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Paper des Monats
- ja (7)
The chapter gives a brief introduction to (nano)compositecomposite materials having the focus on polymer-based nanocomposites. The different dimensionalities of nanoparticles are introduced, along with their distribution in the matrix.
Different application fields of polymer-based nanocomposites, like flame retardancy, filled rubbers, nanofilled thermosets and thermoplastics, separation membranes and nanodielectrics, are considered in greater detail.
Alkali-silica reaction (ASR) is a chemical reaction within concrete which can lead over time to cracking and spalling. Due to the complexity of the problem, it still causes damage to concrete constructions worldwide.
The publication aims to illustrate the interdisciplinary research of the German Federal Institute for Materials Research and Testing (BAM) within the last 20 years, considering all aspects of ASR topics from the macro to the micro level. First, methods for characterization and assessment of ASR risks and reaction products used at BAM are explained and classified in the international context. Subsequently the added value of the research approach by combining different, preferably nondestructive, methods across all scales is explained using specific examples from a variety of research projects. Aspects covered range from the development of new test-setups to assess aggregate reactivity, to analysis of microstructure and reaction products using microscopical, spectroscopical and X-ray methods, to the development of a testing methodology for existing concrete pavements including in-depth analysis of the visual damage indicator and the de-icing salt input using innovative testing techniques. Finally, research regarding a novel avoidance strategy that makes use of internal hydrophobization of the concrete mix is presented.
Protein adsorption at the air–water interface is a serious problem in cryogenic electron microscopy (cryoEM) as it restricts particle orientations in the vitrified ice-film and promotes protein denaturation. To address this issue, the preparation of a graphene-based modified support film for coverage of conventional holey carbon transmission electron microscopy (TEM) grids is presented. The chemical modification of graphene sheets enables the universal covalent anchoring of unmodified proteins via inherent surface-exposed lysine or cysteine residues in a one-step reaction. Langmuir–Blodgett (LB) trough approach is applied for deposition of functionalized graphene sheets onto commercially available holey carbon TEM grids. The application of the modified TEM grids in single particle analysis (SPA) shows high protein binding to the surface of the graphene-based support film. Suitability for high resolution structure determination is confirmed by SPA of apoferritin. Prevention of protein denaturation at the air–water interface and improvement of particle orientations is shown using human 20S proteasome, demonstrating the potential of the support film for structural biology.
Carbons doped with iron and nitrogen (Fe–N–Cs) are highly promising electrocatalysts for energy conversion reactions in the oxygen, nitrogen and carbon cycles. Containing no platinum group metals, they nevertheless compete with platinum-based catalysts in crucial fuel cell reactions, such as oxygen reduction in acid. Yet deployment of Fe–N–Cs in fuel cells requires also a flow-enhancing pore structure, and a scalable synthesis procedure – a rarely-met combination of requirements. We now report such a simple synthesis of over 10 g of an Fe–N–C catalyst with high activity towards oxygen reduction in acid. Atomically-dispersed Fe–N4 active sites were designed orthogonally and simultaneously with hierarchical micro-, meso- and macroporosity, by exploiting a dual role of magnesium ions during pyrolysis. Combining the “active site imprinting” and “self-templating” strategies in a single novel magnesium iminodiacetate precursor yielded a catalyst with high specific surface area (SSA > 1600 m2 g−1), a flow-enhancing hierarchical porosity, and high relative abundance of the most desirable D1-type Fe–N4 sites (43%, by Mössbauer spectroscopy at 4.2 K). Despite the relatively low iron contents, the catalysts feature halfwave potentials up to 0.70 V vs. RHE at pH 1 and a mass activity of 1.22 A g−1 at 0.8 V vs. RHE in RDE experiments. Thanks to the simple and scalable synthesis, this active and stable catalyst may serve as a workhorse in academic and industrial research into atomically-dispersed ORR electrocatalysis.
Cementitious materials are frequently applied in environments in which they are exposed to acid attack, e.g., in sewer systems, biogas plants, and agricultural/food-related industries. Alkali-activated materials (AAMs) have repeatedly been shown to exhibit a remarkably high resistance against attack by organic and inorganic acids and, thus, are promising candidates for the construction and the repair of acid-exposed structures. However, the reaction mechanisms and processes affecting the acid resistance of AAMs have just recently begun to be understood in more detail. The present contribution synthesises these advances and outlines potentially fruitful avenues of research. The interaction between AAMs and acids proceeds in a multistep process wherein different aspects of deterioration extend to different depths, complicating the overall determination of acid resistance. Partly due to this indistinct definition of the ‘depth of corrosion’, the effects of the composition of AAMs on their acid resistance cannot be unambiguously identified to date. Important parallels exist between the deterioration of low-Ca AAMs and the weathering/corrosion of minerals and glasses (dissolution-reprecipitation mechanism). Additional research requirements relate to the deterioration mechanism of high-Ca AAMs; how the character of the corroded layer influences the rate of deterioration; the effects of shrinkage and the bond between AAMs and substrates.
Natural zeolite clinoptilolite CLIN with a framework ratio of Si/Al ≥ 4 containing mainly potassium and calcium ions in its internal channel system was used as a starting material. The acidic HCLIN catalysts were prepared under soft conditions avoiding the use of environmental less benign mineral acids. The starting material was ion exchanged using a 0.2 M aqueous ammonium nitrate solution at a temperature 80 ◦C for 2 h. The obtained NH4CLIN was converted into the acid HCLIN catalyst by calcination at 300–600 ◦C. The obtained samples were characterized by XRD, FTIR, SEM/TEM, AAS, and EDX element mapping. The state of aluminium and silicon was studied by 27Al- and 29SiMAS NMR spectroscopy. The textural properties of the catalysts were investigated by nitrogen adsorption and desorption measurements. The Brønsted acidity of the HCLIN catalysts was studied by temperature-programmed decomposition of the exchanged ammonium ions releasing ammonia as well as 1H MAS NMR, {1H–27Al} Trapdor, and {1H–27Al}
Redor experiments. The strongly agglomerated samples were crystalline and thermally stable up to >500 ◦C. Although a part of the clinoptilolite framework is maintained up to 600 ◦C, a loss of crystallinity is already observed starting from 450 ◦C. The specific surface areas of the starting CLIN and ammonium exchanged NH4CLIN are low with ca. 26 m2/g. The pores are nearly blocked by the exchangeable cations located in the zeolite pores. The thermal decomposition of the ammonium ions by calcination at 400 ◦C causes an opening of the pore entrances and a markable increase in the specific micropore area and micropore volume to ca. 163 m2/g and 0.07 cm3/g, respectively. It decreases with further rising calcination temperature indicating some structural loss. The catalysts show a broad distribution of Brønsted acid sites (BS) ranging from weak to strong sites as indicated the
thermal decomposition of exchanged ammonium ions (TPDA). The ammonium ion decomposition leaving BS, i.e., H+ located at Al–O–Si framework bridges, starts at ≥250 ◦C. A part of the Brønsted sites is lost after calcination specifically at 500 ◦C. It is related to the formation of penta-coordinated aluminium at the expense of tetrahedral framework aluminium. The Brønsted sites are partially recreated after repeated ammonium ion exchange. The catalytic performance of the acidic HCLIN
catalysts was tested in the etherification of glycerol as a green renewable resource with different C1 -C4 alcohols. The catalysts are highly active in the etherification of glycerol, especially with alcohols containing the branched, tertiary alkyl groups. Highest activity is observed with the soft activated catalyst HCLIN300 (300 ◦C, temperature holding time: 1 min). A total of 78% conversion of glycerol to mono and di ether were achieved with tert-butanol at 140 ◦C after 4 h of reaction.
The mono- and di-ether selectivity were 75% and 25%, respectively. The catalyst can be reused.
ADAMTS4-specific MR-probe to assess aortic aneurysms in vivo using synthetic peptide libraries
(2022)
The incidence of abdominal aortic aneurysms (AAAs) has substantially increased during the last 20 years and their rupture remains the third most common cause of sudden death in the cardiovascular field after myocardial infarction and stroke. The only established clinical parameter to assess AAAs is based on the aneurysm size. Novel biomarkers are needed to improve the assessment of the risk of rupture. ADAMTS4 (A Disintegrin And Metalloproteinase with ThromboSpondin motifs 4) is a strongly upregulated proteoglycan cleaving enzyme in the unstable course of AAAs. In the screening of a one-bead-one-compound library against ADAMTS4, a low-molecular-weight cyclic peptide is discovered with favorable properties for in vivo molecular magnetic resonance imaging applications. After identification and characterization, it’s potential is evaluated in an AAA mouse model. The ADAMTS4-specific probe enables the in vivo imaging-based prediction of aneurysm expansion and rupture.
Flexible organic crystals (elastic and plastic) are important materials for optical waveguides, tunable optoelectronic devices, and photonic integrated circuits. Here, we present highly elastic organic crystals of a Schiff base, 1-((E)-(2,5-dichlorophenylimino)methyl)naphthalen-2-ol (1), and an azine molecule, 2,4-dibromo-6-((E)-((E)-(2,6-dichlorobenzylidene)hydrazono)methyl)phenol (2). These microcrystals are highly flexible under external mechanical force, both in the macroscopic and the microscopic regimes. The mechanical flexibility of these crystals arises as a result of weak and dispersive C−H⋅⋅⋅Cl, Cl⋅⋅⋅Cl, Br⋅⋅⋅Br, and π⋅⋅⋅π stacking interactions. Singly and doubly-bent geometries were achieved from their straight shape by a micromechanical approach using the AFM cantilever tip. Crystals of molecules 1 and 2 display a bright-green and red fluorescence (FL), respectively, and selective reabsorption of a part of their FL band. Crystals 1 and 2 exhibit optical-path-dependent low loss emissions at the termini of crystal in their straight and even in extremely bent geometries. Interestingly, the excitation position-dependent optical modes appear in both linear and bent waveguides of crystals 1 and 2, confirming their light-trapping ability.
Both essential aspects of the surface of solid matter, its morphology and chemistry, are studied traditionally at BAM starting in the 60’s with different cyclical research focus areas, mostly related either to applicative research or method development. In the recent years, the focus has shifted almost exclusively to the nano-analytics of advanced materials such as complex nanoparticles, (ultra)thin films/coatings, nanocomposites, 2D materials, energy materials, etc. This is also the reason why BAM has established recently the new Competence Center nano@BAM (www.bam.de/Navigation/DE/Themen/Material/Nanotechnologie/sichere-nanomaterialien.html) with the five sub-fields nanoCharacterisation, nanoMaterial, nanoSafety, nanoData and nanoTechnology. The link to the BAM central guidelines to the safety in technology and chemistry is given by the development of reference products such as reference measurement procedures, reference (nano)materials, and newly reference data sets. Thus, an internationally well-networked group in surface analysis has been established @BAM, with regular contributions to integral analytical characterization with metrological and standardization background.
Examples of newly developed methodical approaches will be given with an emphasis on correlative nano-analysis of morphology and chemistry of nanomaterials. Correlative imaging by STEM-in-SEM with high-resolution SEM and EDX, and further with AFM or the new technique TKD (Transmission Kikuchi Diffraction) will be explained on various examples of nanostructures, both as starting materials and embedded/functionalized nanoparticles in products. The unique analytical benefits of the Auger electron probe as a veritable nano-tool for surface chemistry will be highlighted. The panoply of advanced surface characterization methods @BAM is completed by discussing examples of hybrid analysis of the bulk of nanomaterials by X-ray Spectroscopy with the highest surface-sensitive methods X-ray Photoelectron Spectroscopy (XPS) and Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS). Particularly for the analysis of the surface chemistry of nanostructures, such as the completeness of the shells of core-shell nanoparticles or in-depth and lateral gradients of chemistry within mesoporous thin layers, the latter methods are inherent.
Other special developments like approaches for the quantitative determination of the roughness of particle surface by electron microscopy or for the quantitative determination of the porosity of thin mesoporous layers by electron probe microanalysis (EPMA) with SEM will be presented.
Immunoanalytical Techniques, i.e., antibody-based analytical methods, have been used for decades in clinical diagnostics. What makes them attractive for other fields of application is their short time-to-result and high sensitivity. Microplate-based assays such as ELISA have been adopted early in environmental and food analysis. Yet, to make immunoassays even faster, more sensitive, robust, and, most desirable, portable, advanced materials, sometimes developed for other purposes, can be profitably used to achieve these goals. Materials can be novel labels, e.g., chemical or particle labels, such as fluorophores or nanoparticles. Carrier particles, such as magnetic or polymer beads, make it possible to adopt the assays to meso- or microfluidic set-ups and encoding them opens the path to multiplex analysis. Specialty electrodes can enable for higher sensitivity in electrochemical detection. All this broadens the scope of application and lowers effort and cost for analysis at the point-of-need.
With the increasing production of renewable energy and concomitant depletion of fossil resources, the demand for efficient water splitting electrocatalysts continues to grow. Iridium (Ir) and iridium oxides (IrOₓ) are currently the most promising candidates for an efficient oxygen evolution reaction (OER) in acidic medium, which remains the bottleneck in water electrolysis. Yet, the extremely high costs for Ir hamper a widespread production of hydrogen (H₂) on an industrial scale. Herein, the authors report a concept for the synthesis of electrode coatings with template-controlled mesoporosity surface-modified with highly active Ir species. The improved utilization of noble metal species relies on the synthesis of soft-templated metal oxide supports and a subsequent shape-conformal deposition of Ir species via atomic layer deposition (ALD) at two different reaction temperatures. The study reveals that a minimum Ir content in the mesoporous titania-based support is mandatory to provide a sufficient electrical bulk conductivity. After ALD, a significantly enhanced OER activity results in dependency of the ALD cycle number and temperature. The most active developed electrocatalyst film achieves an outstanding mass-specific activity of 2622 mA mg(Ir)⁻¹ at 1.60 V(RHE) in a rotating-disc electrode (RDE) setup at 25 °C using 0.5 m H₂SO₄ as a supporting electrolyte.
minimum explosion concentration (MEC) and limiting oxygen concentration (LOC) in our recent works. This work further studies the reasonability and reliability of the alternative method experimentally and theoretically. Six different dust samples were tested via a 20-L spherical explosion chamber. The experimental results showed that the data of MEC and LOC determined by using the alternative and the standardized methods are in good agreement. The minimum flame propagation velocity (Sf) and the corresponding maximum combustion duration time (tc) were found at its MEC and LOC, suggesting that the theoretical analysis can well explain all the experimental data. It is the first time to study the theoretical basis of the explosion criterion, thus helping to improve our understandings of dust explosion characteristics, and to amend the explosion criterion in future test standards.
The incorporation of nanoscale particles into elastomers enable a boost in performance and/or a distinct reduction of conventional filler loadings due to their high surface to volume ratio. 2D layered nanoparticles like graphene and graphene-related materials provide a great potential as effective fillers in rubber, especially by enhancing mechanical and barrier properties. The type and properties of the nanoparticles, their interface and the elastomeric matrix materials influence the technical behavior, and therefore the potential application fields of such rubber nanocomposites. Especially crucial for the efficiency of the nanofiller, however, is its best possible incorporation into the elastomer. The dispersing of nanoparticles without agglomerates usually constitutes a challenge when using conventional two-roll milling or internal mixing. Academic approaches for highly dispersed nanocomposites solve this problem but are often energy and time consuming with no feasible scale up possibility. Therefore, an ultrasonic assisted NR latex premixing process was established to produce highly filled masterbatches, enabling the main processing with conventional rubber processing techniques.
Two carbon-based nanoparticles with similar specific surface areas were investigated and incorporated in natural rubber as nanocomposites: A commercially available multilayer graphene (MLG) and a nanoscale carbon black (nCB). The mentioned premixed masterbatches were further processed to nanocomposites by the addition of matrix NR, two-roll milling, and hot pressing (vulcanization). By this procedure an increase in Young’s modulus of 157% (MLG) and 71% (nCB) could be obtained at a concentration level of 3 phr. As anisotropic material behavior was observable for the nanocomposites containing MLG, different measurement methods were investigated to quantify the orientation of the nanoparticles in the nanocomposites: Sorption measurements (swelling in 2 dimensions), hardness and dynamical mechanical analysis (in-plane vs. cross-plane), X-Ray diffraction and transmission and scanning electron microscopy.
Bioanalytical, diagnostic, and security applications require the fast and sensitive determination of a steadily increasing number of analytes or events in parallel in a broad variety of detection formats and increased sensitivities. This – flanked by recent technical advancements and the availability of simple to use, commercial time-resolved photoluminescence measuring devices at reasonable costs - calls for the exploitation of the species- and environment-specific photoluminescence parameter luminescence lifetime. In this context, time-resolved photoluminescence measurements of different classes of molecular and nanocrystalline emitter and luminescent particles in different time windows are presented and examples for applications such as lifetime multiplexing and barcoding in conjunction with fluorescence lifetime imaging microscopy (FLIM) and flow cytometry are given.
Plastic debris in micron and nanometer scale pollutes the nature all over the world. The potential dangers of these pollutants remain unpredictable. While risk assessment studies on microplastics are already popular, nanoplastic has not yet reached the same focus of investigation. The reason for this difference is simple: There is a "methodological gap" in the analytics of plastic particles with a diameter smaller than 1 µm. Submicron and nanoplastic particles are currently not detectable in environmental matrices. Therefore, it is important for researchers to have a well-characterized nanoplastic material, that serves as a reference for nanoplastics found in nature.
Our aim was to synthesize nanoplastics made from the most common used plastics such as polypropylene (PP). We found an easy way to form nanoparticles consisting of PP (nano-PP), adapting and improving the method presented for polystyrene (PS). Nano-PP was formed via a top-down method where the polymer was dispersed to acetone and then transferred to water. No additional surfactant is needed to obtain a dispersion which is stable for more than 35 weeks.
The success of forming nanoplastics and their size was detected via scattering methods, predominantly dynamic light scattering (DLS). The chemical analysis of the nanoplastics was performed via Fourier Transform Infrared spectroscopy. To examine the good stability of the nanoparticles, zeta potential measurements were performed, which revealed zeta potentials of -30 to -40 mV.
Aqueous dispersions of polypropylene: towards referencematerials for nanoplastics characterization
(2022)
Plastic pollution in the environment is a rising concern for the health of our planet. The plastic litter that pollutes our environment leads to microplastic particles. They can be found (nearly) everywhere. The processes that lead to microplastic can also form nanoplastic particles, which have a size below 1 µm. Because of the small size they can penetrate tissue more easily. Only few risk assessment studies of nanoplastics were carried out so far.
Using polystyrene (PS) nanoparticles to test effects on organisms is easy because it is commercially available. However, this falls a little short, as the polyolefins i.e., polypropylene (PP) and polyethylene (PE), are produced in a larger proportion than PS. Moreover, these plastics are mainly used for disposable products, which means that they also account for a large proportion of plastic waste. Therefore, the percentage of polyolefins in environmental nanoplastic is presumably high. It is important to test the toxicological effects also with nanoplastics made of PP and PE to have more realistic results.
Herein, we present an easy and repeatable method to prepare an aqueous dispersion of polypropylene nanoplastics (nano-PP). They are stabilized electrostatically, resulting in a strongly negative zeta potential of -43 mV (± 2 mV) and making no surfactant necessary to keep the dispersion stable.
The size and the size distribution were determined via Dynamic Light Scattering (DLS) and gives a hydrodynamic diameter of 180.5 nm (± 5.8 nm) and a PDI of 0.084 (± 0.023).
Finally, ca. 480 bottles of the dispersion with a volume of 10 mL each were prepared to serve as a potential reference material for further testing of detection methods or risk assessments.
Luminescent semiconductor quantum dots (QDs) are frequently used in the life and material sciences as reporter for bioimaging studies and as active components in devices such as displays, light-emitting diodes, solar cells, and sensors. Increasing concerns regarding the use of toxic elements like cadmium and lead, and hazardous organic solvents during QD synthesis have meanwhile triggered the search for heavy-metal free QDs using green chemistry syntheses methods. Interesting candidates are ternary AgInS2 (AIS) QDs that exhibit broad photoluminescence (PL) bands, large effective Stokes shifts, high PL quantum yields (PL QYs), and long PL lifetimes, which are particularly beneficial for applications such as bioimaging, white light-emitting diodes, and solar concentrators. In addition, these nanomaterials can be prepared in high quality with a microwave-assisted (MW) synthesis in aqueous solution. The homogeneous heat diffusion and instant temperature rise of the MW synthesis enables a better control of QD nucleation and growth and thus increases the batch-to-batch reproducibility. In this study, we systematically explored the MW synthesis of AIS/ZnS QDs by varying parameters such as the order of reagent addition, precursor concentration, and type of stabilizing thiol ligand, and assessed their influence on the optical properties of the resulting AIS/ZnS QDs. Under optimized synthesis conditions, water-soluble AIS/ZnS QDs with a PL QY of 65% and excellent colloidal and long-term stability could be reproducible prepared.
Friction at the microscale during reciprocal sliding tribotests was studied for the first time with self-mated steel (100Cr6/AISI 52100) taking advantage of an atomic force microscope (AFM). To this aim, microsized steel particles were glued to the AFM-cantilever and employed as colloidal tips to perform tribotests on a steel disc. The torsion of the cantilever, which correlates with the friction force, was measured during the tests. Few tests with the same load did not yield any wear and show that the load and adhesion contributions to friction stay constant when the shape of the test particle does not change. Most of the presented tribotests engendered wear. For those tests, the increase of friction during the tribotests was attributed to the emerging plowing contribution. Furthermore, analysis of both torsion and local slope gives information on the creation of wear particles and their influence on friction.
The separation of colloidal nanocrystals from their original synthesis medium is an essential process step towards their application, however, the costs on a preparative scale are still a constraint. A new combination of approaches for the purification of hydrophobic Quantum Dots is presented, resulting in an efficient scalable process in regard to time and solvent consumption, using common laboratory equipment and low-cost materials. The procedure is based on a combination of solvent-induced adhesion and solid phase extraction. The platform allows the transition from manual handling towards automation, yielding an overall purification performance similar to one conventional batch precipitation/centrifugation step, which was investigated by thermogravimetry and gas chromatography. The distinct miscibility gaps between surfactants used as nanoparticle capping agents, original and extraction medium are clarified by their phase diagrams, which confirmed the outcome of the flow chemistry process. Furthermore, the solubility behavior of the Quantum Dots is put into context with the Hansen solubility parameters framework to reasonably decide upon appropriate solvent types.
Whereas the characterization of nanomaterials using different analytical techniques is often highly automated and standardized, the sample preparation that precedes it causes a bottleneck in nanomaterial analysis as it is performed manually. Usually, this pretreatment depends on the skills and experience of the analysts. Furthermore, adequate reporting of the sample preparation is often missing. In this overview, some solutions for techniques widely used in nano-analytics to overcome this problem are discussed. Two examples of sample preparation optimization by au-tomation are presented, which demonstrate that this approach is leading to increased analytical confidence. Our first example is motivated by the need to exclude human bias and focuses on the development of automation in sample introduction. To this end, a robotic system has been de-veloped, which can prepare stable and homogeneous nanomaterial suspensions amenable to a variety of well-established analytical methods, such as dynamic light scattering (DLS), small-angle X-ray scattering (SAXS), field-flow fractionation (FFF) or single-particle inductively coupled mass spectrometry (sp-ICP-MS). Our second example addresses biological samples, such as cells exposed to nanomaterials, which are still challenging for reliable analysis. An air–liquid interface has been developed for the exposure of biological samples to nanomaterial-containing aerosols. The system exposes transmission electron microscopy (TEM) grids under reproducible conditions, whilst also allowing characterization of aerosol composition with mass spectrometry. Such an approach enables correlative measurements combining biological with physicochemical analysis. These case studies demonstrate that standardization and automation of sample preparation setups, combined with appropriate measurement processes and data reduction are crucial steps towards more reliable and reproducible data.
BAM Inside #1/2022
(2022)
BAM Update #5/2022
(2022)
The work on Tribology, digitalisation, and the harmonised procedures developed in i-TRIBOMAT Open Innovation Testbed was presented. The project develops procedures and shares ideas on how to deal with characterisation techniques and provide services to end users in different places and locations, which is realised by adopting a common and widely agreed procedures. i-TRIBOMAT is active also via YouTube platform to enhance communication and spread the word amongst the interested parties and society.
Mit dem stetigen weltweiten Anstieg der Nachfrage nach Polymerprodukten nimmt auch die potenzielle Menge an Kunststoffabfällen in der Umwelt zu. Problematisch ist, dass viele der wirtschaftlich relevantesten Kunststoffe sehr lange brauchen, um in der Umwelt abzubauen, sich dort akkumulieren und in kritisch betrachtetes Makro- und Mikroplastik zu zerfallen. Auf der Grundlage des Vorsorgeprinzips fordert die Europäische Kommission daher die Entwicklung neuer polymerer Materialien, die diesem Problem der Persistenz entgegenwirken und unter natürlichen Umweltbedingungen schneller abgebaut werden können. 1,2
Um dieses Problem anzusprechen, wurden mittels additiver Fertigung Polymerblends aus photooxidationsempfindlichem Polystyrol (PS) und hydrolyseempfindlicher Polymilchsäure (PLA) hergestellt. Die Hypothese war, dass sich die beiden Thermoplaste aufgrund ihrer unterschiedlichen Abbauprozesse gegenseitig in ihrem Abbau unterstützen, wenn sie unter moderaten, realitätsnahen Umweltalterungsbedingungen (45 °C) abwechselnd der Photooxidation und Hydrolyse ausgesetzt werden.
In der Praxis zeigten die Ergebnisse, dass die Degradation von PLA durch die Anwesenheit von PS deutlich beschleunigt worden ist – wohingegen die Degradation von PS gehemmt wurde. In diesem Vortrag werden die detaillierten Ergebnisse der Oberflächen- (ATR-FTIR, REM) und Bulk-Analysen (DSC, TGA, FTIR-Transmission, TED-GC/MS) der Blends sowie ergänzende Mikroplastik-Ergebnisse des umgebenden Wassermediums (TED-GC/MS) erörtert.
Im Vortrag werden das Messprinzip des Zentrifugen-Sedimentationsverfahrens erläutert und die Anforderungen der zugrundeliegenden Normen diskutiert. Es schließen sich umfangreiche Ausführungen zur praktischen Durchführung der Messung, insbesondere auch zu den vorbereitenden Arbeiten, sowie zur Auswertung der Rohdaten an. Gezeigt werden die Validierung sowie ein Beispiel zur regelmäßigen Verifizierung des Verfahrens. Nach Beispielen und Vergleichen zu Ergebnissen mit anderen Messverfahren, wird das Verfahren in einer Zusammenfassung bewertet.
Vortrag zum Kick-off des Projektes.
Ziel des Projektes ist es, die Eignung der Bestimmung eines oder mehrerer der genannten anthropogenen Marker im Abwasser zur Volumenkorrektur („Kalibration“) im SARS-CoV-2-Monitoring von Abwässern auf der Basis eines von der BAM zu erhebenden Messdatensatzes zu evaluieren.
Im Rahmen des Forschungsprojektes IGF 20470N wurden Untersuchungen zum Alterungsverhalten von reaktiven Brandschutzsystemen (RBS) auf Stahlbauteilen durchgeführt. Mithilfe der Ergebnisse einer umfangreichen Literaturrecherche sowie experimentellen und numerischen Untersuchungen sollte ein Vorschlag für ein Prüfkonzept zum Nachweis einer Nutzungsdauer von RBS von mehr als 10 Jahren auf Basis von Kurzzeitversuchen abgeleitet werden. Dabei setzt die Bewertung des Alterungsverhaltens von RBS voraus, dass die Mechanismen der Alterung hinreichend bekannt sind.
Dafür wurden zunächst systematisch Daten von Kurz- und Langzeitversuchen von nationalen Zulassungsprüfungen der letzten Jahrzehnte ausgewertet. Anschließend wurden umfangreiche experimentelle Untersuchungen an einer wasserbasierten sowie einer epoxidharzbasierten Richtrezeptur durchgeführt. Da aus der Literatur bekannt ist, dass die Einflüsse der Bewitterung zu einer Veränderung der Konzentration der Bestandteile innerhalb der Beschichtung führen können, wurden Untersuchungen mit Mangelrezepturen durchgeführt, wobei systematisch einzelne Bestandteile reduziert wurden. Neben optischen Untersuchungen wurden thermoanalytische Verfahren (DSC-TG-, ATR-FTIR-, Elementar-, Farbanalyse) angewandt sowie Brandversuche an beschichteten Stahlplatten durchgeführt. Des Weiteren wurden die Richtrezepturen den beschleunigten Kurzzeitversuchen gemäß EAD 350402-00-1106 (2017) unterzogen, welche die Zulassung von Produkten auf europäischer Ebene regelt. Für die wasserbasierte Richtrezeptur wurden die Bewitterung für den feuchten Innenraum (Typ Z1) mehrfach wiederholt (1x, 3x, 6x). Für die epoxidharzbasierte Richtrezeptur entsprach die Bewitterung dem Zyklus für die Außenanwendung (Typ X). In Brandversuchen sowie thermoanalytischen und optischen Untersuchungen wurde das Alterungsverhalten sowie die thermische Schutzwirkung analysiert.
Anschließend wurden numerische Simulationen von Stahlbauteilen mit gealterten RBS durchgeführt und anhand der experimentellen Untersuchungen validiert. Mithilfe der numerischen Modelle kann eine Bewertung der thermischen Schutzwirkung von Stahlbauteilen mit gealterten RBS vorgenommen werden.
Mithilfe der gesammelten Erkenntnisse wurde ein Vorschlag für ein Prüfkonzept für den Nachweis einer Nutzungsdauer von mehr als 10 Jahren abgeleitet. Das Prüfkonzept besteht dabei aus einem Katalog von Möglichkeiten, die aktuellen Zulassungsprüfungen auf europäischer Ebene für eine Nutzungsdauer von 10 Jahren auf einen längeren Zeitraum zu erweitern.
The development of the microbiologically influenced corrosion ( MIC ) -specific inductively coupled plasma-time of flight-mass spectrometry ( ICP-ToF-MS ) analytical method presented here, in combination with the investigation of steel-MIC interactions, contributes significantly to progress in instrumental MIC analysis. For this, a MIC-specific staining procedure was developed, which ensures the analysis of intact cells. It allows the analysis of archaea at a single cell level, which is extremely scarce compared to other well-characterized organisms. The detection method revealed elemental selectivity for the corrosive methanogenic strain Methanobacterium -affiliated IM1. Hence, the possible uptake of individual elements from different steel samples was investigated and results showed the cells responded at a single-cell level to the different types of supplemented elements and displayed the abilities to uptake chromium, vanadium, titanium, cobalt, and molybdenum from solid metal surfaces. The methods developed and information obtained will be used in the future to elucidate underlying mechanisms, compliment well-developed methods, such as SEM-EDS, and develop novel material protection concepts.
The continuously increasing use of plastics is supposed to result in a rising exposure of MNPs to humans. Available data on human health risks of microplastics after oral uptake increased immensely in the past years and indicates very likely only low risks after oral consumption. Concerning nanoplastics, uptake, transport and potential adverse effects after oral uptake are less well understood. This study aims to investigate differences between microplastic particles and particles in the submicron- and nanoscaled size derived from food-relevant polymers with a particle size range consistent with higher potential for cellular uptake, fate, and effects when applied to human intestinal and liver cells. This work includes the development of cellular and subcellular detection methods for synthetic polymeric particles in the micro- and nanometer-range, using Scanning Electron Microscopy, Small-Angle X-ray and Dynamic Light Scattering methods, Asymmetric Flow Field Flow Fractionation, octanol-water fractionation, fluorescence microscopy and flow cytometry. Polylactic acid (250 nm and 2 μm (polydisperse)), melamine formaldehyde (366 nm) and polymethylmethacrylate (25 nm) were thoroughly characterized. The submicro- and nanoplastic test particles showed an increased uptake and transport quantity through intestinal cells. Both types of particles resulted in observed differences of uptake behavior, most likely influenced by different lipophilicity, which varied between the polymeric test materials. Toxic effects were detected after 24 h only in overload situations for the particles in the submicrometer range. This study provides further evidence for gastrointestinal uptake of submicro- and nanoplastics and points towards differences regarding bioavailability between microplastics and smaller plastic particles that may result following the ingestion of contaminated food and beverages. Furthermore, the results reinforce the importance for studying nanoplastics of different materials of varying size, surface properties, polymer composition and hydrophobicity.
Results:
- Four types of inks were measured iron gall (vitriolic and non vitriolic), carbonic, mixed and vegetable inks.
- We need to start analyzing systematically the organic part of the inks.
- Great variety in the composition of the inks.
- No correlation between the type of ink used and any other criteria apart from a personal preference.
- Inks purchased by (some) scribes.
- Reconstruction of the chronology of writing and signing of certain legal documents.
- Comparison with documents written by the Muslim court.
Antimicrobial resistance (AMR) is a global health problem with the environment being an important compartment for the evolution and transmission of AMR. Previous studies showed that de-novo mutagenesis and horizontal gene transfer (HGT) by conjugation or transformation – important processes underlying resistance evolution and spread - are affected by antibiotics, metals and pesticides. However, natural microbial communities are also frequently exposed to biocides used as material preservatives, but it is unknown if these substances induce mutagenesis and HGT. Here, we show that active substances used in material preservatives can increase rates of mutation and conjugation in a species- and substance-dependent manner, while rates of transformation are not increased. The bisbiguanide chlorhexidine digluconate, the quaternary ammonium compound didecyldimethylammonium chloride, the metal copper, the pyrethroid-insecticide permethrin, and the azole-fungicide propiconazole increase mutation rates in Escherichia coli, whereas no increases were identified for Bacillus subtilis and Acinetobacter baylyi.
Benzalkonium chloride, chlorhexidine and permethrin increased conjugation in E. coli. Moreover, our results show a connection between the RpoS-mediated general stress and the RecA-linked SOS response with increased rates of mutation and conjugation, but not for all biocides. Taken together, our data show the importance of assessing the contribution of material preservatives on AMR evolution and spread.
Clerodin was isolated from the medicinal plant Clerodendrum infortunatum, and CSD search showed the first crystal structure of clerodin by a single-crystal X-ray diffraction study. We checked its binding potential with target proteins by docking and conducted network pharmacology analysis, ADMET analysis, in silico pathway analysis, normal mode analysis (NMA), and cytotoxic activity studies to evaluate clerodin as a potential anticancer agent. The cell viability studies of clerodin on the human breast carcinoma cell line (MCF-7) showed toxicity on MCF-7 cells but no toxicity toward normal human lymphocyte cells (HLCs). The anticancer mechanism of clerodin was validated by its enhanced capacity to produce intracellular reactive oxygen species (ROS) and to lower the reduced glutathione content in MCF-7 cells.
Models for TOPAS/Geant4 to estimate the microscopic dose received by biomolecules during bioSAXS experiments.
The C++ classes in this repository extend the functionality of the TOPAS (http://www.topasmc.org/) Monte-Carlo program, which is itself a wrapper of the Geant4 MCS Toolkit (http://geant4.org).
Additive manufacturing (AM) processes are opening new design possibilities for large scale electrical devices such as power generators. Conventional manufacturing methods use copper rods which are wrapped, vacuum impregnated, bend and welded. These processes are labor-intensive and time-consuming. The introduction of AM methods for manufacturing the copper conductor and electrical insulation can reduce the size of the generator head, the most complex part of the generator.
In this study, the electrical and dielectrical properties of additively deposited ceramic layers are investigated and compared with the properties of conventionally fabricated bulk ceramics. The ceramic layers are thermally deposited by atmospheric plasma spraying of a commercially available alumina powder. Bulk ceramics are fabricated by dry pressing and sintering of the same powder. Microstructure and porosity were analyzed by scanning electron microscopy (SEM). Electrical and dielectrical properties such as DC resistance, dielectric strength, dielectric loss, and relative permittivity were determined according to the standards.
The microstructures of sprayed and sintered alumina show significant differences with respect to grain form and porosity. The density of the bulk ceramic is lower than the density of the sprayed layer due to the coarse particle size (d50 = 33 μm). Therefore, data from dense samples of the same chemical composition but lower particle size alumina powder were used for comparison.
Chromium(III) complexes can show phosphorescence from the spin-flip excited doublet states 2E/2T1 in the near-infrared with high photoluminescence quantum yields and extremely long lifetimes in the absence of dioxygen. The prototype molecular ruby, [Cr(ddpd)2]3+ (ddpd = N,N’-dimethyl-N,N’-dipyridine-2-ylpyridine-2,6-diamine), has a photoluminescence quantum yield and a luminescence lifetime of 13.7% and 1.1 ms in deaerated acetonitrile, respectively. However, its luminescence is strongly quenched by 3O2 via an efficient Dexter-type energy transfer process. To enable luminescence applications of molecular rubies in solution under aerobic conditions, we explored the potential of sterically demanding ddpd ligands to shield the chromium(III) center from O2 using steady state and time-resolved photoluminescence spectroscopy. The structures of the novel complexes with sterically demanding ligands were investigated by single crystal X-ray diffraction and quantum chemically by density functional theory calculations. The O2 sensitivity of the photoluminescence was derived from absolutely measured photoluminescence quantum yields and excited state lifetimes under inert and aerobic conditions and by Stern–Volmer analyses of these data. Optimal sterically shielded chromium(III) complexes revealed photoluminescence quantum yields of up to 5.1% and excited state lifetimes of 518 μs in air-saturated acetonitrile, underlining the large potential of this ligand design approach to broaden the applicability of highly emissive chromium(III) complexes.
Calibration-free methods in laser-induced breakdown spectroscopy, CF LIBS, serve as an alternative to calibration-based LIBS techniques. Their major advantage is the ability for fast chemical analysis in situations where matrix-matched standards are not readily available (as, e.g., in the analysis of biological materials and remote analysis) or amount of samples are limited. Their main applications are in the industry, geology, biology, archeology, and even space exploration. This chapter overviews the principle of operation and performance of CF LIBS techniques.
Engineering grain boundaries demands a quantitative description of both their segregation and specific phase behavior. Recently I have proposed a density-based model for grain boundary thermodynamics that enables CALPHAD integrated derivation of grain boundary phase diagrams, broadly applied now in studying various alloys. Combining this model with experimental investigations, in this talk, new aspects of interfacial segregation and phase transformation revealed in polycrystalline alloys are discussed. The effect of elastic interaction on grain boundary phase behavior is incorporated. We consider Al alloys and novel high-entropy alloys and discuss a general strategy for grain boundary engineering.
Carbon nanomembranes are synthetic two-dimensional sheets with nanometer thickness, macroscopic lateral dimensions, and high structural homogeneity. They have great application potential in various branches of nanotechnology. Because of their full carbon structure, it is not clear whether macromolecules like poly(methyl methacrylate) (PMMA) can be irreversibly adsorbed on their surface. Here, irreversible adsorption means that the polymer chains cannot be removed by a leaching process, which is assumed in technological transfer processes. However, if polar defects are present on the carbon nanomembranes (CNMs), it may occur that polymers can be irreversibly adsorbed. To address this question, PMMA was spin-coated on top of CNMs, annealed for a specific time at different temperatures, and then tried to be removed by a acetone treatment in a leaching approach. The samples were investigated in detail by atomic force microscopy, X-ray photoelectron spectroscopy, and broadband dielectric spectroscopy, where the latter method has been applied to CNMs for the first time. Unambiguously, it was shown that PMMA can be adsorbed on the surface of CNMs after annealing the sample above the glasstransition temperature of PMMA. The general occurrence of polar defects on the surface of CNMs and the adsorption of polymers open opportunities for advanced innovative hybrid materials combining the properties of the CNM with those of the polymer.
Poly (ether ether ketone) (PEEK) has a high continuous service temperature, excellent mechanical properties, and good solvent and abrasion resistance, which can be further improved through the addition of carbon nanotubes (CNTs). CNT-PEEK nanocomposites are promising matrices for continuous carbon fibre composites; powder processing can mitigate the high melt viscosities in these systems. In this study, model single fibre (hierarchical) composites were produced by embedding sized and desized carbon fibres in nanocomposite CNTPEEK powders followed by single fibre pull-out tests to assess interfacial characteristics. Carbon fibre-PEEK interfacial shear strength is typically 40–45 MPa. Increasing CNT loadings increased fibre-matrix interfacial shear strength linearly up to ~70 MPa at 5.0 wt%, which was attributed to the CNT-based mechanical modification of the PEEK matrix. Apparent interfacial shear strength was inversely correlated with the embedded fibre length irrespective of carbon fibre sizing or CNT loading, indicating brittle fracture of the fibre-matrix interface.
Pulled out carbon fibres were still coated with the matrix, which indicated strong adhesion at the interface in all samples, likely related to a transcrystalline region. Adhesion was, however, negatively affected by the presence of epoxy sizings. Frictional shear strength was independent of embedded fibre length and CNT content for all samples.
The fabrication of nanostructures with ever-decreasing sizes has increased the demand of suitable characterization methods which allow to determine their shape and size at the true nanoscale, and similarly important, enable the investigation of their optical properties beyond the diffraction limit. Due to its high spectral and spatial resolution down to the (sub-) nanometer range, electron beam-based techniques, namely cathodoluminescence (CL) has become a powerful characterization tool, particularly to study plasmonic and dielectric nanostructures. However, the interpretation of the resulting spectral CL maps is not always unambiguously straightforward.
In this work, Mie resonances in single Si nanospheres of different sizes have been systematically studied, using experimental CL spectroscopy and an analytical CL model. For smaller spheres (r ~ 75 nm), the eigenmodes can be unequivocally identified, with relative changes in intensity of the electric and magnetic dipole depending on the electron beam position within the sphere. However, in larger spheres (r ~ 105 nm), the modal assignment becomes increasingly difficult due to a larger number of Mie modes in the visible spectral range. Additionally, penetrating electron beams generate two radiating dipoles at the two Si interfaces – due to the electron and its image charge collapsing at those interfaces – which can, depending on the electron beam’s velocity and its path length inside the particle, produce distinct resonances or dips (constructive or destructive interference of those two radiative dipoles). It is demonstrated that superimposed on the eigenmodes of the studied nanospheres, these resonances can distort the recorded spectrum and lead to potentially erroneous assignment of modal characters to the spectral features. An intuitive analogy is developed to unambiguously distinguish those resonance induced by transition radiation from the nanoparticle-specific Mie resonances.
The novel lab-based HAXPES spectrometer (ULVAC-PHI Quantes) gives us the possibility to measure XPS at 1486.6 eV (monochromatic Al Kα source) and HAXPES at 5414.9 eV (monochromatic Cr Kα source) on a sample at the same position. The surface analysis with this spectrometer leads to an information depth of about 10 nm for XPS and in comparison, to an analysis of deeper regions of about 30 nm for HAXPES measurements. This method provides a nondestructive way to distinguish between the near-surface region of the nanoparticles and the whole nanoparticle. Additionally, HAXPES gives access to deeper core levels at higher energy.
An application of this technique is presented using nanoparticles. The results shown were obtained with nanoparticles, that were treated differently by means of sterilization for nanosafety (i.e., before studying their toxicity it is important to establish whether nanomaterials are sterile and, if not, to be treated either via microwave or autoclave sterilisation). As a complementary method, the data is compared with SEM and EDX measurements. All methods demonstrate the influence of sterilization. More specifically, these results show that the sterilization step must be considered in the physical-chemical description of the particles for establishing reliable (quantitative structure-activity) relationships.
Many advanced materials consist of fibers. They are used as nonwovens, fabrics, or in composite materials. Characterization of individual fibers allows us to predict resulting material properties. We present a measurement setup and analysis software to characterize individual, micrometer-sized fibers fast and reliably. The setup is based on the lock-in thermography principle. Thermal diffusivity values of seven reference samples agree very well with previously reported values. We use our setup to investigate critical measurement parameters like excitation frequency, excitation power, pixel size, and fiber orientation. Our results show that fibers with subpixel diameters can be measured even if they are not aligned. However, special care has to be taken to choose an adequate excitation power. Measurements at high intensities can underestimate thermal diffusivity even though the raw data looks reasonable. By automatically measuring at different excitation powers, our setup solves this issue.
The structural build-up of fresh cement paste is often considered as a purely thixotropic phenomenon in literature even though cementitious materials undergo a non-reversible hydration process that can have an influence on the structuration process. In the current paper a method is proposed to validate the impact of the non-reversible structural build-up. It is shown that fresh cement paste samples lose their structural gain almost completely due to thixotropy while the structural build-up due to hydration can be observed but occurs in a significantly lower order of magnitude over the course of the first hours of hydration. In addition, it is shown, that the chemical component of the structural build-up accelerates with the onset of the acceleration period of hydration, while its contribution in the entire structural build-up remains constant.
Clarifying the Electro-Chemo-Mechanical Coupling in Li10SnP2S12 based All-Solid-State Batteries
(2022)
A fundamental clarification of the electro-chemo-mechanical coupling at the solid–solid electrode|electrolyte interface in all-solid-state batteries (ASSBs) is of crucial significance but has proven challenging. Herein, (synchrotron) X-ray tomography, electrochemical impedance spectroscopy (EIS), time-of-flight secondary-ion mass spectrometry (TOF-SIMS), and finite element analysis (FEA) modeling are jointly used to decouple the electro-chemo-mechanical coupling in Li10SnP2S12-based ASSBs. Non-destructive (synchrotron) X-ray tomography results visually disclose unexpected mechanical deformation of the solid electrolyte and electrode as well as an unanticipated evolving behavior of the (electro)chemically generated interphase. The EIS and TOFSIMS probing results provide additional information that links the interphase/electrode properties to the overall battery performance. The modeling results complete the picture by providing the detailed distribution of the mechanical stress/strain and the potential/ionic flux within the electrolyte.
Collectively, these results suggest that 1) the interfacial volume changes induced by the (electro)chemical reactions can trigger the mechanical deformation of the solid electrode and electrolyte; 2) the overall electrochemical process can accelerate the interfacial chemical reactions; 3) the reconfigured interfaces in turn influence the electric potential distribution as well as charge transportation within the SE. These fundamental discoveries that remain unreported until now significantly improve the understanding of the complicated
electro-chemo-mechanical couplings in ASSBs.
Colours, nano and surface
(2022)
The basic ideas of colours and pigments are presented. The correlation between nanomaterials and colours are explained. Different methods are presented for investigating nanoparticles and their surface. At the end a case study is presented explaining the importance of coating for the properties of nanoparticles.
ZnO nanopillars were implanted with Au-400 keV and Ag-252 keV ions with ion fluences from 1 × 10^15 cm^2 to 1 × 10^16 cm^2. We compared ZnO nanopillars solely implanted with Au-ions and dually-implanted with Au and Ag-ions. Rutherford Back-Scattering spectrometry (RBS) confirmed Ag and Au embedded in ZnO nanopillar layers in a reasonable agreement with theoretical calculations. A decreasing thickness of the ZnO nanopillar layer was evidenced with the increasing ion implantation fluences. Spectroscopic Ellipsometry (SE) showed a decrease of refractive index in the nanopillar parts with embedded Au, Ag-ions. XRD discovered vertical domain size decreasing with the proceeding radiation damage accumulated in ZnO nanopillars which effect was preferably ascribed to Au-ions. SE and diffuse reflectance spectroscopy (DRS) showed optical activity of the created nanoparticles at wavelength range 500 – 600 nm and 430 – 700 nm for the Au-implanted and Au, Ag-implanted ZnO nanopillars, respectively. Photoluminescence (PL) features linked to ZnO deep level emission appear substantially enhanced due to plasmonic interaction with metal nanoparticles created by Ag, Au-implantation.
Photocatalytic activity seems to be more influenced by the nanoparticles presented in the layer rather than the surface morphology. Dual implantation with Ag, Au-ions enhanced optical activity to a larger extent without significant morphology deterioration as compared to the solely Au-ion implanted nanopillars.
The diffusive gradients in thin-films (DGT) technique shows in many publications a superior correlation to the amount of plant-available phosphorus (P) in soil. However, this technique cannot give information on the plant-available P species in soil. Therefore, we combined DGT with solution 31P nuclear magnetic resonance (NMR) spectroscopy. This was achieved by using a modified DGT device in which the diffusive layer had a larger pore size, the binding layer incorporated an adsorption material with a higher capacity, and the device had a larger exposure area. The spectroscopic investigation was undertaken after elution of the deployed DGT binding layer in a NaOH solution. Adsorption tests using solutions of known organic P compounds showed that a sufficient amount of these compounds could be adsorbed on the binding layer in order for them to be analyzed by solution 31P NMR spectroscopy. Furthermore, various intermediates of the hydrolysis of trimetaphosphate in soil could be also analyzed over time.
A large and increasing number of scientific domains pushes for high neutron imaging resolution achieved in reasonable times. Here we present the principle, design and performance of a detector based on infinity corrected optics combined with a crystalline Gd3Ga5O12 : Eu scintillator, which provides an isotropic sub-4 μm true resolution. The exposure times are only of a few minutes per image. This is made possible also by the uniquely intense cold neutron flux available at the imaging beamline NeXT-Grenoble. These comparatively rapid acquisitions are compatible with multiple high quality tomographic acquisitions, opening new venues for in-operando testing, as briefly exemplified here.
Considering the availability of serological and molecular biological methods, the bioassay has been paled into insignificance, although it is the only experimental method that can be used to demonstrate the infectivity of a virus. We compared goodness-of-fit and predictability power of five models for the quantification of tomato brown rugose fruit virus (ToBRFV) based on local lesion assays: the Kleczkowski model, Furumoto and Mickey models I and II, the Gokhale and Bald model (growth curve model), and the modified Poisson model. For this purpose, mechanical inoculations onto Nicotiana tabacum L. cv. Xanthi nc and N. glutionosa L. with defined virus concentrations were first performed with half-leaf randomization in a Latin square design. Subsequently, models were implemented using Python software and fitted to the number of local lesions. All models could fit to the data for quantifying ToBRFV based on local lesions, among which the modified Poisson model had the best prediction of virus concentration in spike samples based on local lesions, although data of individual indicator plants showed variations. More accurate modeling was obtained from the test plant N. glutinosa than from N. tabacum cv. Xanthi nc. The position of the half-leaves on the test plants had no significant effect on the number of local lesions.
Through the application of scientific methods of analysis to a corpus of medieval manuscripts found in the Cairo Genizah, this work aims to gain a better understanding of the writing materials used by Jewish communities at that time, shedding new light not only on the production of manuscripts in the Middle Ages, but also on the life of those Jewish communities.
Core–shell nanoparticles have attracted much attention in recent years due to their unique properties and their increasing importance in many technological and consumer products. However, the chemistry of nanoparticles is still rarely investigated in comparison to their size and morphology. In this review, the possibilities, limits, and challenges of X-ray photoelectron spectroscopy (XPS) for obtaining more insights into the composition, thickness, and homogeneity of nanoparticle coatings are discussed with four examples: CdSe/CdS quantum dots with a thick coating and a small core; NaYF4-based upconverting nanoparticles with a large Yb-doped core and a thin Er-doped coating; and two types of polymer nanoparticles with a poly(tetrafluoroethylene) core with either a poly(methyl methacrylate) or polystyrene coating. Different approaches for calculating the thickness of the coating are presented, like a simple numerical modelling or a more complex simulation of the photoelectron peaks. Additionally, modelling of the XPS background for the investigation of coating is discussed. Furthermore, the new possibilities to measure with varying excitation energies or with hard-energy X-ray sources (hard-energy X-ray photoelectron spectroscopy) are described. A discussion about the sources of uncertainty for the determination of the thickness of the coating completes this review.
Liquid crystalline mesophases in nanoconfinement exhibit intriguing phase transition behaviors and relaxation dynamics. Here in, we investigate the molecular dynamics and electrical conductivity of a linear shaped guanidinium based ILC confined in self-ordered nano porous alumina oxide membranes of pore size ranging from 180nm down to 25nm by employing broadband dielectric spectroscopy (BDS) and calorimetry. Calorimetric investigation reveals a complete suppression of the columnar – isotropic transition, while the plastic crystalline – columnar transition temperature decreases with inverse pore size and deviates from the Gibbs – Thomson equation.
For the bulk case, BDS detects two relaxation modes in the crystalline phase, the relaxation and the α1 relaxation, and two relaxation modes in the columnar phase, the α2 and α3 relaxation. For the confined case, all relaxation modes slow down compared to the bulk. However, for the least pore size (25 nm), the α2 relaxation is absent. We discuss the possible molecular origins of the different relaxation modes observed. For the bulk ILC, a clear jump of 4 orders of magnitude in the absolute values of DC conductivity occurs at the transition from the plastic crystalline to hexagonal columnar phase, for the confined ILC, this transition is smooth. DC conductivity is reduced for the confined case, except for the 25nm, where the values is similar to the bulk.
Next-generation thermal management requires the development of low lattice thermal conductivity materials, as observed in ionic conductors. For example, thermoelectric efficiency is increased when thermal conductivity is decreased. Detrimentally, high ionic conductivity leads to thermoelectric device degradation. Battery safety and design also require an understanding of thermal transport in ionic conductors. Ion mobility, structural complexity, and anharmonicity have been used to explain the thermal transport properties of ionic conductors. However, thermal and ionic transport are rarely discussed in direct comparison. Herein, the ionic conductivity of Ag+ argyrodites is found to change by orders of magnitude without altering the thermal conductivity. Thermal conductivity measurements and two-channel lattice dynamics modeling reveal that the majority of Ag+ vibrations have a non-propagating diffuson-like character, similar to amorphous materials. It is found that high ionic mobility is not a requirement for diffuson-mediated transport. Instead, the same bonding and structural traits that can lead to fast ionic conduction also lead to diffuson-mediated transport. Bridging the fields of solid-state ionics and thermal transport, it is proposed that a vibrational perspective can lead to new design strategies for functional ionic conducting materials. As a first step, the authors relate the so-called Meyer-Neldel behavior in ionic conductors to phonon occupations.
NaYF4 as the core and NaGdF4 as the outer layer were used to obtain
NaYF4:Yb3+/Tm3+@NaYF4:Ce3+/Eu3+ nanoparticles. Physical and morphological investigations indicated that the obtained nanoparticles were prepared in a hexagonal shape, with the NaGdF4 shell layer uniformly encapsulated on the NaYF4 core.
Strong Tm3+ upconversion emission peaks were observed for a 980-nm-laser-excited sample, while strong Eu3+ downconversion emission peaks were observed for a 254-nm-laser-excited sample. By zonal doping of Tm3+ and Eu3+, their fluorescence intensity can be significantly increased; more importantly, simultaneous temperature measurements with dual-mode upconversion/downconversion can be achieved. The temperature measurement properties of the dual mode were also investigated, and it was discovered that the upconversion 3F3 → 3H6 and 1G4 → 3F4 thermocouple energy levels gave the best temperature measurements with maximum absolute and relative sensitivities of 0.0877 K−1 and 1.95% K−1, respectively, which are better than the current temperature measurement sensitivities of most rare-earth-based materials. This material was prepared as fiber-optic temperature-sensing probes to detect the temperature in the environment in real time and was found to perform excellently for temperature measurement.
In the present talk the basics of the Raman spectroscopy and particularly of Raman microscopy are explained. Advantages and disadvantages of the method are highlighted through selected case studies. In the second part of the lecture examples of correlative imaging with electron, X-ray, ion and optical microscopies from micro- to the nanoscale are highlighted.
A global transition towards more sustainable, affordable and reliable energy systems is being stimulated by the Paris Agreement and the United Nation's 2030 Agenda for Sustainable Development. This poses a challenge for the corrosion industry, as building climate‐resilient energy systems and infrastructures brings with it a long‐term direction, so as a result the long‐term behaviour of structural materials (mainly metals and alloys) becomes a major prospect. With this in mind “Corrosion Challenges Towards a Sustainable Society” presents a series of cases showing the importance of corrosion protection of metals and alloys in the development of energy production to further understand the science of corrosion, and bring the need for research and the consequences of corrosion into public and political focus. This includes emphasis on the limitation of greenhouse gas emissions, on the lifetime of infrastructures, implants, cultural heritage artefacts, and a variety of other topics.
Aluminum (Al) is highly abundant in the biosphere and can occur in different physico-chemical states. It is present in human food and undergoes transitions between dissolved and particulate species during the passage of the gastrointestinal tract. Moreover, in a complex matrix such as food different inorganic and organic counterions can affect the chemical behavior of Al following oral uptake.
In this work, the effects of different counterions, namely chloride, citrate, sulfate, lactate and acetylacetonate, on Al uptake and toxicity in the human intestine are studied. The respective Al salts showed different dissolution behavior in biological media and formed nanoscaled particles correlating in reverse with the amount of their dissolved fraction. The passage through the intestinal barrier was studied using a Caco-2 Transwell® system, showing counterion-dependent variance in cellular uptake and transport. In addition, Al toxicity was investigated using Al species (Al3+, metallic Al0 and oxidic γAl2O3 nanoparticles) and counterions individually or in mixtures on Caco-2 and HepG2 cells. The strongest toxicity was observed using a combination of Al species, depending on solubility, and the lipophilic counterion acetylacetonate. Notably, only the combination of both led to toxicity, while both substances individually did not show toxic effects. A toxification of previously non-toxic Al-species by the presence of acetylacetonate is shown here for the first time. The dependency on the concentration of free Al ions was demonstrated using sodium hydrogen phosphate, which was able to counteract the toxic effects by complexing free Al ions.
These findings, using Al salts as an example for a common food contaminant, underline the importance of a consideration of the chemical properties of human nutrition, especially dissolution and hydrophobicity, which can significantly influence the cellular uptake and effects of xenobiotic substances.
Electron microscopy (EM) is the gold standard for the characterisation of the morphology (size and shape) of nanoparticles. Visual observation of objects under examination is always a necessary first step in the characterisation process. Several questions arise when undertaking to identify and count particles to measure their size and shape distribution. In addition to challenges with the dispersion and identification of the particles, more than one protocol for counting particles is in use. This paper focuses on precise rules for the counting of particles in EM micrographs, as this influences the measurement accuracy of the number of particles, thus implicitly affecting the size values of the counted particles. We review and compare four different, commonly used methods for counting, which we then apply in case studies. The impact of the selected counting rule on the obtained final particle size distribution is highlighted. One main aim of this analysis is to support the application of a specific, well-defined counting approach in accordance with regulatory
requirements to contribute to achieving more reliable and reproducible results. It is also useful for the new harmonised measurement procedures for determining the particle size and particle size distribution of nanomaterials.
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.
The elastic constants are the most basic mechanical properties of a material and are needed for any structural analysis of a component. For example, they have a major influence on the eigenfrequencies of vibrating parts. Single crystals of Ni-base superalloys are strongly anisotropic, which means that the observed properties are orientation dependent. Tensor algebra is then required to mathematically formulate the elastic properties and their relations to the crystal orientation. Hence, this chapter first summarizes some basic definitions and calculation rules for Rotation matrices, including the definition of the Euler angles, which are most commonly used to define the relative orientations of the crystal and the component. Parts of this chapter closely follow the lines of the excellent exposition of the topic by Olschewski.
The large number of TEM investigations and the regular microstructure
of single-crystal nickel-base superalloys has boosted the development of a number of physically motivated constitutive laws. In contrast to the more phenomenological models discussed in the next chapter, these models use dislocation densities as internal variables. Obvious advantages are that the computed densities can be compared to TEM observations and the Deformation mechanisms can be easier translated into mathematical equations.
Damage induced by electric field (DIEF) that happens in the transmission electron microscope (TEM) when converging the electron beam (e-beam) on microparticles (MPs) can be used to synthesis new nanomaterial and nanomaterial compositions. The research questions are to clarify the limits and possibilities of the method regarding materials that can be produced, systems to which it is applicable and working beam parameters. Synthesis of nano-objects from microparticles using DIEF in TEM could be shown for different materials. Additionally, DIEF using the e-beam in a scanning electron microscope (SEM) can also be used to synthesis nano-objects. A deeper material analysis of this nano-objects was done using TEM and shows that the material of the nanoparticles (NPs) can be gold or/and silicon. Furthermore, the size of the NPs depends on the distance to the center of DIEF whereby the larger NPs are closer to the center. The areas of gold NPs are promising candidates for plasmonic or photonic devices for energy storage or transport.
Phase transitions are a common phenomenon in condensed matter and act as a critical degree of freedom that can be employed to tailor the mechanical or electronic properties of materials. Understanding the fundamental mechanisms of the thermodynamics and kinetics of phase transitions is, thus, at the core of modern materials design. Conventionally, studies of phase transitions have, to a large extent, focused on pristine bulk phases. However, realistic materials exist in a complex form; their microstructures consist of different point and extended defects. The presence of defects impacts the thermodynamics and kinetics of phase transitions, but has been commonly ignored or treated separately. In recent years, with the significant advances in theoretical and experimental techniques, there has been an increasing research interest in modeling and characterizing how defects impact or even dictate phase transitions. The present review systematically discusses the recent progress in understanding the kinetics of defect-characterized phase transitions, derives the key mechanisms underlying these phase transitions, and envisions the remaining challenges and fruitful research directions. We hope that these discussions and insights will help to inspire future research and development in the field.
The need of clean water and the water-poor are increasing daily in the world. In addition, we are facing a dramatic increase in the industrial pollutions of rivers and groundwater, which led us to find a new way to treat industrial pollutants. The plasma discharge technique is one of the important, safe, and applicable for industrial wastewater decontamination. Decolorization of Brilliant Blue R (BBR) dye as a hazard material was noticed when the contaminated solution was exposed to the plasma discharge technique. The combination between the nonthermal plasma and catalysts was evaluated in this work to optimize the degradation efficiency. The PVDF/(MWCNTs/TiO2) as three system composites was employed to enhance the nonthermal plasma performance. The surface area, phase purity, shape, and photonic efficiency were characterized employing XRD, FTIR, SEM, DSC, and UV–Vis. techniques. The obtained results of degradation using NTP technique in presence of the PVDF/MWCNTs catalyst have been enhanced the BBR dye degradation by 19% than only plasma treatment for 20 min.
The durability processes of prepared PVDF/(MWCNTs/TiO2) was investigated and evaluated until 8 solar photocatalytic process repeating times.
pH and oxygen are amongst the most important and frequently measured analytes in the life and material sciences, indicating, e.g., diseases and corrosion processes. This includes the optical monitoring of pH in living cells for studying cellular internalization pathways, such as phagocytosis, endocytosis, and receptor ligand internalization with the aid of molecular and nanoscale fluorescent sensors. Nanoparticle (NP)-based sensors, that are labeled or stained with a multitude of sensor dyes, have several advantages as compare to conventional molecular probes like enhanced brightness, i.e., amplified signals, ease of designing ratiometric systems by combining analyte sensitive and inert reference dyes, and increased photostability. Moreover, this can enable the use of hydrophobic dyes in aqueous environments. Versatile templates and carriers for the fabrication of nanosensors by the staining and/or labelling with different fluorophores and sensor molecules or surface functionalized NP like silica (SiO2-NP) and polystyrene (PS-NP) particles provide. Here we present the design of a versatile platform of color emissive nanosensors and stimuli-responsive microparticles for the measurement of pH, oxygen, and other targets utilizing both types of matrices and sets of spectrally distinguishable sensor and reference dyes and their characterization and demonstrate the applicability of representative sensor particle for cellular studies.
Even though we often do not knowingly recognize them, nanoparticles are present these days in most areas of our daily life, including food and its packaging, medicine, pharmaceuticals, cosmetics, pigments as well as electronic products, such as computer screens. The majority of these particles exhibits a core-shell morphology either intendedly or unintendedly. For the purpose of practicability, this core-shell nanoparticle (CSNP) morphology is often assumed to be ideal, namely a spherical core fully encapsulated by a shell of homogeneous thickness with a sharp interface between core and shell material. It is furthermore widely presumed that all nanoparticles in the sample possess the same shell thickness. As a matter of fact, most real CSNPs deviate in several ways from this ideal model with quite often severe impact on how efficiently they perform in a specific application.
The topic of this cumulative PhD thesis is the accurate characterization of the actual morphology of CSNPs by advanced X-ray analytical techniques, namely X-ray photoelectron spectroscopy (XPS) and scanning transmission X-ray microscopy (STXM). A special focus is on CSNPs which deviate from an ideal core-shell morphology. In the paper from 2019 nanoparticle shell thicknesses are extracted from the elastic-peak intensities in an XPS spectrum based on an ideal particle morphology. This happens for a series of CSNP samples comprising a poly(tetrafluoroethylene) (PTFE) core and either a poly(methyl methacrylate) (PMMA) or polystyrene (PS) shell. The same paper as well as the paper from 2020 demonstrate for the first time, that the analysis of the inelastic background in an XPS spectrum of CSNPs can identify and quantify the heterogeneity of the shell and the incomplete encapsulation of the core.
The result from an XPS experiment is always an average across a large nanoparticle ensemble. Deviations from an ideal morphology within a single particle of the sample cannot be assessed separately. As opposed to that, a spatial resolution of 35 nm enables STXM to visualize the interior of single CSNPs which exhibit a sufficient X-ray absorption contrast between core and shell material. In the paper from 2018 a STXM analysis is demonstrated based on the example of the PTFE-PS CSNP samples already mentioned in the previous paragraph.
In the publication from 2021 (Ca/Sr)F₂ core-shell like nanoparticle ensembles for the practical use in, among others, antireflective coatings are investigated. These nanoparticles do not possess a sharp interface between core and shell material, which is why a shell thickness determination as described in the second paragraph is inappropriate. Instead, in-depth profiles of the chemical composition are obtained by XPS experiments based on synchrotron radiation with variable X-ray photon energy to elucidate the internal morphology of the particles. Additionally, theoretical in-depth profiles of Ca and Sr XPS peak intensities are simulated, in order to facilitate the interpretation of the experiments. Thus, an enrichment of CaF₂ at the particle surface was determined, which could hardly have been assessed by any other analytical technique. Because this kind of non-destructive depth profiling by XPS is very demanding, more than usual effort is spent on gapless documentation of the experiments to ensure full reproducibility.
Due to the vast diversity of nanoparticles differing in material, composition and shape, a measurement procedure cannot unalteredly be transferred from one sample to another. Nevertheless, because the papers in this thesis present a greater depth of reporting on the experiments than comparable publications, they constitute an important guidance for other scientists on how to obtain meaningful information about CSNPs from surface analysis.
Fast and accurate determination of the protein content of a sample is an important and non-trivial task of many biochemical, biomedical, food chemical, pharmaceutical, and environmental research activities. Different methods of total protein determination are used for a wide range of proteins with highly variable properties in complex matrices. These methods usually work reasonably well for proteins under controlled conditions, but the results for non-standard and complex samples are often questionable. Here, we compare new and well-established methods, including traditional amino acid analysis (AAA), aromatic amino acid analysis (AAAA) based on the amino acids phenylalanine and tyrosine, reversed-phase liquid chromatography of intact proteins with UV absorbance measurements at 220 and 280 nm (LC-220, LC-280), and colorimetric assays like Coomassie Blue G-250 dye-binding assay (Bradford) and bicinchoninic acid (BCA) assay. We investigated different samples, including proteins with challenging properties, chemical modifications, mixtures, and complex matrices like air particulate matter and pollen extracts. All methods yielded accurate and precise results for the protein and matrix used for calibration. AAA, AAAA with fluorescence detection, and the LC-220 method yielded robust results even under more challenging conditions (variable analytes and matrices). These methods turned out to be well-suited for reliable determination of the protein content in a wide range of samples, such as air particulate matter and pollen.
Electron Probe Microanalysis (EPMA) provides a non-destructive approach in the dedicated thin film analysis mode with the commercial StrataGem software. Recently, the open-source programme BadgerFilm by Moy and Fournelle became available. Similarly to StrataGem, it is based on the algorithm of Pouchou and Pichoir and needs intensity ratios of the unknown sample and standards (k-values). We have evaluated the k-values measured for the FeNi and SiGe film systems using the BadgerFilm software package and compared the thickness and composition with the results obtained with the established StrataGem software and other reference methods. The thicknesses of the SiGe films obtained by the BadgerFilm software agree within 20% with the StrataGem and TEM results; the elemental compositions BadgerFilm-StrataGEM agree within 2% with one exception (9%).
The thickness of thin films can be measured by various methods, e.g., profilometry, ellipsometry, atomic force microscopy (AFM), or X-ray reflectometry. For the additional determination of thin film composition, techniques like X-ray photoelectron spectroscopy (XPS) or mass spectrometry-based techniques can be used. An alternative non-destructive technique is electron probe microanalysis (EPMA). This method assumes a sample of homogenous (bulk) chemical composition, so that it cannot be usually applied to thin film samples. However, in combination with the thin film software StrataGEM, the thickness as well as the composition of such films on a substrate can be determined.
This has been demonstrated for FeNi on Si and SiGe on Al2O3 film systems. For both systems five samples with different elemental composition and a reference were produced and characterised by Korean research institute KRISS using inductively coupled plasma mass spectrometry (ICP-MS), Rutherford backscattering (RBS), and transmission electron microscopy (TEM). These samples were used for an international round robin test.
In 2021, a new and open-source thin film evaluation programme called BadgerFilm has been released. It can also be used to determine thin film composition and thickness from intensity ratios of the unknown sample and standards (k-ratios).
In this contribution, we re-evaluated the data acquired for the FeNi and SiGe systems using the BadgerFilm software package and compared the resulting composition and thickness with the results of the established StrataGEM software and other reference methods. With the current evaluation, the BadgerFilm software shows good agreement with the composition and thickness calculated by StrataGEM and as the reference values provided by the KRISS.
The development of earth-abundant catalysts for selective electrochemical CO2 conversion is a central challenge. Cu-Sn bimetallic catalysts can yield selective CO2 reduction toward either CO or formate. This study presents oxide-derived Cu-Sn catalysts tunable for either product and seeks to understand the synergetic effects between Cu and Sn causing these selectivity trends. The materials undergo significant transformations under CO2 reduction conditions, and their dynamic bulk and surface structures are revealed by correlating observations from multiple methods—X-ray absorption spectroscopy for in situ study, and quasi in situ X-ray photoelectron spectroscopy for surface sensitivity. For both types of catalysts, Cu transforms to metallic Cu0 under reaction conditions. However, the Sn speciation and content differ significantly between the catalyst types: the CO-selective catalysts exhibit a surface Sn content of 13 at. % predominantly present as oxidized Sn, while the formate-selective catalysts display an Sn content of ≈70 at. % consisting of both metallic Sn0 and Sn oxide species. Density functional theory simulations suggest that Snδ+ sites weaken CO adsorption, thereby enhancing CO selectivity, while Sn0 sites hinder H adsorption and promote formate production. This study reveals the complex dependence of catalyst structure, composition, and speciation with electrochemical bias in bimetallic Cu catalysts.
Functionalized nanomaterials (NM) with their unique size-dependent properties are of increasing relevance for current and future developments in various fields such as medical and pharmaceutical industry, computing, electronics or food and consumer products. The performance and safety of NM are determined by the sum of their intrinsic physicochemical properties.1 Besides other key parameters, the particle surface chemistry, which is largely controlled by the chemical nature and density of functional groups and ligands, must be considered for a better performance, stability, and processibility of NM, as well as their interaction with the environment. Thus, particle standards with well-designed surfaces and methods for functional group quantification can foster the sustainable development of functional and safe(r) NM.2 Here we provide a brief overview of the ongoing research in division Biophotonics to design tailored amorphous silica reference particles with bioanalytically relevant functional groups and ligands, for the development of standardized and validated surface functional group quantification methods.
Die BAM wird kurz mit ihren Eckdaten als Ganzes vorgestellt und dann der Einstieg in die besonderen Möglichkeiten der Versuchsplattform "Wasserstofftankstelle" erläutert. Nach kurzen Vorstellung der Struktur der Tankstelle wird erläutert, wie drei Methoden der ZfP für das Structural Health Monitoring in Verbindung mit KI zur Anwendung kommen werden.
Die Klassik-Stiftung Weimar besitzt eine umfangreiche Sammlung niederländischer und flämischer Zeichnungen vom 15. bis 19. Jahrhundert. Im Rahmen des Forschungsprojektes »Kennerschaft heute« wurde der Bestand der über 1.500 Zeichnungen erstmals wissenschaftlich erschlossen. Das Handbuch führt anhand bedeutender Werkgruppen, darunter Zeichnungen von Lucas van Leyden, Dirck Vellert, Roelant Savery und Rembrandt, den Reichtum der Weimarer Sammlung vor Augen, die zum großen Teil auf die Sammelleidenschaft von Johann Wolfgang Goethe zurückgeht. Im Zentrum des Buches steht aber die Zusammenarbeit von traditioneller Stilkritik und naturwissenschaftlicher Materialanalyse. In zwölf Fallbeispielen wird die Notwendigkeit einer methodischen Neuausrichtung der Kennerschaft darlegt. Einen Schwerpunkt der Untersuchungen bildet hierbei das große Konvolut an Zeichnungen von Rembrandt und seinen Schülern, das erstmals systematisch auf die verwendeten Zeichenmaterialien und Papiere untersucht wird.
Thermal spraying provides a rapid method for additive deposition of various ceramics as electrical insulation in applications where polymers are not suitable. New applications in complex shaped additive manufactured metal parts are emerging for example in large scale electrical devices. Microstructural and dielectric evaluation of coatings is crucial to the employment of such free-form processes. The properties and microstructure of the plasma sprayed alumina coatings are compared with dense reference samples of the same powder produced by spark plasma sintering (SPS). To obtain dense bulk samples from the coarse alumina powder for spray coating, SPS is used.
Samples are fabricated by atmospheric plasma spraying (APS) of commercially available alumina powder (d50 = 33 µm) on copper substrates and by SPS of the same powder. Microstructure and porosity were analyzed by optical microscopy and scanning electron microscopy (SEM). Phase compositions were determined by X-ray diffraction (XRD). Dielectric properties such as DC resistance, dielectric strength, dielectric loss, and relative permittivity were determined according to the standards. The microstructure and dielectric properties of the coating and bulk material are compared to assess whether the coating is suitable for use in electrical insulation application.
Objectives: Using a murine model of multiple sclerosis, we previously showed that repeated administration of gadopentetate dimeglumine led to retention of gadolinium (Gd) within cerebellar structures and that this process was enhanced with inflammation. This study aimed to compare the kinetics and retention profiles of Gd in inflamed and healthy brains after application of the macrocyclic Gd-based contrast agent (GBCA) gadobutrol or the linear GBCA gadopentetate. Moreover, potential Gd-induced neurotoxicity was investigated in living hippocampal slices ex vivo.
Materials and Methods: Mice at peak of experimental autoimmune encephalomyelitis (EAE; n = 29) and healthy control mice (HC; n = 24) were exposed to a cumulative dose of 20 mmol/kg bodyweight of either gadopentetate dimeglumine or gadobutrol (8 injections of 2.5 mmol/kg over 10 days). Magnetic resonance imaging (7 T) was performed at baseline as well as at day 1, 10, and 40 post final injection (pfi) of GBCAs. Mice were sacrificed after magnetic resonance imaging and brain and blood Gd content was assessed by laser ablation-inductively coupled plasma (ICP)-mass spectrometry (MS) and ICP-MS, respectively. In addition, using chronic organotypic hippocampal slice cultures, Gd-induced neurotoxicity was addressed in living brain tissue ex vivo, both under control or inflammatory (tumor necrosis factor α [TNF-α] at 50 ng/μL) conditions.
Results: Neuroinflammation promoted a significant decrease in T1 relaxation times after multiple injections of both GBCAs as shown by quantitative T1 mapping of EAE brains compared with HC. This corresponded to higher Gd retention within the EAE brains at 1, 10, and 40 days pfi as determined by laser ablation-ICP-MS. In inflamed cerebellum, in particular in the deep cerebellar nuclei (CN), elevated Gd retention was observed until day 40 after last gadopentetate application (CN: EAE vs HC, 55.06 ± 0.16 μM vs 30.44 ± 4.43 μM). In contrast, gadobutrol application led to a rather diffuse Gd content in the inflamed brains, which strongly diminished until day 40 (CN: EAE vs HC, 0.38 ± 0.08 μM vs 0.17 ± 0.03 μM). The analysis of cytotoxic effects of both GBCAs using living brain tissue revealed an elevated cell death rate after incubation with gadopentetate but not gadobutrol at 50 mM. The cytotoxic effect due to gadopentetate increased in the presence of the inflammatory mediator TNF-α (with vs without TNF-α, 3.15% ± 1.18% vs 2.17% ± 1.14%; P = 0.0345).
Conclusions: In the EAE model, neuroinflammation promoted increased Gd retention in the brain for both GBCAs. Whereas in the inflamed brains, efficient clearance of macrocyclic gadobutrol during the investigated time period was observed, the Gd retention after application of linear gadopentetate persisted over the entire observational period. Gadopentetate but not gadubutrol appeared to be neurotoxic in an ex vivo paradigm of neuronal inflammation.
In the present work, electron backscatter diffraction was used to determine the microscopic dislocation structures generated during creep (with tests interrupted at the steady state) in pure 99.8% aluminium. This material was investigated at two different stress levels, corresponding to the power-law and power-law breakdown regimes. The results show that the formation of subgrain cellular structures occurs independently of the crystallographic orientation. However, the density of these cellular structures strongly depends on the grain crystallographic orientation with respect to the tensile axis direction, with <111> grains exhibiting the highest densities at both stress levels. It is proposed that this behaviour is due to the influence of intergranular stresses, which is different in <111> and <001> grains.
X-ray absorption spectroscopy (XAS) provides a unique, atom-specific tool to probe the electronic structure of solids. By surmounting long-held limitations of powder-based XAS using a dynamically averaged powder in a Resonant Acoustic Mixer (RAM), we demonstrate how time-resolved in situ (TRIS) XAS provides unprecedented detail of mechanochemical synthesis. The use of a custom-designed dispersive XAS (DXAS) setup allows us to increase the time resolution over existing fluorescence measurements from ∼15 min to 2 s for a complete absorption spectrum. Hence, we here establish TRIS-XAS as a viable method for studying mechanochemical reactions and sampling reaction kinetics. The generality of our approach is demonstrated through RAM-induced (i) bottom-up Au nanoparticle mechanosynthesis and (ii) the synthesis of a prototypical metal organic framework, ZIF-8. Moreover, we demonstrate that our approach also works with the addition of a stainless steel milling ball, opening the door to using TRIS-DXAS for following conventional ball milling reactions. We expect that our TRIS-DXAS approach will become an essential part of the mechanochemical tool box.
A fluorolytic sol–gel method was used for the fast and simple synthesis of small cubic-phase SrF2:Yb3+, Er3+ upconversion (UC) nanocrystals (UCNC) of different composition at room temperature. Systematic studies of the crystal phase and particle size of this Yb3+,Er3+-concentration series as well as excitation power density (P)-dependent UC luminescence (UCL) spectra, UCL quantum yields (ΦUCL), and UCL decay kinetics yielded maximum UCL performance for doping amounts of Yb3+ of 13.5% and Er3+ of 1.3% in the studied doping and P-range (30–400 W cm−2). Furthermore, ΦUCL were determined to be similar to popular β-NaYF4:Yb3+,Er3+. The relative spectral UCL distributions revealed that all UCNC show a strong red emission in the studied doping and P-range (30–400 W cm−2) and suggest that the UCL quenching pathway for unshelled cubic-phase SrF2:Yb3+,Er3+ UCNC differs from the commonly accepted population and depopulation pathways of β-NaYF4:Yb3+,Er3+ UCNC. In SrF2:Yb3+,Er3+ UCNC the 4S3/2 →
4I13/2 transition exhibits a notably stronger sensitivity towards P and reveals increasing values for decreasing Yb3+–Yb3+ distances while the 4I9/2 → 4I15/2 transition is significantly less affected by P and energy migration facilitated UCL quenching. These results emphasize the complexity of the UC processes and the decisive role of the crystal phase and symmetry of the host lattice on the operative UCL quenching mechanism in addition to surface effects. Moreover, the room temperature UCNC synthesis enabled a systematic investigation of the influence of the calcination temperature on the crystal phase of powder-UCNC and the associated UCL properties. Calcination studies of solid UCNC of optimized doping concentration in the temperature range of 175 °C and 800 °C showed the beneficial influence of temperature-
induced healing of crystal defects on UCL and the onset of a phase separation connected with the oxygenation of the lanthanide ions at elevated temperature. This further emphasizes the sensitivity of the UC process to the crystal phase and quality of the host matrix.
We report herein the design of a strip-based rapid test utilizing bioinspired hybrid nanomaterials for the in situ and at site detection of the drug scopolamine (SCP) using a smartphone for readout, allowing SCP identification in diluted saliva down to 40 nM in less than 15 min. For this purpose, we prepared a nanosensor based on mesoporous silica nanoparticles loaded with a fluorescent reporter (rhodamine B) and functionalized with bethanechol, a potent agonist of recombinant human muscarinic acetylcholine receptor M2 (M2-AChR). M2-AChR interaction with the anchored bethanechol derivative leads to capping of the pores. The sensing mechanism relies on binding of SCP to M2-AChR resulting in pore opening and delivery of the entrapped rhodamine B reporter. Moreover, the material was incorporated into strips for lateral-flow assays coupled to smartphone readout, giving fast response time, good selectivity, and exceptional sensitivity. In an attempt to a mobile analytical test system for law enforcement services, we have also developed a dualplex lateral flow assay for SCP and 3,4-methylenedioxypyrovalerone (MDPV) also known as the so-called “cannibal drug”.
Iron-based catalysts are employed in CO2-FTS due to their ability to convert CO2 into CO in a first step and their selectivity towards higher hydrocarbons in a second CO hydrogenation step. According to the literature, iron carbides represent the active phase for hydrocarbon formation and are claimed to emerge in the presence of CO. We propose nanostructured FeOx films as model systems to assess information about the complex phase transformations during CO2-FTS. Mesoporous hematite, ferrihydrite, maghemite, maghemite/magnetite films were exposed to CO2-FTS atmospheres at 20 bar and 300°C. Up to three distinct phases were observed depending on the timeon-stream (TOS): a sintered maghemite/magnetite phase, a carbidic core-shell structure, and a low-crystalline, needle-type oxide phase. Our findings indicate that the formation of an intermediary maghemite/magnetite phase, predominant after short TOS (30 h), precedes the evolution of the carbide phase.
Yet, even after prolonged TOS (185 h), no full conversion into a bulk carbide is observed.
Historically, to tune the properties of a polymer or more general soft matter systems by a second phase is not a new concept and dates back to the 40s of the last century. Beside some successes, the improvement of the properties remained somehow limited. The expectations of the enhancement of the properties of composites changed by the developments of Toyota Central research in the 1990s. It was shown that the incorporation of 5 vol% exfoliated layers of a clay system into a polymer leads to a strong improvement of the mechanical and thermal properties. This discovery stimulated a broad research interest of both fundamental and applied character. Today, polymer-based nanocomposites have reached a billion-dollar global market. The corresponding applications span from components for transportation, commodity plastics with enhanced barrier and/or flame retardancy characteristics, to polymers with electrical properties for shielding, electronics, sensors, and solar cells as well as to live science. Important fields are filled rubbers, reinforced thermoplastics, or thermosets for automotive, aircraft/space and marine industries, but also membranes for separation processes as well as barrier layers, just to mention a few.
For a variety of applications, the molecular mobility in nanocomposites is of great importance. This concerns the molecular mobility needed to form a percolating filler network in rubbers used in tires or in composites employed in electric shielding applications. In general, it is also essential for processing polymer-based nanocomposites. Furthermore, separation processes in composite materials for membranes require a certain molecular mobility. This also concern nanodielectrics used in electrical applications or sensors where the mobility of charge carriers can be related to the fluctuations of molecular groups etc. Finally, the molecular mobility can be taken as probe for structure on a molecular scale.
Broadband dielectric spectroscopy is a powerful tool to investigate the molecular mobility in polymer systems. It is due to the extremely broad frequency and sensitivity range that can be covered by this technique. Information about localized and cooperative molecular fluctuations, polarization effects at interfaces, as well as charge transport processes can be deduced. Therefore, this book focusses on broadband dielectric spectroscopy of composite materials. Moreover, the dielectric studies are accompanied by mechanical spectroscopy, advanced calorimetry, NMR techniques, as well as transmission electron microscopy and X-ray scattering investigations.
Besides a brief introduction to (nano)composites, the book aims to address fundamental aspects of the molecular mobility in this innovative group of materials. Selected examples with scientific interest and some cases with high industrial impact were chosen. Due to the breadth of the subject, unfortunately not all topics could be addressed in detail, such as processing for instance.
Berlin, Andreas Schönhals
July 2021 Paulina Szymoniak
Editorial for special issue "Formation of sulfate minerals in natural and industrial environments"
(2022)
Sulfate is abundant in the environment and, as a result, sulfate-containing minerals constitute a large and important focus of research. These minerals play an important role in many geochemical and industrial processes, including the sulfur cycle, the construction industry (e.g., plaster of Paris), fault tectonics, acid mine drainage, and even rare biominerals. Important to note are the abundant amounts of sulfate (minerals) located on the surface of Mars, and in meteorites, extending the relevance of this mineral group beyond the realm of our planet. In geological systems, sulfate minerals such as barite are also important for indicating certain sedimentation environments. In this regard, sulfate deposits can be used to evaluate the redox state of ancient oceans during early Earth time periods.
Current trends in materials and life sciences are flanked by the need to push detection limits to single molecules or single cells, enable the characterization of increasingly complex matrices or sophisticated nanostructures, speed up the time of analysis, reduce instrument complexity and costs, and improve the reliability of data. This requires suitable analytical tools such as spectroscopic, separation and imaging techniques, mass spectrometry, and hyphenated techniques as well as sensors and their adaptation to application-specific challenges in the environmental, food, consumer product, health sector, nanotechnology, and bioanalysis. Increasing concerns about health threatening known or emerging pollutants in drinking water, consumer products, and food and about the safety of nanomaterials led to a new awareness of the importance of analytical sciences. Another important driver in this direction is the increasing demand by legislation, particularly in view of the 17 sustainable development goals by the United Nations addressing clean energy, industry, and innovation, sustainable cities, clean water, and responsible consumption and production. In this respect, also the development of analytical methods that enable the characterization of material flows in production processes and support recycling concepts of precious raw materials becomes more and more relevant. In the future, this will provide the basis for greener production in the chemical industry utilizing recycled or sustainable starting materials.
This makes analytical chemistry an essential player in terms of the circular economy helping to increase the sustainability of production processes. In the life sciences sector, products based on proteins, such as therapeutic and diagnostic antibodies, increase in importance. These increasingly biotechnologically produced functional biomolecules pose a high level of complexity of matrix and structural features that can be met only by highly advanced methods for separation, characterization, and detection. In addition, metrological traceability and target definition are still significant challenges for the future, particularly in the life sciences.
However, innovative reference materials as required for the health and food sector and the characterization of advanced materials can only be developed when suitable analytical protocols are available. The so-called reproducibility crisis in sciences underlines the importance of improved measures of quality control for all kinds of measurements and material characterization. This calls for thorough method validation concepts, suitable reference materials, and regular interlaboratory comparisons of measurements as well as better training of scientists in analytical sciences.
The important contribution of analytical sciences to these developments is highlighted by a broad collection of research papers, trend articles, and critical reviews from these different application fields. Special emphasis is dedicated to often-overlooked quality assurance and reference materials.
The concept behind this Research Topic (RT) was to collect works, in which Atomic Force Microscopy (AFM) techniques are employed to study tribological phenomena and to push the resolution of measurements towards single asperity contact. Thanks to the direct determination of sample height with sub-nanometer resolution and the possibility of measuring local friction, AFM can be employed after a tribotest to detect topography and friction changes at the nanometer scale. Recently, efforts are being expended to use AFM cantilevers as tribometers, i.e., as probes altering the volume of suitable samples, thereby measuring tip and/or sample wear and friction at the nano/microscale. Thus, single asperity contact, friction, and wear can be investigated. Since friction and wear at the macroscale are the result of asperities interactions, such experiments are of great importance for better understanding of tribological processes.
Understanding the origins of intrinsic stress in Si nanowires (NWs) is crucial for their successful utilization as transducer building blocks in next-generation, miniaturized sensors based on anoelectromechanical systems (NEMS). With their small size leading to ultrahigh-resonance frequencies and extreme surface-to-volume ratios, silicon NWs raise new opportunities regarding sensitivity, precision, and speed in both physical and biochemical sensing. With silicon optoelectromechanical properties strongly dependent on the level of NW intrinsic stress, various studies have been devoted to the measurement of such stresses generated, for example, as a result of harsh fabrication processes. However, due to enormous NW surface area, even the native oxide that is conventionally considered as a benign surface condition can cause significant stresses. To address this issue, a combination of nanomechanical characterization and atomistic simulation approaches is developed. Relying only on low-temperature processes, the fabrication approach yields monolithic NWs with optimum boundary conditions, where NWs and support architecture are etched within the same silicon crystal. Resulting NWs are characterized by transmission electron microscopy and micro-Raman spectroscopy. The interpretation of results is carried out through molecular dynamics simulations with ReaxFF potential facilitating the incorporation of humidity and temperature, thereby providing a close replica of the actual oxidation environment - in contrast to previous dry oxidation or self-limiting thermal oxidation studies. As a result, consensus on significant intrinsic tensile stresses on the order of 100 MPa to 1 GPa was achieved as a function of NW critical dimension and aspect ratio. The understanding developed herein regarding the role of native oxide played in the generation of NW intrinsic stresses is important for the design and development of silicon-based NEMS.
MIKE III apparatus tests were conducted to investigate the minimum ignition energy (MIE) of coal dusts in air and O2/CO2 atmospheres with and without small amount of CH4/H2. The O2 mole fraction (XO2) in the gas mixtures varied from 21% to 50% with the CH4/H2 mole fraction from 0 to 2%. Experimental result showed that MIE of coal dusts significantly decreases even by three orders of magnitude in mJ with increasing XO2 and the addition of CH4/H2. Compared with CH4, H2 had a relatively strong promotion effect on the spark ignition of coal dusts. The inhibiting effect of CO2 was found to be much stronger than N2, but this inhibiting effect of CO2 could be eliminated by 9% increment of XO2. The effect on MIE of coal dusts thus followed by the order: 9% increment of XO2 > CO2 replacing N2 > 2% CH4 or H2 addition. Moreover, two empirical models were used to estimate the MIE of hybrid dust-gas mixture (HMIE), and the results showed that calculated data can well reflect the promoting effect of elevated XO2 and flammable gas addition, and the inhibiting effect of inert gas
microscopy (AFM), or X-ray reflectometry. For the additional determination of thin film composition, techniques like X-ray photoelectron spectroscopy (XPS) or mass spectrometry-based techniques can be used. An alternative non-destructive technique is electron probe microanalysis (EPMA). This method assumes a sample of homogenous (bulk) chemical composition, so that it cannot be usually applied to thin film samples. However, in combination with the thin film software StrataGEM, the thickness as well as the composition of such films on a substrate can be determined.
This has been demonstrated for FeNi on Si and SiGe on Al2O3 film systems. For both systems five samples with different elemental composition and a reference were produced and characterised by Korean research institute KRISS using inductively coupled plasma mass spectrometry (ICP-MS), Rutherford backscattering (RBS), and transmission electron microscopy (TEM). These samples were used for an international round robin test.
In 2021, a new and open-source thin film evaluation programme called BadgerFilm has been released. It can also be used to determine thin film composition and thickness from intensity ratios of the unknown sample and standards (k-ratios).
In this contribution, we re-evaluated the data acquired for the FeNi and SiGe systems using the BadgerFilm software package and compared the resulting composition and thickness with the results of the established StrataGEM software and other reference methods. With the current evaluation, the BadgerFilm software shows good agreement with the composition and thickness calculated by StrataGEM and as the reference values provided by the KRISS.
A competitive advantage in the semiconductors industry is gained through the exploitation of new materials and processes, translating into improved components’ performances. This requires a metrological infrastructure allowing reliable nanoscale characterisation of new materials and devices, particularly in terms of their electrical parameters and properties. Traceability and reliability of nanoscale measurements stand as a major challenge for electrical properties (i.e. resistance, impedance) using conductive atomic force microscopy (C-AFM) and scanning microwave microscopy (SMM) techniques. The non-destructive analysis nature of these two methods is of paramount importance for the characterization of devices and components. However, the state of the art still lacks established measurement protocols, easy to use reference standards, well-defined best practice guides and easy to use 3D models to assess environmental and external stimulation effects. Moreover, costly instrumentation, particularly for high-frequency measurements, still hinders efficient advancements in these directions.
ELENA is a 3-years European project that aims at bringing solutions to the aforementioned difficulties. To achieve this goal, the project uses a combination of nanoscale electrodynamic scanning probe methods in combination with optical tools such as spectroscopic ellipsometry on several lateral length scales to determine the electrical properties of layers and small structures.
The main outcomes of the EMPIR project nPSize are presented and the suitability of the new capabilities, e.g. reference materials, sample preparation protocols, measurement procedures, and data analysis, to be standardized and implemented in accredited analytical laboratories is discussed. Complementation and/or filling gaps of published and ongoing standardisation projects on size, shape and number concentration measurements under ISO/TC 229/JWG 2 are offered.
The two VAMAS inter-laboratory comparisons resulted from the nSPize project and just started under TWA 34 Nanoparticle Populations (Projects #15 and #16) of bipyramidal TiO2 anatase and bimodal SiO2 nanoparticles are presented in detail.
Im Rahmen des EMPIR-Projektes NanoXSpot (Nanometre X-ray Focal Spot Measurement) werden rückführbare Messverfahren zur Bestimmung der Brennfleckgröße und -form von Röntgenröhren im Bereich von 100 nm bis 10 mm entwickelt, welche die Grundlage für die Erarbeitung mehrerer Normentwürfe bilden. Diese werden 2022 parallel bei ISO TC 135 (NDT) SC 5 (RT) und CEN TC 138 (NDT) WG 1 (RT) eingereicht. Entsprechende Normen werden auch bei ASTM vorgestellt. Die Norm EN 12543-4 (Kantenmethode) wird umgeschrieben für die Messung von Brennflecken von 1 μm – 10 mm durch Auswertung von Loch- oder Scheibenaufnahmen. Der im Rahmen des NanoXSpot-Projektes neu entwickelte NxS-Testkörper ist geeignet für den Bereich von 1 μm – 100 μm. Von 100 μm bis 10 mm können ASTM-Lochtestkörper verwendet werden, die bereits bei ASTM E 1165 beschrieben sind. Neu ist die Anwendung eines CT-Algorithmus zur Rekonstruktion der Brennflecke, um Lochblenden-basierte Brennfleckkameras, insbesondere im Bereich unter 100 μm, zu ersetzen. Ein neuer Normteil, EN 12543-6, wurde entworfen, um die Brennfleckmessung im Bereich 100 nm – 20 μm mit hoher Genauigkeit zu ermöglichen. Verschiedene Strichgruppen-Testkörper kommen hier zum Einsatz. Das sind die JIMAPrüfkörper, ein neuer Hochkontrast-Strichgruppentestkörper von YXLON (HiCo) und der neu entwickelte Testkörper NxS. Diese werden vorgestellt. Die Messprozedur für Röhrenhersteller wird auf einer numerischen Fit-Prozedur basieren, die über einen Ringversuch im Projekt validiert wurde. Beide Normen benötigen numerische Auswertealgorithmen zur korrekten Anwendung, die als kommerzielle Software und Public Domain – Software verfügbar gemacht werden. Es wird über die zu erwartenden Standardprozeduren und die erforderliche Hardware zur Anwendung der Normen informiert.
Im Rahmen des EMPIR-Projektes NanoXSpot (Nanometre X-ray Focal Spot Measurement) werden rückführbare Messverfahren zur Bestimmung der Brennfleckgröße und -form von Röntgenröhren im Bereich von 100 nm bis 10 mm entwickelt, welche die Grundlage für die Erarbeitung mehrerer Normentwürfe bilden. Diese werden 2022 parallel bei ISO TC 135 (NDT) SC 5 (RT) und CEN TC 138 (NDT) WG 1 (RT) eingereicht. Entsprechende Normen werden auch bei ASTM vorgestellt. Die Norm EN 12543-4 (Kantenmethode) wird umgeschrieben für die Messung von Brennflecken von 1 μm – 10 mm durch Auswertung von Loch- oder Scheibenaufnahmen. Der im Rahmen des NanoXSpot-Projektes neu entwickelte NxS-Testkörper ist geeignet für den Bereich von 1 μm – 100 μm. Von 100 μm bis 10 mm können ASTM-Lochtestkörper verwendet werden, die bereits bei ASTM E 1165 beschrieben sind. Neu ist die Anwendung eines CT-Algorithmus zur Rekonstruktion der Brennflecke, um Lochblenden-basierte Brennfleckkameras, insbesondere im Bereich unter 100 μm, zu ersetzen. Ein neuer Normteil, EN 12543-6, wurde entworfen, um die Brennfleckmessung im Bereich 100 nm – 20 μm mit hoher Genauigkeit zu ermöglichen.
Verschiedene Strichgruppen-Testkörper kommen hier zum Einsatz. Das sind die JIMAPrüfkörper, ein neuer Hochkontrast-Strichgruppentestkörper von YXLON (HiCo) und der neu entwickelte Testkörper NxS. Diese werden vorgestellt. Die Messprozedur für Röhrenhersteller wird auf einer numerischen Fit-Prozedur basieren, die über einen Ringversuch im Projekt validiert wurde. Beide Normen benötigen numerische Auswertealgorithmen zur korrekten Anwendung, die als kommerzielle Software und Public Domain – Software verfügbar gemacht werden. Es wird über die zu erwartenden Standardprozeduren und die erforderliche Hardware zur Anwendung der Normen informiert.
Im Rahmen des EMPIR-Projektes NanoXSpot (Nanometre X-Ray Focal Spot Measurement) werden rückführbare Messverfahren zur Bestimmung der Brennfleckgröße und -form von Röntgenröhren mit Submikrometerauflösung (100 nm – 20 μm) entwickelt, die die Grundlage für die Erarbeitung eines Standardentwurfes bilden. Der Standardentwurf wird bei CEN TC 138 (Non-destructive testing) WG 1 (Radiographic testing) eingereicht und mit ISO und ASTM harmonisiert. Zur Untersuchung der entwickelten Methoden (Brennfleck-CT, Fit-Prozedur für Strichgruppenkörper) und des im Projekt NanoXSpot neu entworfenen Testkörpers, NxS, wurde ein Ringversuch durchgeführt. Dabei wurde sowohl der angestrebte Überlappungsbereich mit EN 12543 Teil 5 (Messung der effektiven Brennfleckgröße von Mini- und Mikrofokus-Röntgenröhren) und ASTM E 2903 (Standard Test Method for Measurement of the Effective Focal Spot Size of Mini and Micro Focus X-ray Tubes) für Brennflecke >5 μm als auch Brennflecke <5 μm untersucht. Im Mittelpunkt standen dabei Stabilität und Wiederholbarkeit der entwickelten Methoden zur Bestimmung der Brennfleckgröße. In diesem Beitrag werden die Ergebnisse des durchgeführten Ringversuches vorgestellt und diskutiert, um Schlussfolgerungen und Empfehlungen für die Vorbereitung eines erweiterten Ringversuchs mit Partnern und Stakeholdern abzuleiten.
Nanopillars of ZnO were implanted with Au-400 keV ions at various ion fluences from 1 × 1015 cm−2 to 1 × 1016 cm−2 and subsequently annealed at 750 °C for 15 min in order to reduce the implantation damage and to support Au nanoparticle (NP) aggregation. It was found that implantation-induced effects and thermal effects influence the Au NP coalescence as well as the quality of the ZnO nanopillars. Rutherford Back-Scattering spectrometry (RBS) showed the broader Au-depth profiles than it was theoretically predicted, but the Au-concentration maximum agrees well with prediction taking into account the effective ZnO layer density. The implantation at the higher fluences induced the morphology modification of the nanopillar layer evidenced by RBS and scanning electron microscopy (SEM). An indirect evidence of this effect was given by optical ellipsometry due to gradual refractive index changes in the ZnO nanopillars with the increased Au-ion fluence. Optical characterization of the Au-implanted and annealed nanopillars performed by means of photoluminescence (PL) and diffuse-reflectance spectroscopy (DRS) evidenced the surface plasmon resonance (SPR) activity of the embedded Au NPs. The SPR-enhanced scattering and PL emission observed in the spectral range 500–650 nm are ascribed to Au NPs or more complex Au-clusters. In addition, the ellipsometry measurements of extinction coefficient are found to corroborate well results from DRS, both indicating increase of SPR effect with the increase of Au-ion fluence and after the post-annealing.
The overall interest in nanotoxicity, triggered by the increasing use of nanomaterials in the material and life sciences, and the synthesis of an ever increasing number of new functional nanoparticles calls not only for standardized test procedures1,2 and for efficient approaches to screen the potential genotoxicity of these materials, but also for standardized and validated methods for surface analysis.
4,5 The analysis and quantification of surface chemistry is hence in the focus of an increasing number of standardization organizations and interlaboratory comparisons with different analytical methods are being done.5 For the monitoring of nanomaterial synthesis and the fast assessment of the number of functional groups such as carboxyl and amino functionalities, which are very commonly used functionalities in the life sciences, simple and validated methods are needed that can be performed with common laboratory instrumentation. 5,6 Here we provide a brief overview of the ongoing research in division Biophotonics employing quantitative NMR (qNMR), conductometry, and colorimetric and fluorometric optical assays for the determination of the total and the accessible number of carboxyl and amino groups on differently sized polymer and silica nano- and microparticles.5-7
Filigree structures can be manufactured via two-photon-polymerization (2PP) operating in the regime of non-linear light absorption. For the first time it is possible to apply this technique to the powder processing of ceramic structures with a feature size in the range of the critical defect size responsible for brittle fracture and, thus, affecting fracture toughness of high-performance ceramics. In this way, tailoring of advanced properties can be achieved already in the shaping process. Traditionally, 2PP relies on transparent polymerizable resins, which is diametrically opposed to the usually completely opaque ceramic resins and slurries. Here we present a transparent and photocurable suspension of nanoparticles (resin) with very high mass fractions of yttria-stabilized zirconia particles (YSZ). Due to the extremely well dispersed nanoparticles, scattering of light can be effectively suppressed at the process-relevant wavelength of 800 nm. Sintered ceramic structures with a resolution of down to 500 nm were obtained. Even at reduced densities of 1 to 4 g/cm³, the resulting compressive strength with 4,5 GPa is equivalent or even exceeding bulk monolithic yttria stabilized zirconia. A ceramic metamaterial is born, where the mechanical properties of yttria stabilized zirconia are altered by changing geometrical parameters and gives access to a new class of ceramic materials.
Es werden Methoden zur sicherheitstechnischen Bewertung des mechanischen Verhaltens von Brennstabhüllrohren entwickelt, um sprödes Versagen in Belastungsszenarien nach längerfristiger trockener Zwischenlagerung zu verhindern. Unbestrahlte Brennstabhüllrohrsegmente aus der Zirkoniumlegierung ZIRLO® wurden hydriert und thermomechanischen Behandlungen unterzogen, um Hüllrohrmaterial durch Ausscheidung radialer Hydride zu verspröden. Die Proben mit radialen Hydriden wurden im Ring Compression Test (RCT) bei Raumtemperatur untersucht. Bereits bei kleinen Probenverformungen wurden abrupte Kraftabfälle mit instabiler Rissausbreitung durch das Netzwerk radialer Hydride beobachtet. Die Risslängen erreichten in einigen Fällen bis zu 90 % der Wanddicke. Der mikromechanische Versagensmechanismus ist Quasi-Spaltbruch in den Hydriden und Porenbildung, -wachstum und -vereinigung in der Zirkoniummatrix an den duktilen Brücken zwischen benachbarten Hydriden. Es wurde ein Finite-Elemente-Modell des Ring Compression Tests erstellt, um das Versagensverhalten zirkoniumbasierter Legierungen mit radialen Hydriden im RCT zu analysieren. Die Fließkurve für das elastisch-plastische Materialmodell des Matrixmaterials wurde durch eine inverse Finite-Elemente-Analyse ermittelt. Kohäsivzonenmodelle wurden benutzt, um die plötzlichen Kraftabfälle zu reproduzieren. Es wurde ein mikromechanisches Modell mit statistisch generierten Matrix-Hydrid-Verteilungen entwickelt, das zwischen sprödem Versagen entlang der Hydride und duktilem Versagen der Zirkoniummatrix in der Kohäsivzone unterscheidet. Für das jeweilige Materialverhalten wird ein lokales zweiparametriges Versagenskriterium auf Grundlage der Kohäsionsfestigkeit und der Separationsenergie bei einer festgelegten Form des Kohäsivgesetzes vorgeschlagen. Geeignete Kohäsivparameter lassen sich mit einer inversen Finite-Elemente-Analyse des Versagensverhaltens von hydrierten Proben im Ring Compression Test bestimmen. In den Simulationen lag der Schwerpunkt auf dem ersten Kraftabfall. Die Berechnungsergebnisse stimmen gut mit den RCT-Ergebnissen überein. Es konnte gezeigt werden, dass die Rissinitiierung und -ausbreitung stark von der speziellen Anordnung der radialen Hydride und Matrixbrücken in der Bruchzone abhängt. Die numerische Modellbildung wurde an Versuchen mit bestrahlten Proben aus der Zirkoniumlegierung M5® validiert.
Epoxy-Based Nanocomposites—What Can Be Learned from Dielectric and Calorimetric Investigations?
(2022)
Epoxy-based nanocomposites are promisingmaterials for industrial applications (i.e., aerospace, marine, and automotive industries) due to their extraordinary mechanical and thermal properties. Regardless of the broad field of applications, there is still a considerable need to identify their structure–property relationships. Here, a detailed dielectric and calorimetric (DSC and fast scanning calorimetry) study on different epoxy-based nanocomposites was performed. Bisphenol A diglycidyl ether (DGEBA) cured with diethylenetriamine (DETA) was employed as the polymeric matrix, which was reinforced with three diverse nanofillers that exhibit different interaction strengths with the epoxy matrix (halloysite nanotubes, surface modified halloysite nanotubes, and taurine-modified layered double hydroxide). The structure, molecular mobility, and vitrification behavior are discussed in detail, focusing on the intrinsic structural and dynamic heterogeneity, as well as interfacial properties.
Equilibrium model of titanium laser induced plasma in air with reverse deposition of titanium oxides
(2022)
A chemical-hydrodynamic model of laser induced plasma is developed to study a process of deposition of titanium oxides from titanium laser induced plasma to the titanium target surface. The model is relevant to texturing and coating of titanium bone implants that is done by scanning the ablation laser across implant surfaces. Such the procedure improves the biocompatibility and durability of the implants. The model considers plasma chemical reactions, formation of condensed species inside the plasma plume, and deposition and accumulation of these species on the ablation surface. A chemical part of the model is based on minimization of Gibbs free energy of the chemical system; it is used to calculate the chemical composition of the plasma. A hydrodynamic part uses the 2D fluid-dynamic equations that model a 3D axisymmetric plasma plume and assumes the mass and energy exchange between the plasma and the surface. The initial parameters for the model are inferred from experiment.
The model shows that condensed titanium oxides, mostly TiO2, form in a peripheral plasma zone and gradually adhere to the surface during the plasma plume evolution. The model predicts the major component and thickness of the deposit and can be applied for the optimization of experiments aimed at surface modification.