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Ancient papyri are a written heritage of culture that flourished more than 3000 years ago in Egypt. One of the most significant collections in the world is housed in the Egyptian Museum and Papyrus Collection in Berlin, from where the samples for our investigation come. The papyrologists, curators and conservators of such collections search intensely for the analytical detail that would allow ancient papyri to be distinguished from modern fabrications, in order to detect possible forgeries, assess papyrus deterioration state, and improve the design of storage conditions and conservation methods. This has become the aim of our investigation. The samples were studied by a number of methods, including spectroscopic (FTIR, fluorescent-FS, Raman) diffractional (XRD) and chromatographic (size exclusion chromatography-SEC), selected in order to determine degradation parameters: overall oxidation of lignocellulosic material, degree of polymerization and crystallinity of cellulose. The results were correlated with those obtained from carefully selected model samples including modern papyri and paper of different composition aged at elevated temperature in humid air. The methods were classified in the order SEC > FS > FTIR > XRD, based on their effectiveness in discriminating the state of papyri degradation. However, the most trustworthy evaluation of the age of papyri samples should rely on several methods.
Hybrid laser-arc welding of thick-walled ferromagnetic steels with electromagnetic weld pool support
(2018)
The hybrid laser-arc welding (HLAW) process provides many advantages over laser welding and arc welding alone, such as high welding speed, gap bridgeability, and deep penetration. The developments in hybrid laser-arc welding technology using modern high-power lasers allow single-pass welding of thick materials. This technology can be used for the heavy metal industries such as shipbuilding, power plant fabrication, and line-pipe manufacturing. The obvious problem for single-pass welding is the growth of the hydrostatic pressure with increasing thickness of materials leading to drop-out of molten metal. This phenomenon is aggravated at slow welding velocities because of increasing weld seam width followed by a decrease of Laplace pressure compensating the hydrostatic pressure. Therefore, weld pool support is necessary by welding of thick materials with slow welding velocities. The innovative electromagnetic weld pool support system is contactless and has been used successfully for laser beam welding of aluminum alloys and austenitic and ferromagnetic steels. The support system is based on generating Lorentz forces within the weld pool. These are produced by an oscillating magnetic field orientated perpendicular to the welding direction. The electromagnetic weld pool support facilitates a decrease in the welding speed without a sagging and drop-out of the melt thus eliminating the limitations of weldable material thickness.
The study deals with the determination of the influence of an externally applied oscillating magnetic field on the melt pool dynamics in high power laser beam and hybrid laser arc welding processes. An AC magnet was positioned under the workpiece which is generating an upward directed electromagnetic force to counteract the formation of the droplets. To visualise the melt flow characteristics, several experiments were carried out using a special technique with mild steel from S355J2 with a plate thickness of up to 20 mm and a quartz glass in butt configuration. The profile of the keyhole and the melt flow were recorded with a highspeed camera from the glass side. Additionally, the influence of the magnetic field orientation to the welding direction on the filler material dilution on laser hybrid welding was studied with variating oscillation frequency. The element distribution over the whole seam thickness was measured with X-ray fluorescence (XRF). The oscillation frequency demonstrated a great influence on the melt pool dynamics and the mixing of the elements of the filler wire. The highspeed recordings showed, under the influence of the magnetic field, that the melt is affected under strong vortex at the weld root, which also avoids the formation of droplets.
The stability of the keyhole decreases for deep penetrated high-power laser beam welding. The keyhole tends to collapse with increasing laser power and e.g. keyhole induced porosity can occur. This study deals with the observation of the keyhole during high-power laser beam welding in partial penetration mode by means of a high-speed camera. A butt configuration of 25 mm thick structural steel and transparent quartz glass was used for the experiments. An oscillating magnetic field was applied perpendicular to the welding direction on the root side of the steel plate. The keyhole was highlighted with a coaxial diode laser. It was ascertained that the stability of the keyhole and the weld penetration depth were increased by applying an oscillating magnetic field with an oscillating frequency of 1.2 kHz and a magnetic flux density of 50 mT.
It is already known that the laser beam welding (LBW) or hybrid laser-arc welding (HLAW) processes are sensitive to manufacturing tolerances such as gaps and misalignment of the edges, especially at welding of thick-walled steels due to its narrow beam diameter. Therefore, the joining parts preferably have to be milled. The study deals with the influence of the edge quality, the gap and the misalignment of edges on the weld seam quality of hybrid laser-arc welded 20-mm-thick structural steel plates which were prepared by laser and plasma cutting. Single-pass welds were conducted in butt joint configuration. An AC magnet was used as a contactless backing. It was positioned under the workpiece during the welding process to prevent sagging. The profile of the edges and the gap between the workpieces were measured before welding by a profile scanner or a digital camera, respectively. With a laser beam power of just 13.7 kW, the single-pass welds could
be performed. A gap bridgeability up to 1 mm at laser-cut and 2 mm at plasma-cut samples could be reached respectively.
Furthermore, a misalignment of the edges up to 2 mm could be welded in a single pass. The new findings may eliminate the need for cost and time-consuming preparation of the edges.
The application of hybrid laser-arc welding (HLAW) for joining closed circumferential welds is a challenge due to the high risk of forming a defective overlap area with a shrinkage void or solidification cracks in the material thickness. A series of HLAW experiments were performed to understand the development of a faulty overlap area when closing the circumferential weld. Welding trials on flat specimens and pipe segments were supported by numerical analyses in which the thermomechanical behavior of the welds in the overlap area was investigated. Different process control strategies were tested, including variations in defocusing levels and the overlap length. The newly developed HLAW head, including laser optics with a motor-driven collimation system, made it possible to defocus the laser beam during welding without disturbing the stability of the welding process. High-level defocusing of the laser beam of more than 40 mm relative to the specimen surface with a resulting beam diameter of > 2.9 mm, and in combination with a short overlap length of 15 mm, was promising with respect to the formation of a desired cup-shaped weld profile that is resistant to solidification cracks.
The influence of heat input and welding speed on the microstructure and mechanical properties of single-pass hybrid laser arc welded 20mm thick plates of high-strength pipeline steel X120 were presented. The heat Input was varied in the range of 1.4 kJ mm−1 to 2.9 kJ mm−1, while the welding speed was changed between 0.5m min−1 and 1.5m min−1. A novel technique of bath support based on external oscillating electromagnetic field was used to compensate the hydrostatic pressure at low welding velocities. A major advantage of this technology is, that the welding speed and thus the cooling time t8/5 can be variated in a wide parameter window without issues regarding the weld root quality. The recommended welding thermal cycles for the pipeline steel X120 can be met by that way. All tested Charpy-V specimens meet the requirements of API 5 L regarding the impact energy. For higher heat inputs the average impact energy was 144 ± 37 J at a testing temperature of −40 °C. High heat Input above 1.6 kJ mm−1 leads to softening in the weld metal and heat-affected-zone resulting in loss of strength. The minimum tensile strength of 915 MPa could be achieved at heat inputs between 1.4 kJ mm−1 and 1.6 kJ mm−1.
Hybrid laser-arc welding offers many advantages, such as deep penetration, good gap bridge-ability, and low distortion due to reduced heat input. The filler wire which is supplied to the process is used to influence the microstructure and mechanical properties of the weld seam.
A typical problem in deep penetration high-power laser beam welding with filler wire and hybrid laser-arc welding is an insufficient mixing of filler material in the weld pool, leading to a non-uniform element distribution in the seam. In this study, oscillating magnetic fields were used to form a non-conservative component of the Lorentz force in the weld pool to improve the element Distribution over the entire thickness of the material. Full penetration hybrid laser-arc welds were performed on 20-mm-thick S355J2 steel plates with a nickel-based wire for different arrangements of the oscillating magnetic field. The Energy-dispersive X-ray spectroscopy (EDS) data for the distribution of two tracing elements (Ni and Cr) were used to analyze the homogeneity of dilution of the filler wire.
With a 30° turn of the magnetic field to the welding direction, a radical improvement in the filler material distribution was demonstrated. This would lead to an improvement of the mechanical properties with the use of a suitable filler wire.
Static TOF-SIMS results strongly underpin earlier conclusions from ESCA, XANES, and tracer studies that the accumulation of fluorine and chlorine at the surface of chromia by a heterogeneous reaction with a chlorofluorocarbon compound results in the formation of mixed chromium oxide halide species and not in the nucleation of CrCl3 and/or CrF3 phases.
The dismutation of CCl2F2 was used to probe the effect of halogenation of chromia by Cl/F exchange reactions to find out the difference between the halogenated inactive and active catalysts. The heterogeneous reactions were performed in a continuous flow Ni reactor and also under simulated reaction conditions in a reactor where after the reaction X-ray photoelectron spectroscopy (XPS) and X-ray excited Auger electron spectroscopy (XAES) analyses are possible without air exposure of the catalyst, i.e., under so-called "in situ" conditions. The Cr(III) 2p XP spectra, which revealed multiplet splitting features and satellite emission, were used for chemical analysis by using a simple evaluation procedure which neglects this inherent complexity. Chemical analysis was also applied by using chemical state plots for Cr 3s in order to cross-check Cr 2p related results. Both ex and in situ XPS show that as soon as Cr2O3 is exposed to CCl2F2 at 390°C fluorination as well as chlorination takes place at the catalyst surface. When the XPS surface composition reaches approximately 4 at. % fluorination and 6 at. % chlorination, maximum catalytic activity was obtained. Application of longer reaction times did not change significantly the obtained surface composition of the activated chromia. The fluorination and chlorination of chromia was further investigated by various HF and HCl treatments. The activated chromia samples and the Cr2O3, Cr(OH)3, CrF2OH, CrF3·H2O, α-CrF3, β-CrF3, and CrCl3 reference samples with well-known chemical structures were also characterized by X-ray absorption near edge structure (XANES), time-of-flight secondary ion mass spectroscopy (TOF-SIMS), pyridine-FTIR, wet chemical (F and Cl) analysis, X-ray powder diffraction (XRD), and surface area (BET) analysis. The results suggest that the formation of chromium oxide chloride fluoride species, e.g., chromium oxide halides, at the surface is sufficient to provide catalytic activity. The presence of any CrF3 and/or CrCl3 phases on the activated chromia samples was not found.
The formation of a third body layer on a conventional friction material during braking tests was studied in some detail using TEM, SEM, and X-ray photoelectron spectroscopy (XPS) techniques. Plate shaped micro-contact areas representing a compositional mix of all components of the tribocouple and exhibiting a nanocry stalline microstructure were identified after a run-in period.
The surfaces of a brake pad and rotor were investigated after a run-in period during which a stable coefficient of friction had developed. The Focused Ion Beam Technique (FIB) was used to reveal tribologically induced surface films and for cross-sectional preparation of superficial layers. Additional information was obtained by TEM/EDS of thin lamellae prepared with the FIB and by surface analytical methods (GDOS, XPS and RS). Microscopic contact areas of the pad showed bright contrast in Scanning Ion Microscopy (SIM). This was attributed to severe plastic deformation finally leading to a nanocrystalline microstructure. Metallic particles of the pad, the so-called primary contact areas, were mostly covered with a smooth oxide layer of less than 1 µm thickness. Above this layer a thin (100 nm) partly amorphous film was often observed. The film was not only restricted to the metal particles, but also spread over adjacent regions, suggesting that secondary plateaus had formed. Similar layers and films, although with slightly different composition and structure, were also observed at the surface of the rotor.
A rather new tool, the focused ion beam (FIB) technique, was used to characterise superficial layers at micro-contact areas of a commercial brake pad. The friction material was a polymer matrix composite (PMC) with approximately 50% metal content (semi-metallic) and the counter part was a cast iron rotor. Though the contact areas were not visible as topographic features, they could be identified with the aid of their increased secondary electron emission during FIB-scanning of the surface after tribological activation. Target preparation of micron-sized cross-sections with the FIB enabled the study of superficial layers at predetermined sites at high magnification.
Depending on the constituent of the pad, one, two or three layers were identified. The three layer structure comprised: (i) a 100 nm thick friction film containing nanocrystalline metal oxides and an amorphous phase which was enriched with sulphur, (ii) a nanocrystalline friction layer of compacted wear debris accommodating surface roughness and (iii) a severely deformed layer if the supporting constituent was a metal particle. Though the majority of loose wear particles was iron oxide, the friction film which adhered tightly to the pad surface contained a large amount of copper and sulphur, whereas zinc was transferred to the cast iron rotor.
Patches of white etching layers on rail surfaces were investigated using sophisticated techniques like cross-sectional transmission electron microscopy (XTEM) and synchroton X-ray diffraction. Optical microscopy failed to resolve the microstructure, but in the TEM submicron grains with high dislocation densities and occasional twins, which are characteristic features of high carbon martensite, were observed. The martensitic structure was confirmed by evaluation of synchroton X-ray diffraction line profiles. The latter technique also allowed to determine dislocation densities of the order of 1012 cm-2 and residual compressive stresses of about 200 MPa.
Cross-sectional transmission electron microscopy, in combination with energy dispersive X-ray spectroscopy and focused beam microdiffraction, was applied to study the solid-state reactions taking place during contact formation of the system Ge(115 nm)/Pd(50 nm)In0.53Ga0.47As. In order to get information about the sequence of the different processes, rapid thermal, annealing experiments in the range 225400 °C were performed. The following features were observed: at 225 °C Pd reacted with the substrate forming the quaternary phase PdxIn0.53Ga0.47As (x 4), and with the Ge-layer forming mainly PdGe and Pd2Ge. Between PdxIn0.53Ga0.47As and In0.53Ga0.47As, a 5 nm thick amorphous Pd-In-Ga-As layer remained, indicating that the first reaction step was solid-state amorphization. After annealing at 350 °C, PdxIn0.53Ga0.47As disappeared and regrowth of In0.53Ga0.47As occured. Finally, at 400 °C, residual Ge from the amorphous top layer diffused to the interface and grew epitaxially on the regrown In0.53Ga0.47As, thus separating the IIIV compound semiconductor from the Pd-Ge reaction products. The interface remained flat, while only about 10 nm of the active In0.53Ga0.47As layer had been modified during the annealing processes.
Copper is a major ingredient in friction materials used for automotive braking. The purpose of this study was to find out how copper contributes to good brake performance properties in addition to providing good thermal conductivity. Microstructural investigations of copper chips at the surfaces of brake pads revealed a zone of severe plastic deformation which provides high hardness, but there is also evidence of recrystallized copper nano-particles which are incorporated into friction layers as soft ingredient once detached from the pad surface. Thus copper seems to play a dual role, firstly as reinforcing element of the brake pad providing primary contact sites, and secondly as solid lubricant by contributing to the formation of a layer of granular material providing velocity accommodation between the rotating disc and fixed pad. Confirmation for this hypothesis was obtained by modelling contact sites on the nanometre scale with the method of movable cellular automata. Results show both, the similarity of steel fibres and copper macro-particles in respect to providing primary contact sites, as well as similar sliding behaviours of friction layers containing either copper or graphite as soft inclusions. Furthermore, it is shown that not only material properties, but also the concentration of solid lubricant particles in the friction layers, determine conditions for friction force stabilization and smooth sliding behaviour.
The unique nanostructure formed during severe as well as moderate braking on the surface of brake discs was investigated by conventional and analytical Transmission Electron Microscopy. In both cases nanocrystalline magnetite mixed with carbon nanoinclusions and minor amounts of other pad constituents were identified. On the basis of these observations the friction performance of a single micro-contact was simulated with the method of Movable Cellular Automata. Inspite of a simplified nanostructure which was examined in two dimensions only, the calculated mean coefficient of friction fitted well to the value usually demanded for automotive braking. Furthermore, the model predicts that oxide films without soft nanoinclusions are not capable of providing smooth velocity accommodation at the pad–disc interface and thus lead to unstable friction behaviour.
Different, partly complementary and partly redundant characterization methods were applied to study the transition of magnetite, graphite and MoS2 powders to mechanically alloyed nanostructures. The applied methods were: Transmission electron microscopy (TEM), Mössbauer spectroscopy (MS), Raman spectroscopy (RS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The main objective was to prepare a model material providing the essential features of a typical tribofilm forming during automotive braking, and to assess the impact of different constituents on sliding behaviour and friction level. Irrespective of the initial grain size, the raw materials were transferred to a nanocrystalline structure and mixed on a nanoscopic scale during high energy ball milling. Whereas magnetite remained almost unchanged, graphite and molybdenum disulphide were transformed to a nanocrystalline and highly disordered structure. The observed increase of the coefficient of friction was attributed to a loss of lubricity of the latter ingredient due to this transformation and subsequent oxidation.
XTEM and TFXRD investigations of ohmic Ti/Al/Ti/Au/WSiN contacts on AlGaN/GaN HFET layer systems
(2002)
The microstructural features of the high-temperature-stable ohmic contact system Ti/Al/Ti/Au/WSiN on AlGaN/GaN were investigated using analytical transmission electron microscopy and thin film x-ray diffraction. For two typical rapid thermal annealing steps at 750 °C (non-ohmic behaviour) and 850 °C (ohmic behaviour) the intermetallic phases at the metal-semiconductor interface are presented. Increased annealing leads to the transformation of an Al2Au-AlAuTi phase mixture to a mixture of Al2Au-Al3Au8 phases and the formation of Ti-Al-nitride layers at the interfaces. In light of these results the electrical contact properties are discussed.
Residual stress depth profiles of a cast nickel-base superalloy were measured by regarding the deflections occurring in plate-shaped specimens while successively removing layers from the machined or treated surface by electropolishing. The results are in good agreement with previous findings showing (i) the influence of grinding parameters on the width of so-called white layers, which correspond to steep gradients of residual tensile stress, and (ii) a broad zone of compressive residual stress in the case of shot peening.
Mechanical and thermal response of a nickel-base superalloy upon grinding with high removal rates
(1997)
Turbine components from conventionally cast nickel-base alloy René 80 show different hot cracking susceptibilities depending on their heat treatment conditions leading to slightly different microstructures. Electron probe micro-analysis, focused ion beam technique and analytical transmission electron microscopy were applied to reveal and identify grain boundary precipitates and the γγ'-microstructure. The distribution of borides along grain boundaries was evaluated statistically by quantitative metallography. The following features could be correlated with an increase of cracking susceptibility: i) Increasing grain size, ii) increasing fraction of grain boundaries with densely spaced borides, iii) lack of secondary γ'-particles in matrix channels between the coarse cuboidal γ'-precipitates. The latter feature seems to be responsible for linking-up of cracked grain boundary precipitates which occurred as an additional cracking mechanism after one heat treatment, whereas decohesion at the boride-matrix-interface in the heat affected zone of laser-drilled holes was observed for both heat treatments.
This work focuses on surface changes induced by repeated brake applications and tries to provide explanations, how such material modifications might affect friction and wear properties of automotive disc brakes. Surface films were investigated locally by transmission electron microscopy (TEM) after having prepared thin cross-sections with a focused ion beam instrument (FIB). Since the observed friction layers revealed a nanocrystalline structure, modelling with the method of movable cellular automata (MCA) was performed by assuming an array of linked nanometer-sized particles. In spite of complicated material combinations at the pad surface, two very characteristic features were always observed at both the pad and disc surface, namely a steel constituenteither ferritic (pad) or pearlitic (disc), partly covered with patches of nanocrystalline iron oxide, on a zone of severe plastic deformation with fragmented grain structure. When using an automata size of 10 nm, reasonable values for the mean coefficient of friction (COF) were obtained, namely 0.35 and 0.85 for oxide-on-oxide and metal-on-metal contacts, respectively. Immediately after brake application mass-mixing and bond-breaking was observed within a narrow zone at both surfaces.
Tribological screening tests (simple, reciprocating ball-on-flat tests) were performed with the objective to identify an appropriate coating for the articulating surfaces of artificial hip joints whose acetabular cups and femoral stems are made from Ti6Al4V alloy, which is appreciated for its light weight, good biocompatibility and elastic properties similar to those of natural bone. Standard coatings like TiN or CrN performed better than more complicated multi-layer systems, though not as good as different types of amorphous carbon coatings, generally referred to as diamond-like carbon or DLC coatings. Among the latter, hydrogenated amorphous carbon (a-C:H) displayed the best properties, especially if the hydrogen content was increased by reducing the bias voltage during PA-CVD-deposition.
The optimised a-C:H coating revealed the most promising wear behaviour under the applied testing conditions, i.e. the increase of linear wear with the number of cycles was close to zero. Regarding the materials examined in this study, correlation of wear with mechanical properties obtained by nano-indentation revealed that high hardness was not an adequate criterion for selecting appropriate coatings. A high ratio of hardness and elastic modulus (H/E) proved to be more important. Microstructural and micro-analytical investigations revealed transformation of TiN and CrN to TiO2 and Cr2O3, respectively, and amorphous carbon was, at least partly, transformed to graphite. Furthermore, incorporation of Al2O3 from the ball was observed at a very fine scale. The wear debris of favourable coatings always formed agglomerates of nano-scale particles. It was shown that commercial nano-particles of Al2O3, Cr2O3 and carbon black are comparable to particles generated by the tribological tests. However, it is uncertain whether they are comparable to those formed during simulator studies or in vivo. Furthermore, the performance of the favourable coating has to be tested in a hip joint simulator before its potential for application in prostheses can be assessed.
An attempt was undertaken to obtain a better understanding of the tribological properties of two wear-resistant coatings on tool steel by structural and microchemical analysis of wear particles using a transmission electron microscope. Coatings were deposited by physical vapor deposition and plasma-assisted chemical vapor deposition techniques and tribological properties were derived from reciprocating sliding tests of the coatings against alumina balls. Three types of wear particles were identified by electron diffraction and energy dispersive X-ray spectroscopy: nanocrystalline rutile (TiO2), nanocrystalline graphite and microcrystalline graphite. Low coefficients of friction, of the order of 0.2, were attributed to the formation of solid lubricant films of sub-stoichiometric TiO2-x Magnéli phases and/or graphite.
The chemical and microstructural changes occurring during braking simulation tests at the surface of a conventional brake pad material were investigated mainly by scanning and transmission electron microscopy and surface analytical techniques. It can be shown that patches of a third body material develop, comprising a compositional mix of all constituents of the pad and iron oxides from the disk. Milled debris particles still have the crystal structure of barite, the major phase of the pad material, but the grain size is reduced drastically to the nanometer scale. The major wear mechanism is delamination of filler particles from the organic binder, supported by local degradation of the phenolic resin during asperity heating. Quartz crystals are preserved thereby adopting the function of primary contact areas.
We applied a combination of Raman spectroscopy (RS) and cross-sectional transmission electron microscopy (X-TEM) to identify silicone oil residues and tribofilms at steel disc surfaces after tribological testing. Neither chemical cleaning nor mechanical removal of a 50 µm thick surface layer produced a surface without any silicone residue. Nevertheless, long-term tribological properties are not affected due to silicone degradation which has been proved by Raman spectroscopy. Excellent anti-wear and anti-friction properties of a nanocomposite at severe stressing conditions correlated with the formation of a silica-based tribofilm containing amorphous and graphite-like carbon nanoparticles. Since reliable carbon quantification by analytical TEM is difficult, RS is a useful complementary method for carbon identification at wear scars.
X-ray photoelectron spectroscopy (XPS) and cross-sectional transmission electron microscopy (XTEM) were used to study the formation of AlN films by N+2 ion implantation of aluminium at energies of 3 keV and 100 keV. In both cases, a two-stage mechanism was found, comprising first the oriented precipitation of small particles of the hexagonal AlN-phase, followed by growth and coalescence finally forming a continuous AlN-layer while increasing the implantation dose from 1×1017 cm-2 to 2×1017 cm-2. The results of both methods are in excellent agreement and furthermore provide complementary information concerning chemical composition and binding energies as well as microstructural details.
Tribofilms formed during dry sliding usually exhibit a nanocrystalline structure and complicated composition. In the present study, tribofilms consisting mainly of a solid lubricant, namely graphite nanoparticles, are considered. Systems providing such tribofilms are candidates for anti-friction applications. Since sliding action always leads to mixing of the materials at both sides of the tribological interface, it was of major interest to study the impact of different amounts of a hard constituent, SiC in the considered case, within the soft matrix systematically. Furthermore, the impact of normal pressure was considered. A mechanically mixed layer was observed for the whole range of normal pressures and SiC volume fractions. The calculated coefficient of friction decreased significantly with increasing thickness of this layer but was only marginally affected by SiC volume fraction, which is good news for anti-friction applications.
Automotive braking is based on dry friction between fixed pads and a rotating disc. Besides macroscopic thermo-physical properties, the development of topographic features on the mesoscopic scale and the nanostructure of the third body formed by wear processes, determine brake performance properties. Whereas modelling on the atomistic scale is suitable to understand mechanisms leading to nanocrystalline surface films, the properties of such films can be assessed best with a model based on movable cellular automata (MCA). It turned out that the presence of at least 10% of soft nanoinclusions is most essential in respect to smooth sliding conditions. It made no major difference whether graphite or copper particles were assumed as soft nanoinclusions. The third body material is not only the stuff which spreads over contact areas, but it also contributes to contact size by wear particle compaction and formation of secondary contact areas. The evolution of contact size is the major feature of mesoscopic modelling and thus it is capable to model and explain dynamic changes of the coefficient of friction (COF) during certain brake operations. Although it is still ambiguous in many cases which feature has the major impact on friction behaviour, the following conclusions can be drawn. The reinforcing ingredients of the pad material serve as primary contact sites and thus define the starting condition for mesoscopic simulations. A certain amount of wear is necessary to provide a third body which is capable to form secondary contact sites and friction layers screening the first body materials. The composition and nanostructure of the third body is important as well, because it determines the friction level and is responsible for smooth sliding conditions.
A model based on movable cellular automata has been applied to study the sliding behaviour of tribofilms formed during automotive braking. Since it is not possible yet to determine the composition of real tribofilms quantitatively, final verification of modelling results is needed. This was done by preparing artificial third bodies with compositions and nanostructures matching the ones assumed for modelling. Pin-on-disc tests were performed while applying the artificial third bodies to the contact. The results revealed that not only the structure of the third body but also the amount of the applied normal pressure determines the COF obtained by modelling and that much better correlation between experimental and modelling results was obtained while assuming high normal pressures at asperity contacts.
Does ultra-mild wear play any role for dry friction applications, such as automotive braking?
(2012)
Nanostructured third body films and/or storage of wear debris at the surfaces of the first bodies are deemed as prerequisites of sliding under ultra-mild wear conditions. Since such features have been observed experimentally on brake pads and discs, attempts were undertaken to study their sliding behaviour by modelling on the nanoscopic scale with an approach based on Movable Cellular Automata (MCA). The model rendered the possibility to study the influence of different nanostructures systematically and to assess the impact of different brake pad ingredients on the sliding behaviour, velocity accommodation and friction force stabilization at a sliding contact. Besides providing a review on previously published modelling results, some additional new graphs enabling better visualization of dynamic processes are presented. Although ultra-mild wear conditions were considered to be essential for achieving the desired tribological properties, transitions to mesoscopic and macroscopic wear mechanisms were studied as well. The final conclusion is that ultra-mild wear and corresponding smooth sliding behaviour play an important role during automotive braking, even though temporarily and locally events of severe wear may cause friction instabilities, surface damage and release of coarse wear particles.
The tribological properties of nanostructured surface films formed during dry sliding, for example during
automotive braking, were determined by modelling using the method of movable cellular automata.
Starting from a basic model structure, consisting of magnetite with 13% graphite inclusions, the impact of
additional soft and hard particles of different size and volume fraction was studied systematically. It was
revealed that agglomerates of soft particles decomposed and finally mixed with the oxide in the same
way as single nanoparticles. On the other hand, agglomerates of hard particles mixed with the other
components without decomposing. Whereas increasing the amount of soft components in the third body
lowered the coefficient of friction, the opposite occurred with the hard particles. The boundary conditions
for obtaining smooth sliding conditions with minor fluctuations between friction forces at successive time
steps could be defined. In addition to features of the nanostructure, the applied normal pressure
impacted modelling results. Within the parameter range of smooth sliding behaviour, increasing pressure
induced thicker granular interface layers, which lead to a slight decrease of the coefficient of friction.
Changing the amount of soft or hard particles did not change this pressure dependency but only the
friction level.
The composition and nanostructure of a beneficial tribofilm formed during sliding of a hybrid nanocomposite against steel were characterized comprehensively. A similar nanostructure was produced by high energy ball milling of the three identified tribofilm constituents: silica, hematite and graphite. By supplying powders to a pin-on-disc test it has been shown that neither silica, nor hematite, nor a mixture of both provide the low coefficient of friction (COF) observed for the hybrid composite. Only if graphite was blended with the oxides, the low COF was obtained. Thus, a film of finely dispersed stable inorganic wear products containing 15 vol% graphite provides low friction and wear in the considered case.
Excellent tribological properties of an advanced polymer matrix composite were obtained by a combination of micro- and nano-sized fillers. Surface features and the nanostructure of tribofilms were characterized by advanced microscopic techniques, and correlated with the macroscopic behavior in terms of wear rate and friction evolution. A model based on movable cellular automata was applied for obtaining a better understanding of the sliding behavior of the nanostructured tribofilms. The failure of the conventional composite without silica nanoparticles could be attributed to severe oxidational wear after degradation of an initially formed polymer transfer film. The hybrid composite preserves its antiwear and antifriction properties because flash temperatures at micron-sized carbon fibers, lead to polymer degradation and subsequent release of nanoparticles. It has been shown that the released particles are mixed with other wear products and form stable films at the disc surface thus preventing further severe oxidational wear. Furthermore, the released wear product also is embedding carbon fibers at the composite surface thus preventing fiber fragmentation and subsequent third body abrasion. With nanoscale modelling we were able to show that low friction and wear can be expected if the nanostructured silica films contain at least 10 vol.% of a soft ingredient.
The tribological performance of a hydrogenated amorphous carbon coating on Ti6Al4V against ceramic balls was checked by simple reciprocating sliding tests and by more complicated tests in a hip joint simulator. 3 of 4 joints failed during hip simulator testing already after approximately 100 × 10³ cycles and possibly due to coating failures caused by insufficient polishing of the metallic acetabular cups prior to coating deposition. Since such failures occurred only occasionally, the problem was not revealed by reciprocating sliding tests which are stressing a much smaller surface area compared to the tests in the hip joint simulator. Another type of failure, pits of 12 µm in diameter distributed randomly at the coating surface, was frequently observed by Scanning Electron Microscopy and analyzed comprehensively by Focused Ion Beam technique in combination with Transmission Electron Microscopy in one case. Although not necessarily affecting wear, such small failures might cause long-term problems in vivo, by providing access of body fluid to the substratecoating interface making it susceptible to corrosion.
A modified pin-on-disc test was applied to determine tribological properties of typical brake pad constituents. Ball-milling of these ingredients together with iron oxide and graphite provided model materials displaying the main features of real third bodies. Solid lubricants like graphite affected the friction and wear behaviour of Fe3O4 powders considerably whereas further addition of hard nanoparticles induced only minor effects. This was corroborated by comparison with modelling results. MoS2 played a dual role. Depending on special conditions, this ingredient either reduced or increased friction. The latter could be explained, after nanoscopic characterization, by oxidation and destruction of the wear-protecting tribofilm.
Creep and creep damage behavior of stainless steel 316L manufactured by laser powder bed fusion
(2022)
This study presents a thorough characterization of the creep properties of austenitic stainless steel 316L produced by laser powder bed fusion (LPBF 316L) contributing to the sparse available data to date. Experimental results (mechanical tests, microscopy, X-ray computed tomography) concerning the creep deformation and damage mechanisms are presented and discussed. The tested LPBF material exhibits a low defect population, which allows for the isolation and improved understanding of the effect of other typical aspects of an LPBF microstructure on the creep behavior. As a benchmark to assess the material properties of the LPBF 316L, a conventionally manufactured variant of 316L was also tested. To characterize the creep properties, hot tensile tests and constant force creep tests at 600 °C and 650 °C are performed. The creep stress exponents of the LPBF material are smaller than that of the conventional variant. The primary and secondary creep stages and the times to rupture of the LPBF material are shorter than the hot rolled 316L. Overall the creep damage is more extensive in the LPBF material. The creep damage of the LPBF material is overall mainly intergranular. It is presumably caused and accelerated by both the appearance of precipitates at the grain boundaries and the unfavorable orientation of the grain boundaries. Neither the melt pool boundaries nor entrapped gas pores show a significant influence on the creep damage mechanism.
Characterization of Ti-6Al-4V fabricated by multilayer laser powder-based directed energy deposition
(2022)
Laser powder-based directed energy deposition (DED-L) is increasingly being used in additive manufacturing (AM). As AM technology, DED-L must consider specific challenges. It must achieve uniform volume growth over hundreds of layers and avoid heat buildup of the deposited material. Herein, Ti–6Al–4V is fabricated using an approach that addresses these challenges and is relevant in terms of transferability to DED–L applications in AM. The assessment of the obtained properties and the discussion of their relationship to the process conditions and resulting microstructure are presented. The quality of the manufacturing process is proven in terms of the reproducibility of properties between individual blanks and with respect to the building height. The characterization demonstrates that excellent mechanical properties are achieved at room temperature and at 400 °C.
Lanthanides doped coordination polymers (CPs) with different binding motifs were synthesized to investigate the influence of the different fluorine positions in the structure on the decay time τ of the excited states. Fluorine can be integrated into the network mechanochemically via a fluorinated organic linker, here barium tetrafluoroterephthalate Ba(p-BDC-F4)2 or directly via a metal-fluorine bond (barium terephthalate fluoride BaF(p-BDC)0.5). The CP with a metal-fluorine bond shows the highest lifetime of the excited states of lanthanides (Eu3+, Tb3+ or Eu3+& Tb3+). The excitation of the lanthanides can be performed directly via the excitation wavelength typical for lanthanides and via the excitation wavelength of the linker. This enabled the simultaneous excitation of Eu3+ and Tb3+ in one CP. In the emission spectra (λem = 393 nm) of the mixed doped CPs (Eu3+ and Tb3+) the bands of both lanthanides can be observed. The integration into the crystal lattice and the homogeneous distribution of the lanthanides in the CPs is shown by X-ray diffraction, TEM, STEM-EDS measurements and the long decay times.
As the most electronegative element, fluorine has a strong influence on material properties such as absorption behaviour or chemical and thermal stability. Fluorine can be easily integrated into coordination polymers (CPs) via a fluorinated acetate, here trifluoroacetate in Ba(CF3COO)2, or directly via a metal fluorine bond (BaF(CH3COO)). In the present study both possibilities of fluorine integration were tested and their effect on structure and properties of barium coordination polymers was investigated in comparison with the non-fluorinated barium acetate (Ba(CH3COO)2). In addition to the study of their thermal behaviour and their decomposition temperature, the CPs structures were tested for their application as possible anode materials in lithium ion batteries and for their sorption of water and ammonia. The properties of the CPs can be traced back to the individual structural motifs and could thus trigger new design ideas for CPs in LIBs and/or catalysis.
Changes in the global bulk and local structures, of three different barium compounds (BaZrO3, BaF2, and BaFCl),were induced by mechanical milling and followed using X-ray powder diffraction (PXRD), subsequent microstructure analysis, and 137Ba solid state NMR spectroscopy. Harder materials like BaZrO3 experience significantly higher structural changes upon milling than softer materials like BaF2. Moreover, soft materials with layered structures, like BaFCl, show a pronounced structural change during the milling process. By combining PXRD and solid state NMR, detailed information on the changes to the global and local structures were obtained, which are of interest for mechanochemical synthesis, mechanically treated catalysts or ionic conductors.
New coordination polymers with 2D network structures with fluorine directly coordinated to the metal ion were prepared both via mechanochemical synthesis and fluorolytic sol–gel synthesis. Depending on the synthesis route, the samples show different particle sizes, according to SEM imaging. The crystal structures of barium acetate fluoride, strontium acetate fluoride, and lead acetate fluoride (BaFIJCH3COO), SrFIJCH3COO) and PbFIJCH3COO)) were solved from X-ray powder diffraction data. The structure solution is backed by the results from 19F MAS NMR, FT IR data, and thermal analysis. The calculated chemical shifts of the 19F MAS NMR spectra coincide well with the measured ones. It turns out that the grinding conditions have a remarkable influence on the mechanochemical synthesis and its products. Our systematic study also indicates a strong influence of the atomic radii of Ca, Sr, Ba, and Pb on the success of the syntheses.
Designing artificial macromolecules with absolute sequence order represents a considerable challenge. Here we report an advanced light-induced avenue to monodisperse sequencedefined functional linear macromolecules up to decamers via a unique photochemical approach. The versatility of the synthetic strategy—combining sequential and modular concepts—enables the synthesis of perfect macromolecules varying in chemical constitution and topology. Specific functions are placed at arbitrary positions along the chain via the successive addition of monomer units and blocks, leading to a library of functional homopolymers, alternating copolymers and block copolymers. The in-depth characterization of each sequence-defined chain confirms the precision nature of the macromolecules. Decoding of the functional information contained in the molecular structure is achieved via tandem mass spectrometry without recourse to their synthetic history, showing that the sequence information can be read.We submit that the presented photochemical strategy is a viable and advanced concept for coding individual monomer units along a macromolecular chain.
Per- and polyfluoroalkyl substances (PFAS) are widely used for durable water-repellent finishing of different fabrics and textiles like outdoor clothing, carpets, medical textiles and more. Existing PFAS extraction techniques followed by target analysis are often insufficient in detecting widely used side-chain fluorinated polymers (SFPs) that are barely or non-extractable. SFPs are typically copolymers consisting of a non-fluorinated backbone with perfluoroalkyl side-chains to obtain desired properties. We compared the accessible analytical information and performance of complementary techniques based on oxidation (dTOP assay, PhotoTOP), hydrolysis (THP assay), standard extraction, extractable organic fluorine (EOF), and total fluorine (TF) with five functional textiles and characterized 7 further textiles only by PhotoTOP oxidation. The results show that when applied directly to textile samples, oxidation by dTOP and PhotoTOP and also hydrolysis by the THP are able to capture large fractions of the TF in form of perfluoroalkyl side-chains present in the textiles while methods relying on extracts (EOF, target and non-target analysis) were much lower (e.g., factor ~25-50 lower). The conversion of large fractions of the measured TF into PFCAs or FTOHs from fluorinated side chains is in contrast to previous studies. Concentrations ranged from <LOQ to over ~1000 mg F/kg after oxidation/hydrolysis and <LOQ to over 2000 mg F/kg for TF, while EOF and target PFAS in extracts were detected at much lower concentrations (up to ~ 60 mg F/kg) (amount of fluorine in the order: extraction << EOF << oxidation/hydrolysis ≤ TF). Perfluoroalkyl carboxylic acids (PFCAs) and fluorotelomer alcohols (FTOHs) from THP and PhotoTOP both represented the chain-length distribution in the textiles showing that long-chain SFPs are still used in current textiles. Further advantages and disadvantages of the applied methods are discussed.
Abstract Nowadays, Pt-Os binary systems are mainly considered as catalysts and electrocatalysts, but the role of Os in these processes is still poorly understood. The electronic structure of Pt-Os nanosystems remains a few studied as well. Using bimetallic (NH4)2[Pt0.5Os0.5Cl6] as a single-source precursor for preparing Pt-Os nanoalloy through the thermal decomposition in hydrogen and inert atmospheres, the relation of morphology, atomic ordering, and electronic structure of Pt-Os nanoalloy was examined by in situ Quick XAFS, XPS, PXRD, SEM, and HRTEM techniques. Being the only variable parameter, the decomposition atmosphere was found to govern the morphology of the Pt-Os nanoalloy and change the atomic ordering (alloying extent), which involves a change in the electronic structure. In a hydrogen atmosphere, the nanofibers (NFs) (ø ~ 5–6 nm) with the atomic ordering Oscore&Pt-richshell were observed to form; in a nitrogen atmosphere, thin nanoplates (NPLs) (~ 12 nm) with the atomic architecture Os-richcore&Ptrichshell were found out. The depletion in the Os 5d5/2 and Pt 5d5/2,3/2 states was revealed for Pt-Os nanoalloys.
This unusual result disagrees with the known d-band theory and indicates that there is a gain of non-d conduction electron counts at one or both sites. Mixed conductivity may exist in such Pt-Os nanoalloy that may be responsible for a manifestation of new physical properties of this binary system .
To enhance the biological effects of radiation damage in cancerous cells, we present an alternative approach to the use of gold nanoparticles (AuNP), focusing on the synthesis and characterization of highly monodisperse, spherical radioactive gold nanoparticles 198AuNP. The size of the AuNP size was optimized with the help of Geant4/TOPAS particle scattering simulations, and energy deposition per nm3 per decay for varying radii (2–10 nm) was evaluated. This work is the foundation for ongoing experimental work to evaluate cell death induced by 198AuNP which aims for the use of radioactive gold nanoparticles in cancer treatment.
Large temperature gradients inherent to additive manufacturing (AM) processes induce large residual stress (RS) in the final part. Because RS can influence the tribological properties, this study focuses on the relationship between wear sliding properties and RS in IN718 coatings. Such coatings were deposited with a Laser metal deposition (LMD) machine using two different scanning strategies.
The wear resistance and RS state were investigated after surface milling. RS were measured before and after wear tests on a reciprocating sliding test apparatus.
Two different X-ray diffraction techniques were employed to measure the surface and subsurface state RS: Laboratory Energy Dispersive X-ray Diffraction (LEDXD) and Synchrotron X-ray Energy Dispersive Diffraction (SXEDD). Due to the milling process, the coatings show similar depth distributions of RS from 22 to 92 μm depth, but exhibit different magnitudes depending on the scanning strategy used. Reciprocating sliding wear tests induced high compressive residual stresses that erased the initial RS state, and a similar wear behavior was observed in the two samples. These samples possess similar texture and grain morphology. This demonstrates that the influence of RS on wear resistance is a second-order effect. Nevertheless, it was observed that RS can still impact the wear performance at the early testing stages of the repaired parts.
The Stolt Rotterdam tanker ship, filled with nitric acid, was unloading at the Krefeld-Uerdingen terminal on the Rhine River in November 2001. Nitric acid ran out of the stainless steel tanks into the ship's hull and damaged the structural steel. The ship then caught fire and sank at the terminal. Large quantities of nitrogen oxides were emitted, which drifted towards a residential area. Additionally, a mixture of acid and water was introduced into the Rhine River. The area became hazardous to people and the natural environment; however, the imminent danger for the residents and the environment was reduced because of the protective measures against pollution and the good teamwork between local authorities, fire brigades and the Bayer AG company. The acid was drained off of the ship using a controlled discharge of the acid into the river. Through the use of this measure, the ship was salvaged, limiting the pollution to the area and removing the health hazards to the people and the environment. After the ship was salvaged, the river police, along with assistance from the BAM Federal Institute for Materials Research and Testing, impounded the ship and selected corroded parts for further examination. Some of these components have been examined in detail by the BAM. These material investigations contributed to the elucidation of the origin of the leak in the floor panel. The cause of damage was deemed to be a result of a construction flaw at the enamelled valve on the load and discharge pipes.
The results from the comparative corrosion testing using the original structural steel and 60% acid revealed that the valves began to leak at least 8 h prior to the incident at the terminal.
This study investigates the mechanochemical reactions between AgBr 3-picolylamine and 4-picolylamine. The use of different stoichiometry ratios of the reagents allows [(AgBr)(n-pica)]n and [(AgBr)2(n-pica)]n to be obtained, and we report the new structures of [(AgBr)2(3-pica)]n and [(AgBr)2(4-pica)]n which are characterized by the presence of the following: (a) infinite inorganic chains, (b) silver atom coordinated only by bromide atoms and (c) argentophilic interactions. Furthermore, we studied the interconversion of [(AgBr)(n-pica)]n/[(AgBr)2(n-pica)]n by mechanochemical and thermal properties. The in situ experiments suggest that [(AgBr)(3-pica)]n is kinetically favoured while [(AgBr)2(3-pica)]n is converted into [(AgBr)(3-pica)]n only with a high excess of the ligand. Finally, the liquid nature of the ligands is not sufficient to assist the grinding process, and the complete reaction is observed with the addition of a small quantity of acetonitrile.
Bei der thermografischen Prüfung von Widerstandspunktschweißverbindungen wird die Emissivität der Fügeverbindung bisher als Störgröße angesehen und – wenn möglich – unterdrückt. Nachfolgende Arbeit untersucht, ob eine für diese Prüfung nutzbare Korrelation zwischen Emissionsgrad des Kappenabdrucks und Schweißpunktdurchmesser besteht. Dazu werden 60 Blechproben in drei praxisrelevanten Materialkombinationen und mit unterschiedlicher Anbindungsqualität vermessen. Über die thermografische Grundgleichung kann die Emissivität bestimmt werden. Der Punktdurchmesser wird zerstörend ermittelt. Die Ergebnisse zeigen eine Korrelation der beiden Messwerte auf, die umso höher ausfällt, je geringer die Emissivität des Grundwerkstoffes ist. Abschließend wird ein Ausblick auf die Verwendbarkeit dieses Zusammenhangs in der thermografischen Schweißpunktprüfung gegeben.
The progress in X-ray detector electronics (sensitivity and speed) allows meanwhile fast single photon detection by a matrix detector. Combined photon counting and energy discrimination is implemented in the electronic circuit of each detector pixel. The company XCounter developed detectors based on CdTe single crystals, which can be tiled to larger areas and have a pixel size of 100ìm. The largest area available in beginning of 2014 is 50x75 mm². These detectors have very promising properties, which make them very suitable for NDT applications:
1. A CdTe attenuation layer of 750 µm thickness allows efficient X-ray detection up to ca. 300 keV. In counting mode only photon noise is important; no other detector noise sources need to be considered. There is no Offset signal without radiation.
2. Each of the detector pixels has two energy thresholds. These can be used for dual energy imaging for materials separation. Also the suppression of scattered radiation by energy thresholding will improve the image contrast sensitivity. First experiments will be presented which demonstrate the advantages of this new detector technology over the conventional charge integrating detectors.
A challenge is the development of a modified detector calibration procedure, which becomes critical at longer exposure times.
Concepts for digital image evaluation are presented for Computed Radiography (CR) and Digital Detector Arrays (DDAs) used for weld inspection. The precise DDA calibration yields an extra ordinary increase of contrast sensitivity up to 10 times in relation to film radiography. Restrictions in spatial resolution caused by pixel size of the DDA are compensated by increased contrast sensitivity. First CR standards were published in 2005 to support the application of phosphor imaging plates in lieu of X-ray film, but they need already a revision based on experiences reported by many users. One of the key concepts is the usage of signal-to-noise (SNR) measurements as equivalent to the optical density of film and film system class. The contrast sensitivity, measured by IQI visibility, depends on three essential parameters: The basic spatial resolution (SRb) of the radiographic image, the achieved signal-to-noise ratio (SNR) and the specific contrast (µeff - effective attenuation coefficient). Knowing these 3 parameters for the given exposure condition, inspected material and monitor viewing condition permits the calculation of the just visible IQI element. Furthermore, this enables the optimization of exposure conditions. The new ISO/FDIS 17636-2 describes the practice for digital radiography with CR and DDAs. It considers the first time compensation principles, derived from the three essential parameters. The consequences are described.
Spherical lignin nanoparticles (LNPs) fabricated via nanoprecipitation of dissolved lignin are among the most attractive biomass-derived nanomaterials. Despite various studies exploring the methods to improve the uniformity of LNPs or seeking more application opportunities for LNPs, little attention has been given to the fundamental aspects of the solvent effects on the intrinsic properties of LNPs. In this study, we employed a variety of experimental techniques and molecular dynamics (MD) simulations to investigate the solvent effects on the intrinsic properties of LNPs. The LNPs were prepared from softwood Kraft lignin (SKL) using the binary solvents of aqueous acetone or aqueous tetrahydrofuran (THF) via nanoprecipitation. The internal morphology, porosity, and mechanical properties of the LNPs were analyzed with electron tomography (ET), small-angle X-ray scattering (SAXS), atomic force microscopy (AFM), and intermodulation AFM (ImAFM). We found that aqueous acetone resulted in smaller LNPs with higher uniformity compared to aqueous THF, mainly ascribing to stronger solvent−lignin interactions as suggested by MD simulation results and confirmed with aqueous 1,4-dioxane (DXN) and aqueous dimethyl sulfoxide (DMSO).
More importantly, we report that both LNPs were compact particles with relatively homogeneous density distribution and very low porosity in the internal structure. The stiffness of the particles was independent of the size, and the Young’s modulus was in the range of 0.3−4 GPa. Overall, the fundamental understandings of LNPs gained in this study are essential for the design of LNPs with optimal performance in applications.
Heterogeneous Oxysulfide@Fluoride Core/ Shell Nanocrystals for Upconversion-Based Nanothermometry
(2022)
Lanthanide (Ln3+)-doped upconversion nanoparticles (UCNPs) often suffer from weak luminescence, especially when their sizes are ultrasmall (less than 10 nm). Enhancing the upconversion luminescence (UCL) efficiency of ultrasmall UCNPs has remained a challenge that must be undertaken if any practical applications are to be envisaged. Herein, we present a Ln3+-doped oxysulfide@fluoride core/shell heterostructure which shows efficient UCL properties under 980nm excitation and good stability in solution. Through epitaxial heterogeneous growth, a ∼4 nm optically inert β-NaYF4 shell was coated onto ∼5 nm ultrasmall Gd2O2S:20%Yb,1%Tm. These Gd2O2S:20%Yb,1%Tm@NaYF4 core/shell UCNPs exhibit a more than 800-fold increase in UCL intensity compared to the unprotected core, a 180-fold increase in luminescence decay time of the 3H4 → 3H6 Tm3+ transition from 5 to 900 μs, and an upconversion quantum yield (UCQY) of 0.76% at an excitation power density of 155 W/cm2. Likewise, Gd2O2S:20%Yb,2%Er@NaYF4 core/shell UCNPs show a nearly 5000-fold
increase of their UCL intensity compared to the Gd2O2S:20%Yb,2%Er core and a maximum UCQY of 0.61%. In the Yb/Er core−shell UCNP system, the observed variation of luminescence intensity ratio seems to originate from a change in lattice strain as the temperature is elevated. For nanothermometry applications, the thermal sensitivities based on thermally coupled levels are estimated for both Yb/Tm and Yb/Er doped Gd2O2S@NaYF4 core/shell UCNPs.
The synthesis and optimization of superior and eco-friendly sorbents for Pb(II) pose a great challenge in the field of water treatment. The sorbent was developed by introducing graphene oxide (GO) into the matrix of polyvinyl formaldehyde (PVF) foam. The immobilization of GO in PVF results in significant increase in the maximum adsorption capacity (Qt) of GO powder for Pb(II), from ≈800 to ≈1730 mg g−1 in the case of GO/PVF foam. As compared with GO powder in Pb(II) aqueous solutions, PVF matrix keeps GO sheets stable without any agglomeration. The large surface area of GO sheet allows the abundant oxygenated functional groups on its surface to participate effectively in the Pb(II) adsorption process, leading to the huge increase of the Qt. Adsorption isotherms and kinetic studies indicated that the sorption process of Pb(II) on GO/PVF was done on heterogenous surface by ion-exchange reaction. The GO/PVF foam showed an excellent reusability for more than 10 cycles with almost the same efficiency and without any significant change in its physical properties.
In granular soils, long-term cyclically loaded structures can lead to an accumulation of irreversible strain by forming closed convective cells in the upper layer of the bedding. The size of the convective cell, its formation and grain migration inside this closed volume have been studied with reference to different stiffness of the embedded structure and different maximum force amplitudes applied at the head of the structure.
This relation was experimentally investigated by applying a cyclic lateral force to a scaled flexible vertical element embedded in a dry granular soil. The model was monitored with a camera in order to derive the displacement field by means of the PIV technique. Furthermore, the ratcheting convective cell was also simulated with DEM with the aim of extracting some micromechanical information. The main results regarded the different development, shape and size of the convection cell and the surface settlements.
Growth of vehicle traffic density can be observed in many countries all over the world. This accretion is caused by world-wide population growth on the one hand, but also by increasing freight volumes and, thus, freight transports on the streets on the other hand.
This increased exposure becomes more and more of a problem for the civil infrastructure such as bridges. Many of these bridges are nowadays stressed to their limits by higher loads than they were originally designed for and/or operating times beyond the initially predicted life span. This raises questions about structural safety and lifetime prediction, of course, and therefore illustrates the need for accurate structural monitoring.
Since the lifetime of bridge structures is primarily influenced by their traffic loading, an accurate identification of load configurations over the whole length of a structure is most desirable.
In this paper, a method for vehicle load identification is proposed. It involves Bayesian Analysis and (quasi-)static importance functions in order to estimate vehicle positions, velocities and weights. The structure is modeled with finite elements in order to generate model predictions for different load configurations. The model predictions are compared to the actual measured data to identify the most probable loading configuration for that measurement. This involves the use of enhanced Monte Carlo simulations such as MCMC to reduce the computational effort. The measured data from different kinds of sensors can (and should) be combined for accuracy gain – in this case a combination of measured displacements and inclinations.
Since the measurements take place over some time during the passage of the vehicle, these estimations are carried out for several time instants for which the estimation is carried out. The advantage of using Bayesian Updating Method is the embodied learning effect leading to an improvement of the estimation when adding new information in a new calculation step.
Using the estimates for the loading conditions of a bridge structure as well as measurements of the structural responses, Bayesian analysis is again used in order to estimate localized structural parameters such as Young's modulus or Moments of Inertia in form of probability density functions yielding most probable values for the parameters.
Considering the difficulties for load identification close to the support poles of the bridge and therefore for the proposed structural parameter identification procedure, it is clear that this problem is ill posed. Bayesian regularization methods also have proven to be very effective when handling ill posed problems.
In this work, a probabilistic framework for identification of traffic loads on concrete Bridge structures is presented using data from a FE structural model in combination with a finite volume approach for traffic load modelling. The identification approach uses Bayesian Inference to identify traffic loads from measured sensor data from travelling load experiments performed at BAM. The work focuses on the load identification part of the Framework utilizing global structural response measurements only. The obtained information on traffic loads can be forwarded to further analysis such as fatigue and structure state estimation or model updating.
Polymers with intrinsic microporosity are promising candidates for the active separation layer in gas separation membranes. Here, the vibrational density of states (VDOS) for PIM-1, the prototypical polymer with intrinsic microporosity, is investigated by means of inelastic neutron scattering. The results are compared to data measured for a more conventional high-performance polyimide used in gas separation membranes (Matrimid). The measured data show the characteristic low frequency excess contribution to VDOS above the Debye sound wave level, generally known as the Boson peak in glass-forming materials. In comparison to the Boson peak of Matrimid, that of PIM-1 is shifted to lower frequencies. This shift is discussed considering the microporous, sponge-like structure of PIM-1 as providing a higher compressibility at the molecular scale than for conventional polymers. For an annealed PIM-1 sample, the Boson peak shifts to higher frequencies in comparison to the un-annealed sample. These changes in the VDOS of the annealed PIM-1 sample are related to changes in the microporous structure as confirmed by X-ray scattering.
Inelastic incoherent neutron time-of flight scattering was employed to measure the low frequency density of states for a series of addition polynorbornenes with bulky side groups. The rigid main chain in combination with the bulky side groups give rise to a microporosity of these polymers in the solid state. The microporosity characterized by the BET surfaces area varies systematically in the considered series. Such materials have some possible application as active separation layer in gas separation membranes.
All investigated materials show excess contributions to the Debye type density of states characteristic for glasses known as Boson peak. The maximum position of the Boson peak shifts to lower frequency values with increasing microporosity. Data for PIM-1 and Matrimid included for comparison are in good agreement to this dependency. This result supports the sound wave interpretation of the Boson peak.
The microscopic diffusion and the low frequency density of states (VDOS) of PIM-EATB(CH3) are investigated by inelastic and quasi-elastic neutron scattering where also the demethylated counterpart of PIM-EA-TB(H2) is considered. These intrinsic microporous polymers are characterized by large BET surface area values of several hundred m2/g and pore sizes between 0.5 and 2 nm. Detailed comparison is made to the archetype of polymers of intrinsic microporosity, PIM-1, and polynorbornenes also bearing a microporosity. Due to the wavelength of neutrons, the diffusion and vibrations can be addressed on microscopic length and time scales. From the inelastic neutron scattering experiments the low frequency density of states (VDOS) is estimated which shows excess contributions to the Debye-type VDOS known as Boson peak. It was found that the maximum frequency of the Boson peak decreases with increasing microporosity characterized by the BET surface area. However, besides the BET surface area, additional factors such as the backbone stiffness govern the maximum frequency of the Boson peak. Further the mean squared displacement related to microscopic motions was estimated from elastic fixed window scans. At temperatures above 175 K, the mean squared displacement PIM-EA-TB(CH3) is higher than that for the demethylated counterpart PIM-EA-TB(H2). The additional contribution found for PIM-EATB(CH3) is ascribed to the rotation of the methyl group in this polymer because the only difference between the two structures is that PIM-EA-TB(CH3) has methyl groups where PIM-EA-TB(H2) has none. A detailed comparison of the molecular dynamics is also made to that of PIM-1 and the microporous polynorbornene PTCNSi1. The manuscript focuses on the importance of vibrations and the localized molecular mobility characterized by the microscopic diffusion on the gas Transport in polymeric separation membranes. In the frame of the random gate model localized fluctuations can open or close bottlenecks between pores to enable the diffusion of gas molecules.
In this article we present inelastic neutron scattering (INS) experiments on different systems of confined glass-formers. The aim of these experiments is to study the influence of spatial restriction on the microscopic dynamics related to the glass transition. Such results could be helpful for the detection of a currently speculated cooperativity length of the glass transition. The glass-forming component is either a molecular liquid or a polymer. The confining matrices are `hard' (silica glass, silicon) or `soft' (microemulsion droplets). For some experiments the confining structure could be spatially oriented. Except for the soft confinement the naïvely expected acceleration effect could only be found at low temperatures where INS experiments are difficult because of the long relaxation times. A clear effect of confinement could be observed for the glass-typical low energy vibrations (boson peak). This effect seems to be completely different for soft and hard confinement. Surprisingly, the experiments on oriented nanopores did not show any signs of an anisotropy of the dynamics.
Quasielastic neutron scattering by employing a combination of time-of-flight and backscattering techniques is carried out to explore the molecular mobility of a polymer of intrinsic microporosity (PIM-1) at microscopic time scales in comparison with a high-performance polyimide. Molecular fluctuations can change the structure of the temporary network of micropores and open or close pathways for gas molecules. Therefore, the investigation might help to understand the selectivity of PIMs in gas separation processes. The performed neutron scattering experiments provide evidence for a low-temperature relaxation process, which was assigned to methyl group rotation. This methyl group rotation was analyzed in terms of jump diffusion in a three-fold potential. The analysis results in a fraction of methyl groups which are immobilized. For PIM-1 it was found that the fraction of immobilized methyl groups decreases with increasing temperature up to 350 K. At higher temperatures the number of immobilized methyl group increases gain due to an underlying relaxation process. This motional process on a somewhat larger length scale might lead to a reversible structural rearrangement which partially hinders the strongly localized methyl group rotation. In addition, it was found that the activation energy for the methyl group rotation for PIM-1 and the polyimide is significantly higher than for conventional polymers.
In this article, results on the microscopic dynamics of a low-molecular glass former and a polymer confined in nanoporous silica obtained by inelastic neutron scattering are presented. By combining time-of-flight spectroscopy and backscattering spectroscopy we are able to cover a large dynamical range, from the low-frequency vibrations to the relaxation. The most prominent effect was observed on the boson peak in the vibrational spectrum. A strong reduction of the modes at lowest frequencies could be observed in both cases. The main effect on the relaxation is a broadening for the salol system. For the polymeric system a difference of the confinement influence on the methyl-group rotation and the relaxation can be detected from a first qualitative interpretation of the data.
Ceramic parts possessing an ordered porosity were produced for the first time by powder-based three-dimensional printing of a preceramic polymer followed by pyrolysis in an inert atmosphere. The main parameters involved in the process were investigated, and the precision of the printed and ceramized parts was assessed by means of scanning electron microscopy and micro computed tomography. The influence of two different printing solvents was investigated and the use of a mixture of 1-hexanol and hexylacetate in particular allowed the production of parts with a relative density of 80% both in the polymeric and in the ceramic state. The mixing of a cross-linking catalyst directly with the printing liquid greatly simplified the process, minimizing the necessity of preprocessing the starting powder. Three-dimensional printing of a preceramic polymer not containing any inert or active fillers was proved to be a feasible, convenient and precise process for the production of porous ceramic possessing a complex, ordered structure, such as stretch-dominated lattices.
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.
Highly porous (>60% open porosity) glass–ceramic scaffolds with remarkable mechanical properties (compression strength of ~15 MPa) were produced by indirect 3D printing. Precursor glass powders were printed into 3D ordered structures and then heat treated to sinter and develop crystalline phases. The final glass–ceramic contained a β-spodumene solid solution together with a secondary phase of lithium disilicate.
The precision of the printed geometry and the density of the struts in the scaffold depended on several processing parameters (e.g. powder size and flowability, layer thickness) and were improved by increasing the binder saturation and drying time. Two types of powders with different particle size distribution (PSD) and flowability were used. Powders with a larger PSD, could be processed within a wider range of printing parameters due to their good flowability; however, the printing precision and the struts density were lower compared to the scaffolds printed using the powder in a smaller average PSD.
The microstructure of an apatite-wollastonite (code name AP40) glass-ceramic is analyzed in this study by combining 2D microscopy, phase analysis, X-ray absorption and synchrotron X-ray refraction computed tomography (XCT and SXRCT, respectively). It is shown that this combination provides a useful toolbox to characterize the global microstructure in a wide scale range, from sub-micrometer to millimeter. The material displays a complex microstructure comprising a glassy matrix with embedded fluorapatite and wollastonite small crystals. In this matrix, large (up to 200 μm) spike-shaped structures are distributed. Such microstructural features are oriented around a central sphere, thereby forming a structure resembling a sea urchin. A unique feature of SXRCT, in contrast to XCT, is that internal interfaces are visualized; this allows one to show the 3D distribution of these urchins with exceptionally good contrast. Furthermore, it is revealed that the spike-shaped structures are not single crystals, but rather composed of sub-micrometric crystals, which are identified as fluorapatite and diopside phases by SEM-EDX analysis.
As humanity contemplates manned missions to Mars, strategies need to be developed for the design and operation of hospitable environments to safely work in space for years. The supply of spare parts for repair and replacement of lost equipment will be one key need, but in-space manufacturing remains the only option for a timely supply. With high flexibility in design and the ability to manufacture ready-to-use components directly from a computeraided model, additive manufacturing (AM) technologies appear extremely attractive. For the manufacturing of metal parts, laser-beam melting is the most widely used AM process. However, the handling of metal powders in the absence of gravity is one prerequisite for its successful application in space. A gas flow throughout the powder bed is successfully applied to compensate for missing gravitational forces in microgravity experiments. This so-called gas-flow-assisted powder deposition is based on a porous Building platform acting as a filter for the fixation of metal particles in a gas flow driven by a pressure difference maintained by a vacuum pump.
An improved method of powder 3D printing leading to dense ceramic parts is presented. The application of powder-based binder jetting 3D printing technologies to technical ceramics is generally limited by the low packing density of the powder and by the need to use a flowable powder. With layer-wise slurry deposition, it is, however, possible to deposit powder beds with high particle packing and furthermore using submicron powders. This method was combined with the binder jetting technology to develop a novel process, named LSD-print. By means of LSD-print, a submicron Al2O3 powder could be processed to produce samples with a density comparable with that of standard pressed samples, both in the green state and after sintering.
Additive manufacturing of SiSiC by layerwise slurry deposition and binder jetting (LSD-print)
(2019)
The current work presents for the first time results on the Additive Manufacturing of SiSiC complex parts based on the Layerwise Slurry Deposition (LSD) process. This technology allows to deposit highly packed powder layers by spreading a ceramic slurry and drying. The capillary forces acting during the process are responsible for the dense powder packing and the good joining between layers. The LSD process can be combined with binder jetting to print 2D cross-sections of an object in each successive layer, thus forming a 3D part. This process is named LSD-print.
By LSD-print and silicon infiltration, SiSiC parts with complex geometries and features down to 1mm and an aspect ratio up to 4:1 could be demonstrated.
The density and morphology were investigated for a large number of samples. Furthermore, the density and the mechanical properties, measured by ball-on-three-balls method, were in all three building directions close to isostatic pressed references.
Purpose – This paper aims to present an additive manufacturing-based approach in which a new strategy for a thermally activated local melting and material flow, which results in densification of printed structures, is introduced.
Design/methodology/approach – For enabling this self-organized relaxation of printed objects by the viscous flow of material, two interconnected structures are printed simultaneously in one printing process, namely, Structure A actually representing the three dimensional object to be built and Structure B acting as a material reservoir for infiltrating Structure A. In an additional process step, subsequent to the printing job, an increase in the objects’ temperature results in the melting of the material reservoir B and infiltration of structure A.
Findings – A thermally activated local melting of the polymethylsilsesquioxane results in densification of the printed structures and the local formation of structures with minimum surface area.
Originality/value – The present work introduces an approach for the local relaxation of printed three-dimensional structures by the viscous flow of the printed material, without the loss of structural integrity of the structure itself. This approach is not restricted only to the materials used, but also offers a more general strategy for printing dense structures with a surface finish far beyond the volumetric resolution of the 3D printing process.
The direct ink writing of an ink composed of a preceramic polymer and fillers was used to produce hardystonite (Ca2Zn-Si2O7) bioceramic scaffolds. Suitable formulations were developed for the extrusion of fine filaments (350 µm diameter) through a nozzle. The preceramic polymer was employed with the double purpose of contributing to the rheology of the ink by increasing its viscosity and of forming the hardystonite phase upon heat treatment by reacting with the fillers. A control of the rheology is essential when spanning features have to be produced, and therefore the main rheological characteristics of the inks were measured (flow curves, dynamic oscillation tests, viscosity recovery tests) and compared to models reported in the literature. Highly porous scaffolds (up to 80% total porosity) were produced and heat treated in air or in nitrogen atmosphere. The influence of the heat-treatment atmosphere on the morphology, crystalline phase assemblage, and compressive strength of the scaffolds was investigated.
Future lunar exploration can benefit greatly from In-Situ Resource Utilization. Accordingly, the in-Situ Resource Utilization approach highlights the need for detailed analysis of lunar regolith. In this study, JSC-2A Simulant was studied regarding its sintering and melting behaviour using Differential Thermal Analysis under ambient and inert conditions. The minerals at the crystalline peaks were determined using X-Ray Diffraction analysis.
Moreover, melting droplet shape and wetting behaviour of pressed regolith samples of different particle size distributions were studied by Hot Stage Microscopy technique. Hot Stage Microscopy experiments were performed at different heating rates under ambient conditions. Bloating effects within the solidified samples were then qualitatively examined by X-ray tomography. Lastly, the optimization of processing strategies for the Additive Manufacturing of lunar regolith is discussed.
Silicate bioceramics possess an excellent bioactivity; however, shaping them into complex geometries is still challenging. Therefore, this paper aims to present a new strategy for the shaping of a bioglass-ceramic with controlled geometry and properties starting from a glass powder combined with a preceramic polymer, i.e. a silicon resin, and reactive fillers. The powder-based three-dimensional (3D)-printing of wollastonite (CaSiO3)-based silicate bioceramic parts was demonstrated in this work. The resin plays a dual role, as it not only acts as a non-sacrificial binder for the filler powders in the printing process but it also reacts with the fillers to generate the desired bioceramic phases. The mechanical and physical properties, i.e. ball-on-three-balls test, density, porosity and morphology, were evaluated in 3D-printed discs. These samples possessed a total porosity around 64 vol% and a biaxial flexural strength around 6 MPa. The raw materials used in this work also enabled the 3D-printing of scaffolds possessing a designed multi-scale porosity, suitable bioceramic phase assemblage and a compressive strength of 1 MPa (for cylindrical scaffolds with total porosity ~80 vol%). Solubility in TRIS/HCl and in vitro assays, i.e. viability, cytotoxicity and apoptosis assays, were also performed. In vitro tests indicated good cell viability and no cytotoxicity effect on the cells.
Additive manufacturing (AM) is a technology which has the potential not only to change the way of conventional industrial manufacturing processes, adding material instead of subtracting, but also to create entirely new production and business strategies. Since about three decades, AM technologies have been used to fabricate prototypes or models mostly from polymeric or metallic materials. Recently, products have been introduced into the market that cannot be produced in another way than additively. Ceramic materials are, however, not easy to process by AM technologies, as their processing requirements (in terms of feedstock and/or sintering) are very challenging. On the other hand, it can be expected that AM technologies, once successful, will have an extraordinary impact on the industrial production of ceramic components and, moreover, will open for ceramics new uses and new markets.
Tapes, cast by blade deposition of a lithium aluminosilicate glass slurry, were sintered using a YAG-fiber laser, with the aim of finding suitable parameters for an additive manufacturing process based on layer-wise slurry deposition and selective laser densification. The influence of the laser parameters (output power and scan velocity) on the sintering was evaluated, by scanning electron microscopy and by X-ray diffraction, on the basis of the quality of the processed layer. Well densified samples could be obtained only in a small window of values for the output power and the scan velocity. The measurement of the width of a set of single scanned lines allowed also to estimate the minimum resolution of the system along the layer plane.
Elastomers are usually mechanically reinforced with high loadings of carbon black (CB) to achieve the properties demanded; high amounts of mineral flame retardants are used to fulfill fire safety requirements. In this study, multilayer graphene (MLG), a nanoparticle made of only 10 graphene sheets, is applied in low loadings, 3 parts per hundred rubber (phr) to reduce the total amount of filler or boost performance in hydrogenated acrylonitrilebutadiene rubber (HNBR). In the HNBR/MLG nanocomposites, 3 phr MLG replaced 15 phr CB, 3 phr aluminum trihydroxide (ATH), or 15 phr CB + 3 phr ATH. The nanocomposites were prepared via master batch by ultrasonically assisted solution mixing and subsequent conventional two-roll milling. A comprehensive study is presented, illustrating the impact of MLG on curing and mechanical properties; e.g. replacing 2.5 phr ATH with 3 phr MLG increased the Young's modulus by over 60% and hardness by 10%, while improving flame retardancy, and reducing the total heat evolved by 10%. MLG is a multifunctional filler, as demonstrated by various enhancements in terms of the mechanical and flame retardancy properties of the rubber composites.
In this study, multicomponent flame retardant systems, consisting of Ammonium polyphosphate (APP), aluminum trihydroxide (ATH), and polyaniline (PANI), were used in ethylene propylene diene monomer (EPDM) rubber. The multicomponent system was designed to improve flame retardancy and the mechanical properties of the rubber compounds, while simultaneously reducing the amount of filler. PANI was applied at low loadings (7 phr) and combined with the phosphorous APP (21 phr) and the mineral flame retardant ATH (50 phr). A comprehensive study of six EPDM rubbers was carried out by systematically varying the fillers to explain the impact of multicomponent flame retardant systems on mechanical properties. The six EPDM materials were investigated via the UL 94, limiting oxygen index (LOI), FMVSS 302, glow wire tests, and the cone calorimeter, showing that multicomponent flame retardant systems led to improved fire performance.
In cone calorimeter tests the EPDM/APP/ATH/PANI composite reduced the maximum average rate of heat emission (MARHE) to 142 kW·m-2, a value 50% lower than that for the unfilled EPDM rubber. Furthermore, the amount of phosphorus in the residues was quantified and the mode of action of the phosphorous flame retardant APP was explained. The data from the cone calorimeter were used to determine the protective layer effect of the multicomponent flame retardant systems in the EPDM compounds.
Ethylene propylene diene monomer (EPDM) Rubbers with the flame retardants tris(2-ethylhexyl)phosphate, ammonium polyphosphate, polyaniline, and aluminum trihydroxide were prepared and analyzed in this study. The homogenous dispersion of the fillers in the rubber matrix was confirmed by scanning electron microscope. To investigate the interplay of the different flame retardants, the flame retardants were varied systematically. The comprehensive study sought combinations of flame retardants that allow high loadings of flame retardants without deterioration of the physical and mechanical properties of the EPDM rubber. The eight EPDM rubbers were investigated via thermogravimetric analysis and pyrolysis gas chromatography coupled with a mass spectrometer (Py GC/MS) to investigate the potential synergistic effects. In the Py-GC/MS experiments, 27 pyrolysis products were identified. Furthermore, UL 94, limiting oxygen index, FMVSS 302, glow wire tests, and cone calorimeter tests were carried out. In the cone calorimeter test the EPDM rubbers R-1AP and R-1/2P achieved an increase in residue at flameout of 76% and a reduction in total heat evolved of about 35%. Furthermore, the compounds R-1AP and R-1/2P achieved a reduction in MARHE to about 150 kW m−1, a reduction of over 50% compared to the unprotected rubber R.
The impact of polyaniline in phosphorus flame retardant ethylene-propylene-diene-rubber (EPDM)
(2019)
Usually elastomers are loaded with high amounts of flame retardants to fulfill fire safety requirements. In this study the potential char precursor polyaniline (PANI) and the established fire retardant pentaerythritol (PER) were implemented in ethylene-propylene-diene monomer rubber (EPDM). PANI and PER were used in low loadings (7 phr) and combined with two phosphorous flame retardants, Ammonium polyphosphate (APP) and a piperazine-pyrophosphate/phosphoric acid compound (FP), to boost their performance. A comprehensive study is presented, explaining the impact of PANI on curing and mechanical properties, including compensation for the plasticizer-like effect of APP in EPDM, and improved flame retardancy. In the cone calorimeter test, the combination of EPDM/FP/PANI reduced the effective heat of combustion by 20%. All nine EPDM rubber compounds were investigated with the LOI and UL 94 tests, cone calorimeter, FMVSS 302 and glow wire testing to quantify fire performance. The PANI containing EPDM rubbers, EPDM/APP/PANI and EPDM/FP/PANI outperformed the corresponding PER containing, EPDM/APP/PER and EPDM/FP/PER rubbers in various tests. Moreover, the study investigated the impact of PANI and PER on the mode of action of the phosphorus species and showed that the addition of PANI increased the amount of phosphorus in the condensed phase. To receive a broader understanding of the flame retardant mode of action of PANI in combination with APP and FP, calculations were carried out to estimate the impact of PANI on the protective layer effect.
Major accidents in the process industry often lead to the release of light or dense gases, which can mean a thread to employees, local residents or to the environment. Possible scenarios are therefore analyzed and evaluated in advance for approval issues. There is a trend, where simple empirical models are being replaced with more complex numerical models. Gaussian dispersion models or models based on dimensional analysis approaches are for example, increasingly replaced by CFD simulations. The main reason for this is the potentially higher accuracy. However, usually scenarios using sharp parameter values are calculated, since comprehensive consideration of parameter distributions via Monte Carlo or Latin Hypercube Sampling fails due to the numerical effort. This includes the risk that the influence of uncertainties on the simulation results is not taken into account. Response surface methods offer an alternative, with which the CFD problem can be mapped onto an algebraic surrogate model. If this is sufficiently precise, parameter sampling can also be carried out with the surrogate as well, as shown in some publications. Previous investigations only demonstrated the basic principle using trivial dispersion models. In this paper two realistic CFD simulations from the plant safety area are considered: VOC emissions from a storage tank and near-ground dense gas emissions. The entire procedure of response surface determination and parameter studies was automated and parallelized for high-performance-computing, and is carried out on the underlying CFD grids. For the CFD simulations as well as for all visualizations, the commercial software ANSYS CFX and the open source software OpenFOAM were used. The aim of this paper is to demonstrate the method using industry-relevant applications as well as to show how this can be used in practical engineering applications. The quality of surrogate modeling, the numerical effort and advantages that can result from the procedure are discussed as well as advantages which may result from taking parameter uncertainties into account in safety studies.
In this paper, we investigate the evaporation mass flow originating from spills of gas-oline. Large spills of gasoline may form during partial or complete roof sinkings or inthe case of perforations at various deck fittings at external floating roof tanks usedfor the storage. Additionally, spills may form in the retention area in the case of leak-ages at pipes or at the hull. The aim is to predict the order of magnitude of real-scaleevaporation mass flow. The determined evaporation mass flows will be used in arelated project as input values for subsequent dispersion modeling in the vicinity ofthe tanks. This is relevant for questions of fire and explosion protection as well as forenvironmental protection aspects in tank farms or refineries, which use externalfloating roof tanks. The measurements presented in this paper were compared withpredictions by empirical models and investigations of evaporations from small floorspills, round-bottom flask, or from Petri dishes published in the literature. The maingoal of this paper is to test the applicability of empirical models to provide reasonableevaporation mass flows as input for CFD dispersion simulations.