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Due to the growing environmental awareness worldwide, containment provisions for CO2 emissions in mobility systems and increasing performance requirements the demands on mechanical systems and their materials continuously rise. These high demands require the implementation of new technical approaches, for example of light-weight strategies in automotive powertrains, and directly raise questions about the suitability of the most promising technical solution. Two basic parameters, the surface hardness of the tooth flanks and the core fatigue strength of the tooth root, illustrate exemplarily increasing demands on material grades used for gear wheels in automotive powertrains. In addition to light-weight strategies, a reduction in friction and an increase of the fatigue lifetime are two other major development directions to strive the mentioned targets. It is clear that any kind of solution must show an equal application profile, preferably an improvement, compared to the state-of- the-art solutions. For tribological systems, the following paths may offer lower friction and higher load carrying capabilities: 1. Alternative base oils and additives (such as esters, polyglycols), 2. Thin film coatings (e.g. DLC) and/or 3. Novel steel metallurgies. In previous investigations on the slip-rolling resistance of thin film coatings (a-C, ta-C, Zr(C,N)) the substrates were mainly made of the bearing steels 100Cr6H and Cronidur 30. Applying contact pressures of up to P0max = 2.9 GPa (FN = 2,000 N), the samples were tested up to 10 million load cycles in endurance tests. The aim of the present work is to broaden the research by varying the input parameters. Newly developed engine oil mixtures, high performance thin film coatings and alternative steel solutions are intensively investigated in highly stressed slip-rolling contacts at lubricant temperatures of 120°C. Specifically, in using new steel metallurgies, i.e. the high toughness and high strength steels V300 and NC310YW (Aubert & Duval) as well as CSS-42L (Latrobe Specialty Steel Company), in combination with thin film coatings, even if they compete in the uncoated state, the Hertzian contact pressures could be increased up to P0max = 4.2 GPa (FN = 5,000 N) without any surface failures of coating or substrate. It was shown that selected thin film coatings can minimize the wear rates down to nearly ‘zero-wear’ in highly stressed contacts [Woy08] [Woy11]. In addition, the studies revealed not only the high potential in slip-rolling resistance, but also a possible friction reduction down to 0.047 by use of uncoated steels with increased toughness. Compared to steels like 100Cr6H and Cronidur 30 this means a reduction in friction of approximately 40% under identical testing conditions. Different test series with newly developed base oil-additive formulations were investigated with specific emphasis on the frictional behavior of selected bio-no-tox EP/AW additives and friction modifiers. Additional influencing factors like the structural and surface conditions of the steels/coatings before and after the tests were analyzed by means of REM, EDX, XRD and TEM.
OEMs perceive diamond-like carbon (DLC) coatings as part of a strategy for low frictional tribosystems. Especially the automotive industry anticipates a benefit in applying such coatings in association with the lightweight construction of mechanical parts, for instance in gears and engines. In previous investigations it was shown, that DLC, amorphous carbon (a-C) and tetragonal amorphous carbon (ta-C) coatings can be slip-rolling resistant at least up to ten million load cycles at Hertzian contact pressures P0max of 2.9 GPa lubricated by engine oil at 120°C, Further improvements in load carrying capacity up to P0mean of 2.62 GPa (FN= 5,000 N) were achieved with alternative, available Steel metallurgies as Substrates for thin film coatings. Additional factors, such as influences of the lubrication on the surface chemistry (additives and base oils), wear and friction behavior were investigated.
Leichtbaustrategien im Antriebsstrang erhöhen durch Downsizing die Hertz’schen Kontaktpressungen und die mechanischen Lasten. Dadurch müssen neben wälzbeständigen Stählen auch dazu passende reibungsmindernde Konzepte gefunden werden, in der vorliegenden Arbeit wurden alternative, hoch zähe Stähle mit einer Wälzbeständigkeit bis Pomax = 4,2 GPa untersucht, welche mit geeigneten Grundöl- und Additivkombinationen die Reibungszahlen herunter auf 0,025 reduzieren konnten. Diese alternativen Stahllegierungen erlauben nicht nur an der Zahnflanke sehr hohe Kontaktpressungen, sie bieten außerdem entsprechende Zähigkeits- und Festigkeitseigenschaften für den Zahnfuß. In vorangegangenen Untersuchungen wurde eine Vielzahl verschiedener Dünnschichten auf ihre Überrollbeständigkeit unter Extrembeanspruchungen validiert. Allerdings zeigte sich bei den meisten Dünnschichten ein Qualitätsunterschied von Charge zu Charge. Unter Verwendung verschiedener organischer, metallorganischer und anorganischer Additive konnten, sich daran anschließende Versuche, vielversprechende Ergebnisse erzielt werden. Sämtliche Versuche unter extremen Beanspruchungen wurden bei +120°C Öltemperatur auf Zwei-Scheiben-Tribometern vom Typ AMSLER und 2Disk von Optimol Instruments unter Misch-/Grenzreibungsbedingungen durchgeführt und die tribologischen Eigenschaften der neuartigen, unbeschichteten Stähle und in Relation zu leistungsstarken DLC-/ZrCN Dünnschichten gesetzt.
The slip-rolling resistances of hard and stiff thin films under high Hertzian contact pressures can be improved by optimizing the 'coating/substrate systems'. It is known from former investigations that the so-called 'egg-shell' effect is no general hindrance for high slip-rolling resistance of thin hard coatings. The coating stability depends more on specific deposition process and coating/substrate interface design. In this article it is experimentally shown, that pure amorphous carbon thin films with hardness between 15 and 63 GPa can be slip-rolling resistant several million load cycles under a maximum Hertzian contact pressures of up to 3.0 GPa. Whereas all coatings were stable up to 10 million load cycles in paraffin oil at room temperature, reduced coating lifetime was found in SAE 0W-30 engine oil at 120°C. It was shown how the coating hardness and the initial coating surface roughness influence the running-in process and coating lifetime. No clear correlation between coating hardness and coating lifetime could be observed, but friction coefficients seem to be reduced with higher coating hardness. Very low friction down to ~0.03 in unmodified engine oils was found for the hardest ta-C film.------------------------------------------------------------------------------------------------------------------------------------------------
Die Wälzbeständigkeit von harten und steifen Dünnschichten unter hohen Hertzschen Kontaktpressungen kann durch die Optimierung des 'Beschichtung/Substrat Systems' deutlich verbessert werden. Aus vorangegangenen Untersuchungen ist bekannt, dass der so genannte 'Eierschaleneffekt' kein generelles Hindernis für eine hohe Wälzbeständigkeit für harte Dünnschichten darstellen muss. Die Stabilität der Beschichtungen hängt vielmehr von dem spezifischen Prozessparametern und dem Schicht/Substrat Grenzflächendesign ab. In diesem Artikel wird experimentell nachgewiesen, dass reine amorphe Kohlenstoffdünnschichten mit Härtewerten zwischen 15 und 63 GPa für mehrere Millionen Lastzyklen unter maximalen Hertzschen Kontaktpressungen bis 3.0 GPa überrollbeständig sein können. Während alle Beschichtungen bis 10 Millionen Lastzyklen in Paraffinöl bei Raumtemperatur keine Defekte aufweisen wurde unter Verwendung eines SAE 0W-30 Motorenöls bei 120°C eine Verringerung der Überrollbeständigkeit nachgewiesen. Es wurde nachgewiesen, wie die Schichthärte und ursprüngliche Oberflächenrauheit der Beschichtung den Einlaufprozess und die Lebensdauer beeinflussen. Es konnte keine offensichtliche Korrelation zwischen Schichthärte und Lebensdauer festgestellt werden, allerdings wurde eine scheinbare Reduktion des Reibwertes mit steigender Schichthärte beobachtet werden. Dabei zeigte die härteste ta-C Schicht unter Verwendung des Motorenöls sehr geringe Reibwerte mit ~0.03.
Time-optimized 15N quantitative NMR (qNMR) is described for the precise determination of Lewis and Brønsted site concentrations per gram catalyst, enabling a measurement time reduction of more than a factor of 10. The proof-of-principle is demonstrated for amorphous aluminum hydroxide fluorides with their tunable Lewis to Brønsted functionalities and relevance to highly active and selective heterogeneous catalysis using pyridine as a widely accepted probe molecule for Lewis and Brønsted sites. Two different Lewis centers were found, and reliable site concentrations down to the micromole per gram region can be determined. Furthermore, 1H{15N} REDOR NMR for the acid proton at the Brønsted site yields a distance of the 15N atom of bonded pyridine to this acid proton of (0.112 ± 0.002) nm, such that fast motion/diffusion of the Brønsted site-bonded pyridine at the surface can be excluded.
This study reports three new crystalline aluminum isopropoxide oxide fluorides with molar ratios of Al:F equal to 1:1 and 1:1.25. These are the first three representatives isolated without the incorporation of external donor molecules. Compound 1 Al4F4(µ4-O)(µ-O'Pr)5[H(O'Pr)2] contains a tetranuclear unit consisting of two different five fold coordinated AlFO4-units, with F exclusively in the terminal position. Compound 2, Al4F4(µ4-O)(µ-O'Pr)5[H(O'Pr)2]·Al5F5(µ5-O)(µ-O'Pr)8, contains both a tetranuclear unit (as in 1) and a pentanuclear Al-unit. Al-atoms in the latter are five- and six fold coordinated. Compound 3, Al16F20(µ4-O)4(µ-O'Pr)20·2('PrOH), exhibits a slightly higher fluorination degree and contains an oligomeric chain of four F-linked tetranuclear Al-units. In addition to X-ray structure analysis, compound 1 was characterized by different solid state MAS NMR techniques, including 27Al triple quantum MAS NMR and 1H, 1H→13C CP, 19F and 27Al MAS NMR. On the basis of the collected data, a reliable decomposition of 27Al single pulse MAS NMR spectra and an unambiguous assignment of the resonances to the respective structural AlFO4-units are given. The new crystalline aluminum isopropoxide oxide fluorides are direct evidence of the fluorolytic sol–gel mechanism previously discussed.
A series of crystalline aluminum hydroxy fluorides in cubic pyrochlore structure AlFx(OH)3-x·H2O with variable F-content x were investigated by solid-state NMR by applying different magnetic fields up to 21.1 T. Distinguishable octahedral species AlFx(OH)6-x (x = 1-6) were identified in the crystalline aluminum hydroxy fluorides. The subsequent analysis of the highfield 27Al MAS NMR data allows the derivation of the trend analysis graphs giving correlations between the 27Al chemical shifts and the quadrupolar frequencies and the F-content x in AlFx(OH)6-x. Clear trends were obtained for both, which are, along with the 19F MAS chemical-shift trend analysis presented earlier, valuable tools for the interpretation of MAS NMR spectra of amorphous AlFx(OX)3-x compounds (X = H, alkyl). Following the dehydration of the pyrochlores by solid-state NMR eventually reveals a remarkable influence of the incorporated solvent molecules (H2O) on the 19F chemical shift. On that basis, a new chemical-shift trend analysis for 19F chemical shifts in correlation with x in AlFx(OH)6-x units for proton-poor substances (in the Al, F, O, H system) was determined. By using this correlation, high-surface AlF3 has a mean bulk Al:F ratio similar to that found for ACF, namely, AlF2.8(O/OH)0.2.
Aluminas resulting from sols prepared via a modified Yoldas procedure were studied with differential thermal analysis (DTA), differential thermal gravimetrie (DTG), 27Al nuclear magnetic resonance (27Al MAS NMR) and X-ray diffraction (XRD) concerning their thermal properties, aluminum speciation and phase content.
Hydrolysis of aluminum-sec-butoxide in aluminum nitrate solutions allowed to prepare stable sols with varying NO3-/Al molar ratios, solids contents and pH values. Resulting sols contained different aluminum species including also Al13 polycations. Sol preparation conditions also determined aluminum speciation in solid products obtained after thermal treatments of gels obtained from these sols. Al13 polycations and AlO5 species were found to play an important role for thermally induced transformation from amorphous products via eta-Al2O3 to alpha-Al2O3. Intermediately formed eta-Al2O3 promotes the phase transformation to alpha-Al2O3.
Stick-slip and wear behavior of ceramic and polymer materials under reciprocating sliding conditions
(2013)
In many technical applications not only the actual friction coefficient is of importance, but rather the constancy relevant for the functionality. Due to inconstant ffiction values, positioning processes can be substantially influenced as well as vibrations can be induced. The appearance of this tribological effect, named stick-slip, depends on different factors such as sliding speed, relative humidity and ambient temperature occurring primarily after long operating periods. Beside ambient conditions the choice of materials in contact is the main influencing factor of an inconstant coefficient of friction during operating. Certain polymers are well known for their stick-slip tendencies in technical applications. These are on the one hand different modifications of PTFE (polytetrafluoroethylene) reinforced with glass fibers, bronze or graphite and on the other hand thermoplastics such as PE (polyester) or Pf (polyimide). The difference between static and dynamic values of the ffiction force is decisive for stick-slip phenomena. Furthermore, the stick-slip tendency of polymers strongly depends on the elastic material properties. Main softening material areas, which can be found in the contact, represent particularly vulnerable areas. The high friction value in the contact area decreases in most cases by increasing sliding speeds. However, beside polymers ceramic materials can also offer tendencies to stick-slip motion. Klaffke et al. already investigated the influence of ceramic materials on the stick-slip behavior in.
Highly concentrated or loaded contacts in powertrain and gear applications offer significant weight savings in C02 emissions. Today, thin film coatings, alternative base oils and new additives are populär as working fields and strategies of OEMs to realize low friction tribosystems. Especially the automotive industry anticipates environmental and performance benefits in applying light-weight construction of mechanical parts, for instance in gears and engines. Light-weight strategies increase the contact stresses above 2.14 GPa (or FZG load stage 14) due to the reduction of component sizes. These demands directly raise questions about the suitability of the most promising technical solution. Alternative steels with improved mechanical properties, i.e. toughness values, which offer low coefficients of friction, optimal resistance to high contact pressure and potential to apply low friction surface coatings representing a valid alternative to conventional gear steels. Traditional bearing and gear steels, such as 100Cr6 (SAE E52100) or 16MnCr5 (1.7131) have reached their mechanical limits at contact pressures above FZG load stage 14.
Nowadays, diamond-like carbon (DLC) coatings are mainly used in many low loaded applications such as in machine tools, computer devices and many more.
Especially the automotive industry anticipates a benefit in applying such coatings in association with the lightweight construction of mechanical parts, for instance in gear components.
The ulterior motive is a global performance increase regarding environmental impact and power efficiency.
In recent years, the slip-rolling resistance of DLC, a-C and ta-C thin film coatings was improved considerably.
In view of the mechanical application of thin film coatings, there is still room for improvements.
It was experimentally shown, that a-C and ta-C coatings can be slip-rolling resistant at room temperature in unaddivated paraffin oil up to ten million cycles under Hertzian contact pressures up to P0max = 2.9 GPa.
Typically, the prime coated steel substrates were made of the hardened and tempered steels 100Cr6H and Cronidur 30.
The aim of the work this to overtake these results, i.e. at higher maximum Hertzian pressures up to P0max = 4.2 GPa.
Under such extreme conditions, it is necessary to choose special steels to avoid the failure of the substrate and to permit a higher load carrying capacity of the coating-substrate-system.
In consideration of the increased substrate properties, two high toughness spring steels and an ultra-high toughness aerospace steel were tested on a twin disc tribometer of the Amsler type as well as on an Optimol TwinDisc test rig under mixed/boundary conditions.
Different factors such as residual stresses of the substrate, influences of the lubrication, and wear behaviour were investigated.
The respective results are presented here.
Stick-slip and wear behavior of ceramic and polymer materials under reciprocating sliding conditions
(2013)
Coatings for slip-rolling
(2014)
Diamond-like carbon (DLC) coatings are perceived as part of a strategy for low frictional tribosystems. Especially the automotive industry anticipates a benefit in applying such coatings in association with the lightweight construction of mechanical parts, for instance in gear and engine components. Therefore, in previous investigations amorphous carbon (a-C) and tetragonal amorphous carbon (ta-C) coatings were inspected. For up to ten million cycles at Hertzian contact pressures P0max of 2.9 GPa it was shown that these coatings are slip-rolling resistant not only at room temperature in the presence of unaddivated paraffin oil, but also up to 120 °C oil temperature. The steel substrates in this investigation were made of the hardened and tempered steels 100Cr6H and Cronidur 30. The aim of the current work is manifold. The Hertzian contact pressures should be increased up to P0max of 4.2 GPa by using new steel metallurgies as substrates for thin film coatings. These steel metallurgies are also assessed, if they can compete as uncoated couples. Two high toughness spring steels and an ultra-high toughness aerospace steel were tested in a twin disc tribometer of the Amsler type as well as in an Optimol 2Disk test rig under mixed/boundary conditions in a factory fill SAE 0W-30 engine oil. Different factors such as influences of the lubrication, surface chemistry and wear behaviour were investigated.
This study presents for the first time an NMR spectroscopic characterization of the room and high temperature phases of (NH4)3InF6 using 19F and 115In as probe nuclei. The reversible phase transition to the cubic phase at 353 K was followed by MAS NMR in situ. Static NMR experiments of the room temperature phase and MAS NMR experiments of the high temperature phase allowed the determination of the NMR parameters of both nuclei. Finally, the scalar In–F coupling, rarely observed in solid state NMR, is evidenced in both room and high temperature phases of (NH4)3InF6, and measured in the high temperature phase.
Performance and efficiency of piezo-electric stick-slip actuators are dependent on the waveform of the electrical actuation of the piezo-stack. This paper compares between a conventional saw-tooth actuation with two waveforms that feature softer acceleration in order to minimize the duration of the slip-phase. It is shown that the proposed waveforms increase both maximum mechanical output power (by 43%) and overall efficiency (by 25%) of the examined actuator.
The inevitable increase of torque or load, because of lightweight approaches, pushes the oil-film temperatures on the teeth flanks of gears above 200°C, and requires alloys with higher strength and toughness properties. Furthermore, the real temperature on surfaces during the physical vapor deposition (PVD) or chemical vapor deposition (CVD) of thin films can exceed the annealing temperature of the state-of-the-art bearing and gear materials, such as AISI 52100 (1.3505), 16MnCr5 (1.7131), 21NiCrMo (1.6523), and 30CrMoV9 (1.7707). Such trends call for slip-rolling-resistant, alternative alloys suited for contact stresses above P0max of >2.2 GPa. The tribological profile under slip-rolling conditions at 120°C in a factory engine oil (SAE 0W-30, ACEA A3/B4, ν120°C = 5.33 mPa, HTHS150°C = 3.0 mPa) until 10 × 106 load cycles between P0max of 2.25 GPa to 3.92 GPa of uncoated 100Cr6 (1.3505, PBQ), 102Cr6 (1.2067), Cronidur 30 (1.4108, DESU), 45SiCrMo6 (1.8062, CVEM), 40SiNiCrMo1 [vacuum arc remelting (VAR)], CSS-42L (AMS 5932, vacuum induction melting (VIM)-VAR, and carburized), 36NiCrMoV1-5-7 (CAB), ASP2012 (ASP), and 20MnCr5 (1.7131, carburized) was established in twin disk machines (Amsler-type and 2Disk). The present benchmark illuminates the tribological impact of uncoated bearing steels in comparison to uncoated alternative steel alloys on friction, wear and slip-rolling resistance, as well as load carrying capacity. Iron-based steel alloyed with silicon or molybdenum reduces alloying costs and avoids thermo-chemical treatments. This benchmark suggests considering an extension to fracture toughness from hardness and strength as a relevant property for slip-rolling alloys. If slip-rolling resistant, the wear rates of the metallurgical different steels were more or less within one order of magnitude, but the influence of increasing contact stresses on the tribological profile differed significantly.
The approaching CO2 targets have now enforced automotive OEMs to engage R&D efforts also in powertrain to reduce friction, increase lifetime properties, and load carrying capacities of running systems. Martensitic steels such as 36NiCrMoV1-5-7 have a great potential to be used in automotive powertrain applications due to its favorable mechanical properties. In order to realize lightweight strategies, it is essential that steels with improved fracture toughness values and higher annealing temperatures with regard to higher contact pressures and possible thin film coating application be considered. State-of-the-art steels, like 16MnCr5, 21NiCrMo, 30CrMoV9, and 100Cr6 are not able to sustain a further increase in torque or load during operating time as well as annealing effects under higher oil or deposition temperatures. Therefore, the recent research on the slip-rolling resistance, frictional, and wear behavior of steels such as 36NiCrMoV1-5-7, Cronidur 30 (AMS 5898), 20MnCr5 (SAE 4820 or 5120), and 100Cr6H (SAE E52100) showed that possible lean alloying concept alternatives with promising performance characteristics are already available.
The very strong Lewis acid aluminium chlorofluo-ride (ACF) was loaded with anhydrous HF. The interactionbetween the surface of the catalyst and HF was investigatedusing a variety of characterization methods, which revealed he formation of polyfluorides. Moreover, the reactivity ofthe HF-loaded ACF towards the hydrofluorination of alkyneswas studied.
Stepping piezoelectric actuators based on the stick-slip effect inherently make use of a friction contact between strator and rotor. This contact defines not only the actuator's performance but also is prone to wear and tear. For broad use, the actuator has to be able to perform around 1 million strokes. To assess the actuator's performance in terms of force, speed, mechanical output, electrical input, and long-term stability under different load- and environmental conditions, as well as different friction partners, a dedicated test-bed for a LSPA30µXS motor by Cedrat Technologies has been set up.
Mechanochemically synthesized metal–organic Framework material HKUST-1 in combination with acrylonitrile butadiene styrene polymer was used to form a polymer metal–organic framework composite material by a simple extruder.
This composite filament was used for 3D printing. Xray diffraction measurements were used to prove the homogeneous distribution of the metal–organic framework in the polymer on a centimeter scale, whereas X-ray Absorption Edge Tomography using a synchrotron radiation source was able to evaluate the 3D distribution of the metal–organic framework material both in the filament and the resultant printed sample with a resolution of a few lm. Our very first data indicate that, apart from a few clusters having significantly higher Cu concentration, HKUST-1 is distributed homogeneously down to the 100 lm length scale in both polymer bulk materials in the form of clusters with a size of a few lm. Absorption Edge Tomography in combination with data fusion also allows for the calculation of the metal–organic framework amount located on the external polymer surface.
The acid catalyzed solgel type synthesis of polyorganosiloxane core-shell nanoparticles with removable PDMS core in aqueous dispersion leads to the inherent formation of a bimodal size distribution with smaller spheres having approximately 26 nm radii and larger nanoparticles with 60 nm in radius. The origin of the self-organized bimodality is investigated and finally attributed to a combination of stabilization of the growing particles due to i) a miniemulsion-type stabilization by the ultrahydrophobe PDMS and ii) by surface co-stabilization by the employed surfactant. The significant influence of temperature, pH, stirrer speed and amount of the surfactant on the particle sizes allows for the design and fine-tuning of different nanoparticles sizes and distributions.
Ananion-dopedaluminiumchlorofluoride AlCl0.1F2.8(OTeF5)0.1(ACF-teflate) was synthesized.The material contains pentafluor-oorthotellurate(teflate)groups, which mimic fluoride ions electronically, but are sterically more demanding. They are embedded into the amorphous structure. The latter was studied by PDF analysis, EXAFS data and MAS NMR spectroscopy. The mesoporous powder is a Lewis superacid, and ATR-IR spectra of adsorbed CD3CN reveal a blue-shift of the adsorption band by73 cm-1, which is larger than the shift for SbF5. Remarkably,ACF-teflate catalyzes dehydrofluorination reactions of mono-fluoroalkanes to yield olefins in C6D6. In these cases,no Friedel-Crafts products were formed.
Thermo-Desorption Gas Chromatography-Mass Spectrometry (TD-GC-MS) was used to investigate the thermal degradation of two different polyurethanes (PU). PU samples were heated at different heating rates and the desorbed products were collected in a cold injection system and thereafter submitted to GC-MS. Prospects and limitations of the detection and quantification of semi-volatile degradation products were investigated. A temperature dependent PU depolymerization was
found at temperatures above 200 °C proved by an increasing release of 1,4-butanediol and methylene diphenyl diisocyanate (MDI) representing the main building blocks of both polymers. Their release was monitored quantitatively based on external calibration with authentic compounds. Size Exclusion Chromatography (SEC) of the residues obtained after thermodesorption confirmed the initial competitive degradation mechanism indicating an equilibrium of crosslinking and depolymerization as previously suggested. Matrix-Assisted Laser Desorption Ionization (MALDI) mass spectrometry of SEC fractions of thermally degraded PUs provided additional hints on degradation mechanism.
The chemical state of antimony and vanadium species in municipal solid waste incineration bottom ash
(2023)
Due to the large quantity as residual mineral waste, municipal solid waste incineration - bottom ash (MSWI-BA) is an interesting secondary raw material that can be utilized for road construction. However, leaching of chloride, sulfate and potentially hazardous heavy metals from MSWSI-BA into the environment may cause problems in utilization of it in civil engineering. In a previous study, we performed a long-term leaching test of MSWI-BA in a lysimeter for almost six years to investigate the efficiency of the treatment process on the release of hazardous substances. While concentrations of chloride, sulfate and the majority of the heavy metals started to decrease rapidly with progressive liquid-to-solid ratio (L/S), the ecotoxic hazardous elements antimony (Sb) and vanadium (V) behaved differently. To unravel these unusual release behaviors and the oxyanion-formation of Sb and V we will apply HERFD-XANES spectroscopy to analyze their chemical state.
The use of ashes from municipal solid waste incineration as secondary building materials is an important pillar for the circular economy in Germany. However, leaching of potential toxic elements from these materials must be at environmentally acceptable levels. Normally, a three-month ageing period immobilizes most hazardous heavy metals, but antimony (Sb) and vanadium (V) showed previously unusual leaching. In order to clarify the mechanisms, we analyzed the Sb and V species in various bottom and fly ashes from municipal waste incineration by XANES spectroscopy. Antimony oxidizes from Sb(+ III) species used as flame retardants in plastics to Sb(+ V) compounds during waste incineration. However, owing to the similarity of different Sb(+ V) compound in the Sb K- and L-edge XANES spectra, it was not possible to accurately identify an exact Sb(+ V) species. Moreover, V is mainly present as oxidation state + V compound in the analyzed ashes. However, the coarse and magnetic fraction of the bottom ashes contain larger amounts of V(+ III) and V(+ IV) compounds which might enter the waste incineration from vanadium carbide containing steel tools. Thus, Sb and V could be critical potential toxic elements in secondary building materials and long-term monitoring of the release should be taken into account in the future.