration time compared to the conditions specified in ISO/TS 21268-3, with equilibration periods of 48 h and flow rate of 12 mL/h. We tested three equilibration periods (0, 12–16, and 48 h) and two flow rates (12 and 36 mL/h)on four different soils and compared the inorganic constituent releases. For soils A and D, we observed similar values for all conditions except for the 0 h–36 mL/h case. For soil B, we observed no appreciable differences between the tested conditions, while for soil C there were no consistent trends probably due to the difference in ongoing oxidation reactions between soil samples. These results suggest that column percolation tests can be shortened from 20 to 30 days to 7–9 days by decreasing the equilibration time to 12–16 h and increasing the flow rate to 36 mL/h for inorganic substances.
Synthesis of Molybdenum and Niobium Mono- and Binary Silicides by the Method of SHS-Metallurgy
(2016)
The process of self-propagating high-temperature synthesis of the Mo–Nb–Si silicides from the powder mixtures has been investigated. Based on performed experiments, the composition of powder mixtures as well as technological parameters are proposed which provide the synthesis of monosilicides MoSi₂, NbSi₂, and binary silicides Mo₁-хNbxSi₂ with different ratios of Nb/Mo by adding different contents of MoO₃ and Nb₂O₅. Microstructure and phase compositions of the obtained silicide ingots are characterized by scanning electron microscopy, electron probe microanalysis, X-ray diffraction, and backscatter electron diffraction.
The paper investigates the dynamic characterisation, the numerical model tuning and the seismic risk assessment of two monumental masonry towers located in Italy: the Capua Cathedral bell tower and the Aversa Cathedral bell tower. Full-scale ambient vibration tests under environmental loads are performed. The modal identification is carried out using techniques of modal extraction in the frequency domain. The refined 3D finite element model (FEM) is calibrated using the in situ investigation survey. The FEM tuning is carried out by varying the mechanical parameters and accounting for the restraint offered by the neighbouring buildings and the role of soil–structure interaction. The assessment of the seismic performance of the bell towers is carried out through a nonlinear static procedure based on the multi-modal pushover analysis and the capacity spectrum method. Through the discussion of the case studies, the paper shows that the modal identification is a reliable technique that can be used in situ for assessing the dynamic behaviour of monumental buildings. By utilising the tuned FEM of the towers, the theoretical fundamental frequencies are determined, which coincide with the previously determined experimental frequencies. The results from seismic performance assessment through a pushover analysis confirm that the masonry towers in this study are particularly vulnerable to strong damage even when subjected to seismic events of moderate intensity.
The purpose of this paper is to numerically simulate the in-plane behaviour of rammed earth walls under cyclic shear-compression tests. The experimental testing allowed obtaining the maximum horizontal loads, the displacement capacity and the level of non-linear behaviour of the respective loaddisplacement relationships as well as the failure modes. The calibration of the numerical model (finite element method) was carried out based on the experimental results. Within this framework, a micromodelling approach was considered. The behaviour of the rammed earth material was simulated using a total strain rotating crack model. A Mohr-Coulomb failure criterion was used to reproduce the behaviour of the interfaces between the layers.
Although the numerical results achieved a satisfactory agreement with the experimental results a sensitivity analysis of the parameters involved was performed. The sensitivity analysis aimed at determining which parameters of the model have a significant impact in the model’s results. As expected the sensitivity analysis pointed out that the sliding failure occurrence is mainly influenced by two parameters of the interface elements: the interface tensile strength fit and the friction angle u. Moreover the cohesion c and the layers thickness showed a limited effect on the shear behaviour. It should be noted that the results mentioned above are related to the cases where a significant level of vertical compressive stress r is employed.
Central venous port devices made of two different polymeric materials, thermoplastic polyurethane (TPU)and silicone rubber (SiR), were compared due their material properties. Both naïve catheters as well as catheters after removal from patients were investigated. In lab experiments the influence of various chemo-therapeutic solutions on material properties was investigated, where as the samples after removal were compared according to the implanted time inpatient. The macroscopic,mechanical performance was assessed with dynamic, specially adapted tests for elasticity. The degradation status of the materials was determined with common tools of polymer characterisation, such as infrared spectroscopy, molecular weight measurements and various methods of thermal analysis. The surface morphology was an alysed using scanning electron microscopy. A correlation between material properties and clinical performance was proposed. The surface morphology and chemical composition of the polyurethane catheter materials can potentially result in increased susceptibility of the catheter to bloodstream infections and thrombotic complications. The higher mechanic failure,especially with increasing implantation time of the silicone catheters is related to the lower mechanical performance compared to the polyurethane material as well as loss of barium sulphate filler particles near the surface of the catheter. This results in preformed microscopic notches, which act as predetermined sites of fracture.
A new cocrystal of pyrazinamide with oxalic acid was prepared mechanochemically and characterized by PXRD, Raman spectroscopy, solid-state NMR spectroscopy, DTA-TG, and SEM. Based on powder X-ray diffraction data the structure was solved. The formation pathway of the reaction was studied in situ using combined synchrotron PXRD and Raman spectroscopy. Using oxalic acid dihydrate the initially neat grinding turned into a rapid self-accelerated liquid-assisted grinding process by the release of crystallization water. Under these conditions, the cocrystal was formed directly within two minutes.
Earth, timber, fibre boards and insulation materials based on wooden and other natural fibres offer a variety of properties beneficial for eco innovative constructions that are able to improve the energy and resource efficiency of buildings.
Due to their porosity, natural building materials are vapour active and are able to buffer moisture. In combination with highly insulated and airtight but vapour permeable building envelopes, modern earth-timber constructions provide stable indoor humidity levels and can therefore be naturally ventilated while achieving highest energy efficiency standards. Experimental evidence suggests that monitored pilot buildings in Berlin do show healthy indoor air humidity levels (around 50%) in wintertime, while mechanically ventilated buildings demonstrate significantly lower values (around 25%), which have to be considered as uncomfortable and unhealthy.
The application of building materials being poor in chemical emissions, particularly volatile organic compounds (VOC) and radon, improves the indoor air quality further, so that intermittent ventilation twice a day will be sufficient to provide healthy indoor air quality. The air quality in critical rooms (e.g. small bedrooms), demonstrating a smaller air volume, should be monitored if appropriate ratios of room size to occupancy level cannot be realised.
Through night time ventilation in summer, vapour active earth-timber constructions provide evaporative cooling (humidity adsorption at night time and desorption during the day). As a result, indoor temperatures of earth-timber buildings range around 8 °C below the outside temperature peak, when an appropriate glazing ratio is reflected. The EU funded research project H-house is investigating various construction materials regarding water vapour adsorption as well as emission and absorption of harmful substances. Based on this investigation new wall constructions are designed to provide a healthier indoor environment.
In situ crack detection in the mushy zone and the solid weld of a gas tungsten arc (GTA) weld using X-ray imaging during welding is a new research area for NDT inspection. Usually, NDT flaw detection is done after the complete solidification of the weld seam. In this paper, we present the use of real-time radiography with a minifocus X-ray source (YXLON X-ray tube Y.TU 225-D04) and a 75μm pixel size digital detector array (Dexela 1512) for the acquisition of 2D radiographic images by a sequence of exposures with time intervals of 80 ms for hot crack detection during single pass bead-on-plate GTA welding of 3 mm thick plates of aluminium alloy AlMgSi (6060). An analysis of the crack distribution in the weld sample is conducted from the acquired 2D radiographs and its corresponding 3D volumetric reconstruction achieved by linear coplanar digital laminography.
This in situ approach opens new possibilities in the field of hot crack research by having the direct information of both the crack initiation and growth and its correlation to the welding parameters.
We introduce azobenzene-functionalized polyelectrolyte multilayers as efficient, inexpensive optoacoustic transducers for hyper-sound strain waves in the GHz range. By picosecond transient reflectivity measurements we study the creation of nanoscale strain waves, their reflection from interfaces, damping by scattering from nanoparticles and propagation in soft and hard adjacent materials like polymer layers, quartz and mica. The amplitude of the generated strain ε∼5×10−4 is calibrated by ultrafast X-ray diffraction.
Triphenylamines (TPAs), boron dipyrromethenes (BODIPYs) and fullerenes C60 are excellent building blocks for the design of artificial photosynthetic systems. In the present work, we report the synthesis, characterization and detailed photophysical studies of a novel (TPA)2–BODIPY–C60 tetrad in polar and nonpolar solvents. The absorption spectrum of this compound covered virtually the entire visible Region (350–700 nm) and could be interpreted as a superposition of the spectra of individual components.
Upon TPA-part excitation, a fast and very efficient excitation energy transfer (EET) delivers the excitation to the BODIPY moiety resulting in complete quenching of the TPA first excited singlet state as well as the appearance of the BODIPY fluorescence. The efficiency of EET process was estimated to be 1. Direct or indirect (via EET) excitation of the BODIPY-part of the tetrad is followed by photoinduced charge transfer to the charge-separated state BODIPY+–C60- irrespective of the solvent used. In polar N,N-dimethylformamide (DMF)charge recombination occurs directly to the ground state with the Charge recombination rate, kCR, slower than 108 s-1, whereas in nonpolar toluene (TOL) a small energy gap between the charge-separated state and first excited singlet state of the BODIPY moiety facilitates the back charge transfer process. The latter results in the appearance of thermally activated delayed fluorescence. The rate of charge separation was found to be ca. 2 times faster in TOL than in DMF.
Determination of the elastic behavior of silicon nanowires within a scanning electron microscope
(2016)
Three-point bending tests were performed on double-anchored, <110> silicon nanowire samples inside a scanning electron microscope (SEM) via a micromanipulator equipped with a piezo-resistive force sensor. Representing the upper and lower boundaries achievable in a consistent manner, silicon nanowires with widths of 35 nm and 74 nm and a height of 168 nm were fabricated. The nanowires were obtained monolithically along with their 10-m-tall supports through a top-down fabrication approach involving a series of etching processes. Hence, no interface compliance was introduced between supports and nanowires. Exact nanowire dimensions and cross-sectional features were determined by transmission electron microscopy (TEM) following sample preparation through focused ion beam (FIB) machining. Conducting the experiments inside an SEM chamber further raised the opportunity of the direct observation of any deviation from ideal loading conditions such as twisting, which was taken into consideration in simulations. Measured force-displacement behavior was observed to exhibit close resemblance to simulation results obtained by finite element modeling, when the bulk value of 169 GPa was taken as the modulus of elasticity for <110> silicon. Hence, test results show neither any size effect nor evidence of residual stresses for the considered nanoscale objects. The increased effect of the native oxide with reduced nanowire dimensions was captured as well. Thus this very simple in-situ testing method was found to be an alternative to elaborate AFM measurements on geometrically formidable nanostructures. The results demonstrate the applicability of the developed fabrication approach to the incorporation of silicon nanowires in functional micromechanical devices.
Als umweltschonende Alternative zu portlandzementgebundenen
Betonen werden derzeit in der Betonindustrie und in der
Baustoffforschung Betone mit alkaliaktivierten Bindemitteln,
sog. Geopolymerbetone, intensiv erforscht. Die auf industriellen
Reststoffen wie Flugasche und Hüttensand basierenden anorganischen
Bindemittel weisen bei geeigneter Zusammensetzung
einen hohen Widerstand gegenüber aggressiven Salzlösungen
und Säuren auf. Als Grundlage für den rechnerischen
Nachweis der Tragfähigkeit von brandbeanspruchten Betonbauteilen
auf Basis von alkaliaktivierten Bindemitteln werden
deshalb an der Bundesanstalt für Materialforschung und -prüfung
(BAM) die mechanischen Hochtemperatureigenschaften
von flugaschebasierten Geopolymerbetonen systematisch
untersucht.
Die bis zu 750 °C erhitzten Probekörper mit quarzitischer
und leichter Gesteinskörnung zeigen einen Festigkeitsverlust
bis ca. 300 °C, der auf entwässerungsbedingte Mikrorissbildung
zurückgeführt werden kann. Bei weiter zunehmender
Temperatur steigt aufgrund von Sinterungsprozessen ab
ca. 500 °C die Festigkeit der untersuchten Geopolymerbetone
wieder an. Diese im Vergleich zu herkömmlichem Beton günstigere
Materialeigenschaft eröffnet potenziell auch Anwendungsmöglichkeiten
in brandschutztechnisch kritischen Infrastrukturbereichen.
Die Ergebnisse der thermomechanischen
Prüfungen werden für numerische Bauteilberechnungen als
temperaturabhängige Spannungs-Dehnungs-Beziehungen aufbereitet.
Three types of hybrid modified magnetite (Fe₃O₄) nanoparticles, functionalized with either chitosan, chitosan/iron (II) oxalate or chitosan/iron (III) citrate, were synthesized by chemical precipitation method.
The obtained nanomaterials were characterized by energy dispersive X-ray spectroscopy, X-ray diffraction, Brunauer–Emmett–Teller analysis, scanning and Transmission electron microscopy, Fourier transform infrared spectroscopy and vibrating sample magnetometry. The prepared composites were further tested as magnetic catalysts for the removal of bisphenol A (BPA) in aqueous media. The kinetic Degradation experiments were performed at laboratory scale, while the best operational parameters for all three materials were established: 1.00 g L⁻¹ of catalyst, 10 mmol L⁻¹ H₂O₂, under simulated solar light irradiation.
After 15 min of UVA irradiation under the experimental conditions mentioned above, it was possible to decompose up to 99% of the micropollutant over all catalysts. Fe₃O₄/chitosan/iron oxalate catalyst showed the highest and fastest catalytic activity in BPA removal. Catalytic wet peroxide oxidation of non-biodegradable micropollutants on such iron-based hybrid nanoparticles can be a suitable pre-treatment method for wastewater decontamination, as an environment-friendly simplified Approach for water clean-up.
The study presents the results from the development of a grouting material based on hydrated lime with addition of pozzolana, which is referred to as hydraulic lime, suitable for the repair of cracks in a variety of earthen building techniques. The goal was to develop a material also compatible with earthen structures exposed to dynamic loads. The grouting mortar was designed to be adaptable in strength properties and at the same time to have sufficient robustness for preparation and use on the construction site.
Results showed a satisfactory performance of the grout concerning fresh and hardened mortar properties as well as injectability.
We report on the development of ultra-small core-shell silver nanoparticles synthesized by an up-scaled modification of the polyol process. It is foreseen to use these thoroughly characterized particles as reference material to compare the catalytic and biological properties of functionalized silver nanoparticles. Small-angle X-ray scattering (SAXS) analysis reveal a narrow size distribution of the silver cores with a mean radius of RC = 3.0 nm and a distribution width of 0.6 nm. Dynamic light scattering (DLS) provides a hydrodynamic radius of RH = 10.0 nm and a PDI of 0.09. The particles’ surface is covered with poly(acrylic acid) (PAA) forming a shell with a thickness of 7.0 nm, which provides colloidal stability lasting for more than six months at ambient conditions. The PAA can be easily exchanged by biomolecules to modify the surface functionality. Replacements of PAA with glutathione (GSH) and bovine serum albumin (BSA) have been performed as examples. We demonstrate that the particles effectively catalyze the reduction of 4-nitrophenol to 4-aminophenol with sodium borohydride. With PAA as stabilizer, the catalytic activity of 436 ± 24 L g⁻¹ s⁻¹ is the highest reported in literature for silver nanoparticles. GSH and BSA passivate the surface substantially resulting in a catalytic activity of 77.6 ± 0.9 and 3.47 ± 0.50 L g⁻¹ s⁻¹, respectively.
Internal damage of an AlSi12CuMgNi alloy reinforced with planar random short fibres has been investigated after compression. This damage strongly influences the load partition between matrix and reinforcement. For fibres perpendicular to the applied load, breakage and interconnected cracks appear in significantly higher volume fraction than with fibres parallel to load.
The influence of second phase arrangements on the corrosion resistance of extruded Mg97Y2Zn1 alloy has been evaluated in a 0.1 M NaCl solution. The microstructure of the alloy consists of a high volume fraction of coarse elongated particles of a long period stacking ordered phase aligned along the extrusion direction. Corrosion rate of transversal sections is lower than that of longitudinal sections. Such difference is attributed to the different orientation of second phases in longitudinal and transversal sections. The corrosion front advances mainly perpendicular to the surface in transversal samples while perpendicular and lateral growth occur in longitudinal samples
This article reports a comprehensive investigation of the average and local structure of La5.6WO12-δ, which has excellent mixed proton, electron and oxide ion conduction suitable for device applications. Synchrotron X-ray and neutron powder diffraction show that a cubic fluorite supercell describes the average structure, with highly disordered lanthanum and oxide positions. On average, the tungsten sites are sixfold coordinated and a trace [3.7 (1.3)%] of anti-site disorder is detected. In addition to sharp Bragg reflections, strong diffuse neutron scattering is observed, which hints at short-range order. Plausible local configurations are considered and it is shown that the defect chemistry implies a simple 'chemical exchange' interaction that favours ordered WO6 octahedra. The local model is confirmed by synchrotron X-ray pair distribution function analysis and EXAFS experiments performed at the La K and W L-3 edges. It is shown that ordered domains of similar to 3.5 nm are found, implying that mixed conduction in La5.6WO12-δ is associated with a defective glassy-like anion sublattice. The origins of this ground state are proposed to lie in the nonbipartite nature of the face-centred cubic lattice and the pairwise interactions which link the orientation of neighbouring octahedral WO6 sites. This 'function through frustration' could provide a means of designing new mixed conductors.
A combined experimental numerical approach is applied to determine the transformation induced plasticity (TRIP)-parameter K for different strength low-alloy steels of grade S355J2+N and S960QL as well as the super martensitic filler CN13-4-IG containing 13 wt% chromium and 4 wt% nickel. The thermo-physical analyses were conducted using a Gleeble® 3500 facility. The thermal histories of the specimens to be tested were extracted from corresponding simulations of a real gas metal arc weldment. In contrast to common TRIP-experiments which are based on complex specimens a simple flat specimen was utilized together with an engineering evaluation method. The evaluation method was validated with literature values for the TRIP-parameter. It could be shown that the proposed approach enables a correct description of the TRIP behavior.
The corrosion resistance of martensitic stainless steels (MSS) depends strongly on the chemical composition and the applied heat treatment. Both determines the distribution of the alloying elements in the microstructure and the resulting material properties. The addition of nitrogen is known to be beneficial for the pitting corrosion resistance of stainless steels. In case of MSS this effect is not only connected to nitrogen itself because nitrogen can be used to substitute carbon which also influences the result of the heat treatment process. This paper shows the effect of nitrogen on the corrosion resistance in relation to the hardening process of MSS. Therefore the effects of austenitization duration, austenitization temperature and cooling rate on microstructure, hardness and corrosion resistance were studied on the MSS X30CrMoN15 1 and X50CrMoV15. The effect of different cooling rates was studied in the range of > 100 K/s down to 1 K/s using the jominy end quench test. The changes in corrosion resistance were detected with electrochemical potentiodynamic reactivation (EPR) and by the determination of critical pitting potentials. Besides this experimental approach thermodynamic calculations with the software thermocalc will be presented and used for the interpretation of the effect of nitrogen on the corrosion resistance of MSS.
Polymer Testing - Editorial
(2016)
Due to the adsorption of biomolecules, the control of the biodistribution of nanoparticles is still one of the major challenges of nanomedicine. Poly(2-ethyl-2-oxazoline) (PEtOx) for surface modification of nanoparticles is applied and both protein adsorption and cellular uptake of PEtOxylated nanoparticles versus nanoparticles coated with poly(ethylene glycol) (PEG) and non-coated positively and negatively charged nanoparticles are compared. Therefore, fluorescent poly(organosiloxane) nanoparticles of 15 nm radius are synthesized, which are used as a scaffold for surface modification in a grafting onto approach.
With multi-angle dynamic light scattering, asymmetrical flow field-flow fractionation, gel electrophoresis, and liquid chromatography-mass spectrometry, it is demonstrated that protein adsorption on PEtOxylated nanoparticles is extremely low, similar as on PEGylated nanoparticles. Moreover, quantitative microscopy reveals that PEtOxylation significantly reduces the non-specific cellular uptake, particularly by macrophage-like cells. Collectively, studies demonstrate that PEtOx is a very effective alternative to PEG for stealth modification of the surface of nanoparticles.
The phenomenon of creep of structural steel in fire engineering is gaining more and more interest. Due to shortcomings of the EC3 constitutive model and other approaches based on classical creep theory an alternative approach mainly based on the ideas of Krempl is proposed. Due to this so-called operator approach the material as well as the constitutive model is looked upon as an operator. The application of this view serves as a guide through the analysis of the relationship between experimental facts and constitutive theory especially in the context of transient creep.
Biological erosion is a key process for the recycling of carbonate and the formation of calcareous sediments in the oceans. Experimental studies showed that bioerosion is subject to distinct temporal variability, but previous long-term studies were restricted to tropical waters. Here, we present results from a 14-year bioerosion experiment that was carried out along the rocky limestone coast of the island of Rhodes, Greece, in the Eastern Mediterranean Sea, in order to monitor the pace at which bioerosion affects carbonate substrate and the sequence of colonisation by bioeroding organisms. Internal macrobioerosion was visualised and quantified by micro-computed tomography and computer-algorithm-based segmentation procedures. Analysis of internal macrobioerosion traces revealed a dominance of bioeroding sponges producing eight types of characteristic Entobia cavity networks, which were matched to five different clionaid sponges by spicule identification in extracted tissue. The morphology of the entobians strongly varied depending on the species of the producing sponge, its ontogenetic stage, available space, and competition by other bioeroders. An early community developed during the first 5 years of exposure with initially very low macrobioerosion rates and was followed by an intermediate stage when sponges formed large and more diverse entobians and bioerosion rates in-creased. After 14 years, 30 % of the block volumes were occupied by boring sponges, yielding maximum bioerosion rates of 900 g m.
Solidification cracking phenomena taking place under controlled tensile weldability (CTW) test conditions have already been investigated both experimentally and numerically via FEA in order to get a better understanding of the mechanisms of hot crack formation during laser beam welding of austenitic steel grades. This paper develops a threedimensional finite element model employing the contact element technique to simulate the formation and propagation of solidification cracks during laser full penetration welding of fully austenitic stainless steel 1.4376. During the experimental procedure, the resulting strain and displacement directed to the laser beam in the close vicinity of the weld pool was measured at the surface of the workpiece using a digital image correlation (DIC) technique with an external diode laser as an illuminating source. Local strain fields, global loads and crack lengths predicted by the model are in good agreement with those observed in experiments.
A multiproxy approach to evaluate biocidal treatments on biodeteriorated majolica glazed tiles
(2016)
The Fishing House located on the grounds of the Marquis of Pombal Palace, Oeiras, Portugal, was built in the 18th century. During this epoch, Portuguese gardens, such as the one surrounding the Fishing House, were commonly ornamented with glazed wall tile claddings. Currently, some of these outdoor tile panels are covered with dark colored biofilms, contributing to undesirable aesthetic changes and eventually inducing chemical and physical damage to the tile surfaces. Phylogenetic analyses revealed that the investigated biofilms are mainly composed of green algae, cyanobacteria and dematiaceous fungi. With the aim of mitigating biodeterioration, four different biocides (TiO2 nanoparticles, Biotin® T, Preventol® RI 80 and Albilex Biostat®) were applied in situ to the glazed wall tiles. Their efficacy was monitored by visual examination, epifluorescence microscopy and DNA-based analysis. Significant changes in the microbial community composition were observed 4 months after treatment with Preventol® RI 80 and Biotin® T. Although the original community was inactivated after these treatments, an early stage of re-colonization was detected 6 months after the biocide application. TiO2 nanoparticles showed promising results due to their self-cleaning effect, causing the detachment of the biofilm from the tile surface, which remained clean 6 and even 24 months after biocide application.
In the present work, the influence of deuterium on the microstructure of a duplex stainless steel type EN 1.4462 has been characterized by Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) supported by scanning electron microscopy (SEM), focused ion beam (FIB), electron back scattered diffraction(EBSD) and energy dispersive x-ray (EDX) investigations. Characterization has been carried out before and after electrochemical charging with deuterium which has been used as a tracer, due to its similar behavior to hydrogen in the steel microstructure. In a first approach, the distribution of the deuterium occurring at temperatures above 58 °C has been visualized. Further it turned out that sub-surface micro blisters are formed in the ferrite-austenite interface, followed by the formation of needle shaped plates and subsequent cracking at the ferrite surface. In the austenite phase, parallel cracking alongside twins and hexagonal close packed (martensitic) regions has been observed. In both phases and even in the apparent interface, cracking has been associated with high deuterium concentrations, as compared to the surrounding undamaged microstructure. Sub-surface blistering in the ferrite has to be attributed to the accumulation and recombination of deuterium at the ferrite-austenite interface underneath the respective ferrite grains and after fast diffusing through this phase. Generally, the present application of chemometric imaging and structural analyses allows characterization of hydrogen assisted degradation at a sub-micron lateral resolution.
A new concept that comprises both time- and lateral-resolved X-ray absorption fine-structure information simultaneously in a single shot is presented. This uncomplicated set-up was tested at the BAMline at BESSY-II (Berlin, Germany). The primary broadband beam was generated by a double multilayer monochromator. The transmitted beam through the sample is diffracted by a convexly bent Si (111) crystal, producing a divergent beam. This, in turn, is collected by either an energy-sensitive area detector, the so-called color X-ray camera, or by an area-sensitive detector based on a CCD camera, in θ–2θ geometry. The first tests were performed with thin metal foils and some iron oxide mixtures. A time resolution of lower than 1 s together with a spatial resolution in one dimension of at least 50 mm is achieved.
The successful mechanochemical syntheses of three cadmium phenylphosphonates indicates that mechanochemistry is ideally suited for synthesizing metal phosphonates. With this powerful synthesis tool it is possible to synthesize rapidly and efficiently both known and novel phosphonates. The Crystal structures of the two new compounds, and, were solved from PXRD data. They contain monodeprotonated phenylphosphonate and neutral phenylphosphonic acid ligands. The synthesis pathways of all three compounds were investigated in situ. A diffusion mechanism is corroborated by our findings.
Intermediates could be detected and identified. The kinetically favored product (3) could always be detected during the syntheses. The thermodynamic stability of the compounds and the stoichiometric ratio of the starting materials are the two directing factors for the synthesis of the final products.
HNBR, EPDM and FKM O-rings were aged uncompressed and compressed at 75 °C, 100 °C, 125 °C and 150 °C for up to 1 year. HNBR exhibited the strongest ageing effects with high increases of hardness and glass transition temperature. Furthermore, heterogeneous ageing caused by diffusion-limited oxidation effects had a significant influence for HNBR at ageing temperatures of 125 °C and 150 °C. EPDM showed similar property changes as HNBR, but less pronounced. FKM displayed only minor ageing effects. O-rings aged in compression exhibited considerable compression set (CS). CS data was used for a time-temperature shift and resulting master curve construction. Leakage rate measurements showed that O-rings can remain leak tight under static conditions even if material properties have already deteriorated strongly.
Polyurethane versus silicone catheters for central venous port devices implanted at the forearm
(2016)
Purpose: We aimed to analyse short and long-term complications of polyurethane (PU) versus silicone catheters used in totally implantable venous-access ports (TIVAPs) implanted at the forearm.
Methods: Retrospective analysis of 698 consecutively implanted TIVAPs was performed. Primary end-points were defined as rates of major complications associated with either type of central venous port catheter. Technical success rate, device service interval as well as minor complications not requiring port explantation were defined as secondary end-points.
Results: A total of 698 port devices were implanted in 681 patients, 396 equipped with a PU catheter, 302 with a silicone catheter. The technical success rate was 99.9% with no major periprocedural complications. During follow-up a total of 211 complications in 146 patients were observed (1.0/1000 catheter days), 183 occurred associated with PU catheters (1.8/100 catheter days), 28 (0.3/1000 catheter days) with silicone catheters (log rank test p < 0.0001). Catheter-related bloodstream infections as well as thrombotic complications occurred significantly more frequently with PU catheters, while silicone catheters exhibited a trend towards a higher rate of mechanical failure such as disconnection or catheter rupture. Major complications requiring explantation of the device occurred more frequently with PU-based catheters (10.6%) compared to silicone catheter carrying ports (4.6%, log rank test p < 0.001).
The use of a biocompatible and thermoresponsive polymer, poly (2-hydroxyethyl methacrylate) (PHEMA) grafted onto the surface of graphene oxide (GO) as an adsorbent for the removal of a cationic dye (methylene blue [MB]) from an aqueous solution is examined in this work. GO–PHEMA forms a hydrogel in water thus overcoming the problem faced by carbon-based adsorbent materials during post-treatment (i.e., separation of adsorbent from the aqueous phase). The GO–PHEMA composite was synthesized using a green approach through dispersion polymerization in supercritical CO2. The successful preparation of this composite was confirmed by a series of characterization techniques. The adsorption behavior of the composite toward MB, such as the effect of the adsorbent dosage, pH, contact time, dye concentration, and recyclability was observed. In addition, the adsorption isotherm, kinetics and thermodynamics were investigated. According to the experimental data, the adsorption parameters were found to fit well into the Freundlich adsorption isotherm with a correlation coefficient of 0.975 and a maximum predicted adsorption capacity of 39.41 mg g−1 at 25 °C. The adsorption kinetics studies showed that the adsorption behavior followed a pseudo-second-order reaction. On the other hand, the thermodynamics studies showed that the adsorption of MB on GO–PHEMA composite followed spontaneous and endothermic adsorption process with an efficient adsorption temperature at 45 °C. The experimental results also showed that the GO–PHEMA composite could remove 99.8 % of the dye in 45 min. Therefore, GO–PHEMA composite is a favorable green adsorbent for environmental applications.
Three high-strength Nb-, Ti- and Ti + Vmicroalloyed S690QL steels were welded to investigate the formation of softened HAZ and its impact on tensile properties. The welding was performed with three levels of heat input to produce softened zones with different characteristics (softening width, minimum hardness and softening ratio), and then, further tensile tests were done to study their influence on weld performance. The results showed that Ti bearing steel exhibited the lowest resistance to softening with the presence of largest soften width and lowest hardness value, causing final tensile failure occurred at softened HAZ. The metallurgical reason for the lower hardness is the high fraction of coarse ferrite. Nb- and Ti + V-bearing steels suffered moderate softening, due to high hardenability with addition of Mo, Nb and V, but the softening effect did not remarkably influence the tensile properties of these two steels.
Enzyme-activatable optical probes are important for future advances in cancer imaging, but may easily suffer from low signal-to-background ratios unless not optimized. To address this shortcoming, numerous mechanisms to modulate the fluorescence signal have been explored.
We report herein newly synthesized probes based on selfimmolative linkers containing chiral J-aggregate-forming dyes.
Signal modulation by formation of chiral J-aggregates is yet unexplored in optical enzyme probe design. The comprehensive characterization of the probes by absorption, CD, fluorescence, and time-resolved fluorescence spectroscopy revealed dye−dye interactions not observed for the free dyes in solution as well as dye−protein interactions with the enzyme. This suggested
that J-aggregate formation is challenging to achieve with current probe design and that interactions of the dyes with the Enzyme may interfere with achieving high signal-to-background ratios. The detailed understanding of the interactions provided herein provides valuable guidelines for the future design of similar probes.
A fracture mechanics model which shall be applied to the fatigue strength determination of weldments has to focus on various aspects such as: (a) the description of mechanical and physical short fatigue crack extension which is characterised by yielding conditions which do not permit the application of the common ΔK concept and by the gradual build-up of the crack closure effect, (b) a consistent methodology for determining the initial crack size, (c) based on this, the determination of a fatigue limit, (d) the treatment of multiple crack propagation at load levels above this limit, (e) the variation of the local geometry along the weld toe, and (f) statistical effects.The paper gives alimited overview of the work the authors did in this field during the last years within the German project cluster IBESS. A model is presented and briefly discussed which covers the questions above.
With the vast exploration of the applications of graphene, researchers are assessing different methods for fabricating graphene-based electrode material with high capacitance but low material and energy costs. In this study, reduced graphene oxide/nickel oxide (RGO/NiO) nanocomposites were prepared using a non-aqueous solvent-based method followed by calcination. Nickel acetate tetrahydrate and tert-butanol were used as the precursor and solvent, respectively. Ultrasmall nickel oxide nanoparticles, ca. 8.0 nm in size, were deposited on the surface of the graphene sheets simultaneously with the partial reduction of graphene oxide. The resulting RGO/NiO electrode exhibited a high capacitance of 689 F g⁻1 at a current density of 0.8 A g⁻1. After 1500 cycles, the specific retention and the coulombic efficiency yielded to 86.34% and 96.39%, respectively, which supports the viability of this composite as an alternative activated material with high electrochemical performance.
A new technique to fix bioceramic powder on a titanium alloy by using femtosecond laser pulses is presented. It is shown that gentle fixation of a bioactive dielectric material on a metallic model implant is successful. This is potentially a new tool for the improvement of bone prostheses. An advantage of the ultrashort pulses is the very low heat influx into the whole sample. There is only a very thin interaction zone during the fixing, which is the metal surface in contact with the ceramic layer. Neither the fixed ceramic particles nor the major part of the metal suffer any modification. The stability of the model implant (ceramic on metal) is investigated by rotating bending fatigue tests. No indication of a reduction of the mechanical stability compared to untreated metallic reference samples was found.
Analytical routines for a comprehensive in-depth morphological, structural, and chemical characterization of functionalized TiO2 films by using different state-of-the-art analytical techniques are presented and discussed with the main objective to identify potential reference TiO2 coating parameters able to be certified at a later stage. TiO2 films fabricated by two different synthetic procedures as representative for two main large-scale applications were selected: (i) pulsed d.c. magnetron sputtering for photocatalytic applications and (ii) screen printing from preformed anatase nanoparticles. The screen-printed films were further loaded with a sensitizing dye for application as a dye-sensitized solar cell. Film properties such as microstructure and crystallographic texture of pulsed d.c. magnetron sputtering synthesized films were systematically studied by means of scanning nanobeam electron diffraction in a transmission electron microscope and the surface and inner morphology by scanning electron microscopy. The dye distribution over the depth of screen-printed TiO2 layers was analyzed before and after dye-loading by means of energy dispersive X-ray spectroscopy at scanning electronmicroscope, Auger electron spectroscopy and time-of-flight secondary ion mass spectrometry. The long-term goal of the present study is the improvement of quality of the TiO2 film parameters as measured by using different types of reference TiO2 coatings having specific parameters certified.
Synergistic multicomponent systems containing melamine poly(metal phosphate)s have been recently proposed as flame retardants. This work focuses on the decomposition pathways, molecular mechanisms and morphology of the fire residues of epoxy resin (EP) flame retarded with melamine poly(zinc phosphate) (MPZnP) to explain the modes of action and synergistic effects with selected synergists (melamine polyphosphate (MPP) and AlO(OH), respectively). The total load of flame retardants was always 20 wt.%. The decomposition pathways were investigated in detail via thermogravimetric Analysis coupled with Fourier transform infrared spectroscopy. The fire residues were investigated via elemental analysis und solid-state nuclear magnetic resonance spectroscopy. The morphology of intumescent fire residues was investigated via micro-computed tomography and scanning electron microscopy.
EP + (MPZnP + MPP) formed a highly voluminous residue that showed structural features of both EP + MPZnP and EP + MPP, resulting in a highly effective protection layer. EP + (MPZnP + AlO(OH)) preserved the entire quantity of phosphorus content during combustion due to the Formation of Zn₂P₂O₇ and AlPO₄.
Multilayer Graphene (MLG), a nanoparticle with a specific surface of BET = 250 m²/g and thus made of only approximately 10 graphene sheets, is proposed as a nanofiller for rubbers. When homogenously dispersed, it works at low loadings enabling the replacement of carbon black (CB), increase in efficiency, or reduction in filler concentration. Actually the appropriate preparation yielded nanocomposites in which just 3 phr are sufficient to significantly improve the rheological, curing and mechanical properties of different rubbers, as shown for Chlorine-Isobutylene-Isoprene Rubber (CIIR), Nitrile-Butadiene Rubber (NBR), Natural Rubber (NR), and Styrene-Butadiene Rubber (SBR). A mere 3 phr of MLG tripled the Young’s modulus of CIIR, an effect equivalent to 20 phr of carbon black. Similar equivalents are observed for MLG/CB mixtures. MLG reduces gas permeability, increases thermal and electrical conductivities, and retards fire behavior. The later shown by the reduction in heat release rate in the cone calorimeter. The higher the nanofiller concentration is (3 phr, 5 phr, and 10 phr was investigated), the greater the improvement in the properties of the nanocomposites. Moreover, the MLG nanocomposites improve stability of mechanical properties against weathering. An increase in UV-absorption as well as a pronounced radical scavenging are proposed and were proved experimentally. To sum up, MLG is interesting as a multifunctional nanofiller and seems to be quite ready for rubber development.
Multilayer graphene/chlorine-isobutene-isoprene rubber nanocomposites: the effect of dispersion
(2016)
Multilayer graphene (MLG) is composed of approximately 10 sheets of graphene. It is a promising nanofiller just starting to become commercially available. The Dispersion of the nanofiller is essential to exploit the properties of the nanocomposites and is dependent on the preparation method. In this study, direct incorporation of 3 parts per hundred of rubber (phr) MLG into chlorine-isobutene- isoprene rubber (CIIR) on a two-roll mill did not result in substantial enhancement of the material properties. In contrast, by pre-mixing the MLG (3 phr) with CIIR using an ultrasonically assisted solution mixing procedure followed by two-roll milling, the properties (rheological, curing, and mechanical) were improved substantially compared with the MLG/CIIR nanocomposites mixed only on the mill. The Young’s moduli of the nanocomposites mixed in solution increased by 38%. The CIIR/MLG nanocomposites produced via solution showed superior durability against weathering exposure.
Self-compacting concrete typically contains a higher content of powder materials than normal concrete. Furthermore it is assumed that the use of superplasticizers yields a more homogenous microstructure in the hardened paste. Both aspects generate a very dense microstructure, which can be assumed to cause material behaviour that differs from than normal concrete when it is exposed to elevated temperatures. However, the paste volumes in SCC can vary significantly based on the mixture composition. At a low paste volumes SCC can be very similar to normal concrete at hardened state while it can vary greatly at higher paste volumes. Since the high temperature behaviour of concrete is strongly affected by the different physical behaviour of the paste and the aggregates, it is likely that the high temperature behaviour is consequently strongly affected by the ratio of these mixture components. In the present study different SCC mixtures were observed with similar mechanical properties, but with significantly differing paste to aggregate ratios. Based on observations of the heat evolution at the fire exposed surface and at different depths inside the specimens as well as based on photogrammetric observations of the spalled dimensions, the results indicate that with increasing paste volumes the heat conductivity is reduced and as a result concrete with higher paste to aggregate ratios shows less spalling.
Time-of-flight secondary ion mass spectrometry (ToF-SIMS) and high-resolution scanning electron microscopy are well-acknowledged tools in materials characterization. The ability to map chemical species on the surface of an investigated sample with often low mass detection limits makes ToF-SIMS an essential tool in fields where many question marks concerning Degradation processes and damage mechanisms exist. The aim of this paper is to describe the power of data fusion of ToF-SIMS and high-resolution scanning electron microscopy results employing computational methods for multivariate data Analysis such as principal component analysis. As a case study the investigation of hydrogen distribution in an artificially charged Duplex stainless steel microstructure is presented aiming on a better understanding of hydrogen embrittlement.
Neutron imaging
(2016)
Neutron imaging methods are appropriate to investigate hydrogen distributions in several metallic systems. The large total neutron cross section of hydrogen compared to those of elements or isotopes, respectively, in usual structural materials like steels or zirconium alloys allows the detection even of small amounts of hydrogen in such materials. The dependence of the total macroscopic neutron cross section of the sample or component on the hydrogen concentration can be determined experimentally by means of calibration specimens with known hydrogen concentrations. Such a calibration allows for a full quantitative determination of the local hydrogen concentration with a spatial resolution better than 20 μm. Because neutron radiography is fast and non-destructive, in situ investigations of time-dependent processes like hydrogen absorption and release or hydrogen bulk diffusion can be performed. This chapter gives an introduction into the main neutron imaging methods, radiography and tomography, and gives as examples results of neutron imaging investigations of hydrogen in different steels and in zirconium alloys,respectively.
Optical constants of harmful and highly energetic liquids for application to THz screening systems
(2016)
The far-infrared (IR) optical constants of a set of hazardous and flammable liquids have been obtained by means of spectroscopic ellipsometry in attenuated total reflection configuration over a broad spectral range. Such liquids recently became of considerable concern for transportation security measures worldwide. Their optical identification at check-in gates can only become possible if the characteristic spectra are already known. The refractive indices and the extinction coefficients reported here contribute to a spectroscopic data base in the far-IR and terahertz (THz) spectral regions and may support modeling the performance of THz screening systems on liquids for airports and other security sensitive areas. Examples of several container material/liquid systems are discussed. From the measured optical constants typical THz waveforms are calculated and discussed.
Dissimilar metal weld overlays of nickel base alloys on low alloy steel components are commonly used in the oil and gas, petro-chemical, and power generation industries to provide corrosion and oxidation resistance in a wide range of service environments and temperatures. Traditionally, weld overlays are produced using cold or hot wire gas tungsten arc welding (GTAW). Potential advantages of cold metal Transfer (CMT) welding, a low heat input gas metal arc welding process, over the conventional GTAW in production of weld overlays were evaluated. Metallurgical characterization was performed on CMT overlays of Alloy 625 filler metal on Grade 11 and Grade 22 steels. Significant grain refinement was found in the high temperature HAZ compared to the traditional coarse-grained HAZ in arc welding. Evidences of incomplete carbide dissolution, limited carbon diffusion, and incomplete transformation to austenite were also found. These phenomena were related to high heating and cooling rates and short dwell times of the high-temperature HAZ in austenitic state. Tempering effects in the steel HAZ were identified, showing a potential for development of CMT temperbead procedures. Based on the results of this study, the steel HAZ regions in CMT overlays were classified as high-temperature HAZ and intercritical HAZ.
Industrial wastes (bottom ash, crushed concrete fines, filter residue, paper ash and lignite fly ash) have potential for use in building materials, for instance as raw materials for clinker production, as supplementary cementitious materials (SCMs) or mineral additions in concrete. The properties of the products are dependent on the reactivity of the waste materials used, which can be classified as inert, latent hydraulic or pozzolanic. In this study, waste materials were first characterised. This was followed by theoretical considerations of the mentioned application options. Experiments were limited to evaluation of potential as SCMs and, for this purpose, activity index measurements and calorimetric and thermogravimetric analyses were performed. Finally, the synergetic effects of various waste materials were considered. Paper ash (calcium oxide source) and filter residue (amorphous silicon dioxide source) showed the best prospects for use as cementitious material components.
The nature of the bound water in solids with hydrogen-bonded networks depends not only on temperature and pressure but also on the nature of the constituents. The collapse and reorientation of these network structures determines the stability of hydrated solids and transitions to other crystalline or amorphous phases. Here, we study the mechanochemically induced loss of bound water in Co₃(PO₄)₂·8H₂O and compare this process to the behavior under hydrostatic pressure.
The associated phase transition and its kinetics were monitored by X-ray powder diffraction with Synchrotron radiation and quantitative IR spectroscopy. High shearing forces are responsible for the degradation of the hydrogen-bonded network and the concomitant crystalline–amorphous transformation. UV/Vis spectroscopy, extended X-ray absorption spectroscopy (EXAFS), and X-ray absorption near-edge spectroscopy (XANES) provided information about the short-range order in the amorphous solid, and thermal analysis revealed its composition and showed that the moderate charge densities of the Co²⁺ and PO₄³⁻ ions, which make the hydration enthalpy comparable to the binding energy of the counteranions, and the Formation of hydrogen-bonded networks favor multistage crystallization processes associated with the release and uptake of coordinated water. The changes of the Co²⁺ coordination induce a color change from pink to blue; therefore, Co₃(PO₄)₂·8H₂O can be used as an overheat temperature indicator.
We describe a fast and effective synthesis for molecular metal phosphonates. Isomorphic compounds [M(II)(HO₃PPh)₂(H₂O₃PPh)₂(H₂O)₂] (M = Mn (1), Co (2), Ni (3); Ph = C₆H₅) were obtained by grinding. The complexes are mononuclear compounds containing neutral and monodeprotonated phenylphosphonic acid and water as ligands. The crystal structures were determined using powder X-ray diffraction (PXRD) data and validated by extended X-ray absorption fine structure (EXAFS) data. Combined synchrotron XRD measurements and Raman spectroscopy were conducted for investigating the reactions in situ. Based on these data, the intermediates were characterized and the formation mechanism was derived.
As consequence for increasing threats by IEDs (Improvised Explosive Devices) on vehicles, the blast resistance of the welded frames and bodies becomes increasingly important. Considering vehicle welds subjected to blasting, the real configurations of the joints in the structure and the position of the blast loads have to be considered. The present contribution thus focuses on a weld joint at the explosion endangered wheel well of a tactical truck. The high-strength steel welds were subsequently impacted by explosion loads within the upper range from those experienced in practical military operation to cause not only deformation, but also to investigate the ultimate fracture behaviour of the high-strength weld. The interaction between cooling time t8/5 and displacement, crack path as well as fracture surface was analysed. The analyses of the fracture surfaces revealed ductile overload failure and also the size of the dimples was influenced by the cooling time t8/5. As a prominent feature, these investigations showed that the crack path of such high-strength steel welds under blasting is less influenced by the final hardness level in the respective weld microstructures but much more affected by the hardness gradient at the fusion line and inside the Heat Affected Zone (HAZ).
Waste disposal of carbon nanotube (CNT) containing products is expected to be the most important pathway for release of CNTs into the environment. In the present work, the use of radiolabelled CNTs (14C-CNT) for polycarbonate polymer nanocomposites with 1 wt% 14C-CNT content allowed for the first time to quantify and differentiate the CNT release according to the type of impact along the materials' ageing history. After an initial exposure of the nanocomposite by solar-like irradiation, further environmental impacts were applied to composite material. They aimed at mimicking disposal site conditions that may induce further ageing effects and CNT release. This study included shaking in water, rapid temperature changes, soaking in humic acid solution as well as waste water effluent, and, finally, gentle mechanical abrasion. All ageing impacts were applied sequentially, both on pristine (control) and on solar-irradiated nanocomposites. All experiments were accompanied by absolute quantification of radioactive release as well as chemical and morphological analyses of the nanocomposite surfaces using infra-red (IR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The morphological analysis showed that spectral irradiation can uncover CNT networks on the outer nanocomposite surface layers by polymer degradation. After having subjected the solar-irradiated nanocomposite to all studied disposal site effect, the total radioactive release was quantified to amount to 64 mg CNT/m2, whereas only 0.8 mg CNT/m2 were found for the un-irradiated control sample. Solar degradation of polymers was thus found to significantly increase the propensity of the studied polymer nanocomposites to release CNTs during ageing effects at the product's end-of-life typical for disposal sites.
For inspection of thick-walled (50mm) copper canisters for final disposal of spent nuclear fuel in Sweden, ultrasonic inspection using phased array technique (PAUT) is applied. Because thick-walled copper is not commonly used as a structural material, previous experience on Phased Array Ultrasonic Testing for this type of application is limited. The paper presents the progress in understanding the amplitudes and attenuation changes acting on the Phased Array Ultrasonic Testing inspection of copper canisters. Previous studies showed the existence of a low pass filtering effect and a heterogeneous grain size distribution along the depth, thus affecting both the detectability of defects and their "Probability of Detection" determination. Consequently, the difference between the first and second back wall echoes were not sufficient to determine the local attenuation (within the inspection range), which affects the signal response for each individual defect. Experimental evaluation of structural attenuation was carried out onto step-wedge samples cut from full-size, extruded and pierced&drawn, copper canisters. Effective attenuation values has been implemented in numerical simulations to achieve a Multi Parameter Probability of Detection and to formulate a Model Assisted Probability of Detection through a Monte-Carlo extraction model.
How much information do we need? A reflection of the correct use of real defects in POD-evaluations
(2016)
To evaluate the capability of a non destructive testing system the “truth” of the used defects is essential. But what exactly is the truth of a real defect? And how much information is usable for the study? This presentation gives an overview about an advanced use of multiple metallographic cuts for the POD evaluation. In the presentation an approach is shown where information of metallographic studies are reconstructed and weighted to gain the essential information about real defects and which information are important for the detection with radiographic testing equipment. Furthermore, different connection points are discussed were additional knowledge from simulation and artificial defects can be used to gain additional certainty for the result of the evaluation. The methodology is used for the evaluation for the digital radiographic testing system for the testing of electron-beam welds, which is one possible choice to seal the Finnish copper canisters for the final deposit of spent nuclear fuel.
This work presents the use of limited experimental measurements to develop a set of calibrated Simulation parameters that can then be used for reliable simulation of subsea pipeline inspections. The modelling software aRTist is used as the simulation tool, and the calibration is through comparison with experimental images of a well characterised sample in a water tank. Image Quality parameters such as signal-to-noise ratio, contrast and basic spatial resolution are compared with the aim of matching simulated values to experimental results. Currently the model is partially calibrated, with signal-to-noise ratio successfully matched while differences are still found in contrast-to-noise ratio comparisons. This means that measurements depending on absolute intensity are not accurate enough in the simulation at this stage. However, the simulation is found to be accurate for wall thickness measurements in tangential images, which are not based on absolute intensity, with simulated and experimental cases producing similar results.
Modifying the level of mostly detrimental welding residual stresses already during the welding process would be highly attractive as time- and cost-consuming post processing may be prevented. The nature of stress buildup during welding-associated cooling is highly affected by phase transformations. Up to now, it is not clear in which way this is applicable to real component welding exhibiting high shrinkage restraint and complex heat input. In this study, two different low transformation temperature (LTT) alloys have been investigated concerning the stress development in restrained multi-run butt welding in order to evaluate the potential of stress reduction. Pulsed gas metal arc welding (P-GMAW) welding was executed on a testing facility designed to simulate real lifelike restraint conditions of component weldments. The effect of reducedMS-temperatures and the heat control on the globally acting stresses was monitored by in-situ measurement of the reaction forces during welding fabrication. Additional local residual stress measurements allowed analyzing global as well as local loading of the welded construction. Although phase transformation has a significant influence on unloading the joint during each weld pass, the reaction stress upon cooling to room temperature seems to be determined mainly by the heat input. On the surface, low longitudinal residual stresses were observed in case of LTT whereas transverse residual stresses are less affected.
Explosion regions of propane, isopropanol, acetone, and methyl acetate/inert gas/air mixtures
(2016)
The explosion regions for propane, isopropanol, acetone, and methyl acetate with air in the presence of nitrogen, argon, helium, and carbon dioxide were determined experimentally according to EN 14756/EN1839, method T. Except for propane, all the measurements were executed at 323 K and 1 bar. Propane experiments were carried out at 293 K and 1 bar. The results show that for the same type of inert gas, propane, isopropanol, and acetone have great closeness concerning the concentration of the inert gas at the apex of the explosion envelope in a ternary diagram with air as oxidizer. This leads to consistency in the limiting oxygen concentration (LOC) and minimum required amount of inert gas (MAI) values. Concerning methyl acetate, the apex was always reached at higher percentages of inert gases compared with the other fuels. This can be attributed to the presence of two oxygen atoms inside the chemical structure. Calculation of the explosion regions was carried out based on calculated adiabatic flame temperature (CAFT) method. The flame temperatures for the experimentally determined fuel/air/N2 mixtures were calculated. Then, these temperatures were used to predict the explosion limits of similar mixtures with other inert gases than nitrogen. The modeling results show reasonable agreement with the experimental results.
Results of rolling contact fatigue (RCF) tests by balls-on-rod (BOR) method and two-roller methods have been compared to those by the balls-on-flat (BOF) method by using three different silicon nitride grades. The results suggest that the two-roller method could differentiate the bearing grade materials in terms of wear behavior.
The topographic effect of steel counterface, finished by mechanical grinding with Ra ranging from 0.01 to 0.95 µm, on the structure and functionality of the tribofilm of a hybrid nanocomposite, i.e. epoxy matrix filled with monodisperse silica nanoparticles, carbon fibers and graphite, was systematically investigated. The nanostructure of the tribofilm was comprehensively characterized by using combined focused ion beam and transmission electron microscope analyses. It was identified that oxidation of the steel surface, release, compaction and tribosintering of silica nanoparticles and deposition of an epoxy-like degradation product as well as fragmentation of carbon fibers are main mechanisms determining the structure and functionality of the tribofilm. The size of roughness grooves determines the type and size class of wear particles to be trapped at the surface. An optimum groove size leading to a maximum of surface coverage with a nanostructured tribofilm formed mainly from released silica nanoparticles was identified.
The method of movable cellular automata (MCA) and method of molecular dynamics (MD) were applied to simulate the friction and sliding behavior of model-tribofilms formed from a nanocomposite consisting of an epoxy matrix, 10 vol % micron-sized carbon fibers and 5 vol. % silica nanoparticles. Whereas MCA considered the tribofilm as an agglomerate of silica nanoparticles released from the composite and mixed with graphite particles, MD simulated the sliding behavior of an amorphous silica layer supported by stiff crystalline substrates on both sides. The MCA model provided reasonable quantitative results which corroborate experimental findings at moderate stressing conditions. The very low coefficient of friction observed experimentally under severe stressing conditions was not explained by this model. This could be attributed to the lack of mechanical data at the high temperature expected under these conditions. Although based on a simpler assumption of the tribofilm composition, MD-modelling could be easily applied to the expected high flash temperature and was able to predict friction reduction and smooth sliding under these conditions.
Exploring the influence of counterpart materials on tribological behaviors of epoxy composites
(2016)
The dependence of the friction and wear of epoxy (EP) composites materials on counterpart materials, such as standard bearing steel, medium carbon steel and chrome-plating (Cr), was investigated. The conventional composite filled with short carbon fiber (SCF) and graphite shows the highest tribological performance when rubbing against Cr, whereas, the hybrid nanocomposite (EP filled with SCF, graphite and silica nanoparticles) exhibits the lowest friction and wear when sliding against the standard bearing steel. The role of nanoparticles in the tribological performance is distinctly different when sliding against with various counterpart materials. It is demonstrated that counterpart materials exert an important influence on material transfer, tribo-oxidation and mechanical mixing of wear products, resulting in the different formation mechanisms of transfer film.