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Eingeladener Vortrag
- nein (126)
This study presents the synthesis and characterization of zwitterionic core–shell hybrid nanoparticles consisting of a core of iron oxide multicore nanoparticles (MCNPs, γ-Fe2O3) and a shell of sultonated poly(2-vinylpyridine-grad-acrylic acid) copolymers. The gradient copolymers are prepared by reversible addition fragmentation chain transfer polymerization of 2-vinylpyridine (2VP), followed by the addition of tert-butyl acrylate and subsequent hydrolysis. Grafting of P(2VP-grad-AA) onto MCNP results in P(2VP-grad-AA)@MCNP, followed by quaternization using 1,3-propanesultone-leading to P(2VPS-grad-AA)@MCNP with a zwitterionic shell. The resulting particles are characterized by transmission electron microscopy, dynamic light scattering, and thermogravimetric analysis measurements, showing particle diameters of ≈70–90 nm and an overall content of the copolymer shell of ≈10%. Turbidity measurements indicate increased stability toward secondary aggregation after coating if compared to the pristine MCNP and additional cytotoxicity tests do not reveal any significant influence on cell viability.
Water and aqueous reagents are essential in any biological process or system. But apart from a few special low vapor-pressure cases, liquids have not been accessible to any technique requiring UHV conditions. EnviroESCA opens up this exciting field of applications.
In this paper first results from water based samples are presented as a proof of concept to demonstrate the special capabilities of EnviroESCA analyzing liquid samples. The following solutions were investigated under near ambient pressure conditions: i.) water, ii.) brine, iii.) an oil in water dispersion, iv.) aqueous iron(II) sulfate heptahydrate, and v.) a suspension of nano silver particles in water.
Sol-gel synthesis was used to prepare nanoparticles of MgF2 and CaF2. These nanoparticles were tested for their application in wood protection. In comparison to control samples, wood specimens treated with MgF2 and CaF2 showed lower mass loss under exposure to termites and fungi. Samples treated with MgF2 performed better at protecting wood from cellulose degradation when exposed to termites. Conversely, in the presence of fungi, mass loss in treated samples was similar irrespective of the chemical composition (MgF2 and CaF2) of the treatment. A possible explanation for this difference in results between termites and fungi could be their different mechanism of cellulose hydrolysis. Thus, future wood preservatives would need to be customized according to their specific application.
Over the last decade nanoparticles are progressively included in products of our daily life. Due to their antimicrobial properties, silver nanoparticles are used in a high variety of consumer products ranging from food containers over medicine and textiles. Therefore, research on the toxicological potential of nanosilver becomes increasingly important. This includes investigations concerning uptake, distribution and excretion of the particles. However, little attention was paid to changes of physical and chemical properties of the particles in the human body. One of the most important questions is if the particles can pass the digestion process without altering their shape and size. In this study we report on a versatile system of ultra-small silver nanoparticles with a mean volume weighted radius of 3.1 nm and a narrow size distribution width of 20%. The nanoparticles’ coating of poly (acrylic acid) can easily be exchanged by biocompatible ligands like albumin or glutathione. The particles are thoroughly characterized by small angle X-ray scattering (SAXS), DLS, IR and UV/Vis spectroscopy. We used the particles in an artificial digestion procedure which mimics the gastro-intestinal passage (Figure 1). Thereby the changes in the size distribution during the digestion process were analytically monitored by SAXS. Additionally, we used as food components oil, starch, skimmed milk powder and mixture thereof to provide a preferably realistic environment. Large aggregates of up to 56 nm were formed in the absence of food additives. In contrast, the presence of oil and starch limit the radii of aggregates to about 10 nm. Milk powder shows strong protective properties resulting in only small aggregates of 6 nm radii. Our results indicate that silver can indeed pass the digestion process in a nanoscale form depending on the nanoparticle coating and additional ingredients. These results have an impact on future toxicological considerations regarding silver nanoparticle-containing consumer products.
Volume specific surface area (VSSA) by BET: concept and demonstration on industrial materials
(2017)
Volume specific surface area (VSSA) as measured by BET constituites a simple and reliable solution to (most) powders. Porous, coated, polydisperse/multimodal materials are to be treated with care, i.e. doubled by analysis with electron microscopy or more advanced BET analysis (e.g. t-plot)for each material in part.
The current review focuses on vesicles obtained from the self-assembly of two types of dendritic macromolecules, namely amphiphilic Janus dendrimers (forming dendrimersomes) and amphiphilic dumbbells. In the first part, we will present some synthetic strategies and the various building blocks that can be used to obtain dendritic-based macromolecules, thereby showing their structural versatility. We put our focus on amphiphilic Janus dendrimers and amphiphilic dumbbells that form vesicles in water but we also encompass vesicles formed thereof in organic solvents. The second part of this review deals with the production methods of these vesicles at the nanoscale but also at the microscale. Furthermore, the influence of various parameters (intrinsic to the amphiphilic JD and extrinsic—from the environment) on the type of vesicle formed will be discussed. In the third part, we will review the numerous biomedical applications of these vesicles of nano- or micron-size.
Aufgrund von Erfahrungen mit Stäuben mit Partikelgrößen im Mikrometerbereich ist bekannt, dass Stoffe mit abnehmender Partikelgröße kritischer einzustufen sind, da z.B. maximaler Explosionsdruck (pmax), maximaler zeitlicher Druckanstieg (dp/dtmax) und Zündempfindlichkeit durch die Zunahme der reaktiven Oberfläche des Staubes zunehmen. Eine Übersicht des Verlaufes der Explosionsauswirkungen metallischer Stäube vom Mikrometerbereich bis in den Nanometerbereich konnte bislang nur vereinzelt durch wenige Ergebnisse gegeben werden.
Dieser Beitrag präsentiert einen detaillierten Überblick über das Explosionsverhalten von Metallstäuben vom Mikrometer- bis in den Nanometerbereich. Hierfür wurden verschiedene Metallstäube untersucht und deren Explosionsauswirkungen in Abhängigkeit der mittleren Primärteilchengröße entweder durch BET-Messungen, Partikelgrößenverteilung oder REM-Mikroskopie bestimmt. Um den Verlauf des Explosionsverhaltens für diese Metalle darzustellen, wurde einerseits eine umfangreiche Literaturrecherche durchgeführt. Darüber hinaus wurden die im Rahmen deutscher und französischer Forschungsprogramme durchgeführten experimentellen Untersuchungen genutzt, um insbesondere die Datenlage für nanoskalig hergestellte Stäube zu verbessern. Auch bei Metallstäuben im Allgemeinen führt eine Verringerung der Teilchengröße zu einem kritischeren Verhalten der Stäube. Es scheint jedoch, dass diese Aussage nur bis zu einem kritischen Durchmesser gilt, unterhalb dessen die Auswirkungen einer Explosion (pmax, dp/dtmax) für alle betrachteten Stäube wieder abnehmen. Diese kritische Größe kann durch theoretische Überlegungen zur Art der thermischen Übertragung in der Flamme erklärt werden. Der Einfluss der Schlüsselparameter wird in diesem Beitrag ebenfalls diskutiert, um die Mechanismen besser zu verstehen und das Verständnis letztendlich auch auf andere pulverförmige Materialien auszudehnen.
UCST-type thermoresponsive polymers (i.e. that phase separate from solution upon cooling) present a tremendous potential not only in aqueous media where they can be used in drug delivery, diagnostic and microfluidic applications, but also in water/alcohol mixtures, where they can be used for instance in sensing systems for alcohol-soluble drugs. However, only a few thermoresponsive polymers have been reported that present an UCST in a relevant temperature range and “green” solvents such as water or ethanol.
In this context, acrylamide-based monomers can be very useful building blocks for designing novel non-ionic UCST-type polymers because of their hydrophilic nature (with the appropriate side chain) and propensity to form hydrogen bonds. We will present our latest results on the UCST-type thermoresponsive behaviour of acrylamide- and 2,6-diaminopyridine-based homopolymers and copolymers in water or water/alcohol mixtures, and give some insights about the rational design of UCST polymers relying on H-bonding.
UCST-type thermoresponsive polymers (i.e. that phase separate from solution upon cooling) present a tremendous potential not only in aqueous media where they can be used in drug delivery, diagnostic and microfluidic applications, but also in water/alcohol mixtures, where they can be used for instance in sensing systems for alcohol-soluble drugs. However, only a few thermoresponsive polymers have been reported that present an UCST in a relevant temperature range and “green” solvents such as water or ethanol.
In this context, acrylamide-based monomers can be very useful building blocks for designing novel non-ionic UCST-type polymers because of their hydrophilic nature (with the appropriate side chain) and propensity to form hydrogen bonds. We will present our latest results on the UCST-type thermoresponsive behaviour of acrylamide- and 2,6-diaminopyridine-based homopolymers and copolymers in water or water/alcohol mixtures, and give some insights about the rational design of UCST polymers relying on H-bonding.
Advances in functional coatings, batteries, innovative organic electronics, and hybrid materials depend strongly on polymeric materials confined in thin films or adsorbed at surfaces. Subsequently, understanding the materials behavior under confinement and the deviations, from the bulk, that might arise is necessary for optimized technological applications. In the nanometer vicinity, solid interfaces and free surfaces could alter for instance entanglements, glassy dynamics (α-relaxation), and the thermal glass transition temperature (Tg), compared to the bulk behavior. Consequently, this could change macroscopic quantities of thin films like adhesion, wettability, friction, reactivity, and biocompatibility, which are topical problems for hybrid materials. In fact, despite the intense investigations on thin homopolymers films, little is known about polymer blend thin films and how blending affect glass dynamics and glass transition, under confinement.
This work discusses the glassy dynamics of thin films of Poly (vinyl methyl ether) (PVME) with special focus to the dynamics near the interfaces. Further, PVME is then blended with the well-studied polystyrene (PS) in two concentrations; 50:50 and 25:75 wt-%, which are miscible in bulk. The glass dynamics of thin films of both blend concentration are then investigated. Here, a combination of nanosized relaxation spectroscopies; broadband dielectric spectroscopy (BDS) and specific heat spectroscopy (SHS); employing AC nanochip calorimetry, was utilized to probe the glassy dynamics of the thin films, thickness: 7nm – 200 nm. It should be noted that both methods are sensitive to different probes; where SHS senses entropy fluctuations while BDS measures dipole fluctuations. For BDS measurements, a recently developed nano-structured electrode sample arrangement was employed; where ultra-thin films are spin-coated on an ultra-flat highly conductive silicon wafer, sandwiched between a wafer with nanostructured SiO2 nano-spacers with heights between 35 nm and 70 nm. Furthermore, these measurements are then combined with surface analytical techniques; ellipsometry and AFM, for controlled film thickness and topography.
Probing of PVME thin films revealed the existence of an adsorbed layer with a restricted mobility at the polymer/substrate interface, which is independent from the bulk-like behavior and thickness independent. As for PVME/PS thin films, it was shown that the overall segmental dynamics of both blends are strongly affected by a fine counter-balance between a free surface layer at the polymer/air interface, which is PVME-rich layer, and an adsorbed layer at the polymer/substrate interface, which is PS-rich. This is the first example where confinement induced changes were observed by BDS for ultra-thin films. All results were analyzed in details and will be comprehensively discussed.
In thin polymer films, little is known about the dynamics of the adsorbed layers, despite their importance in innovative applications. Here, Broadband Dielectric Spectroscopy (BDS) was utilized to investigate the glassy dynamics of thin films of a low MW Poly (vinyl methyl ether) (PVME) (thicknesses: 7 – 160 nm). A recently developed nano-structured capacitor arrangement was employed; where a silicon wafer with nanostructured SiO2 nano-spacers, with heights of 35 nm and 70 nm, is placed on top of a thin film spin coated on an ultra-flat highly conductive silicon wafer. Further, PVME/SiO2 interactions was confirmed by contact angle measurements, hence an adsorbed layer is allowed to form. For films with thicknesses smaller than 50 nm, BDS measurements showed two relaxation processes. The first process coincided, in its position and temperature dependence, with the -relaxation of bulk PVME, thus it was assigned to the -relaxation of a bulk-like layer. The second process showed a different temperature dependence and was ascribed to the relaxation of polymer segments adsorbed at the substrate. Both processes showed no thickness dependence. The results will be discussed in detail. To our knowledge, this is the first study of the segmental dynamics of an adsorbed layer in thin films.
A combination of nanosized dielectric relaxation (BDS) and thermal spectroscopy (SHS) was utilized to characterize the dynamics of thin films of Poly(vinyl methyl ether) (PVME) (thicknesses: 7 nm – 160 nm). For the BDS measurements, a recently designed nano-structured electrode system is employed. A thin film is spin-coated on an ultra-flat highly conductive silicon wafer serving as the bottom electrode. As top electrode, a highly conductive wafer with non-conducting nanostructured SiO2 nano-spacers with heights of 35 nm or 70 nm is assembled on the bottom electrode. This procedure results in thin supported films with a free polymer/air interface. The BDS measurements show two relaxation processes, which are analyzed unambiguously for thicknesses smaller than 50 nm. The relaxation rates of both processes have different temperature dependencies. One process coincidences in its position and temperature dependence with the glassy dynamics of bulk PVME and is ascribed to the dynamic glass transition of a bulk-like layer in the middle of the film. The relaxation rates were found to be thickness independent as confirmed by SHS. Unexpectedly, the relaxation rates of the second process obey an Arrhenius-like temperature dependence. This process was not observed by SHS and was related to the constrained fluctuations in a layer, which is irreversibly adsorbed at the substrate with a heterogeneous structure. Its molecular fluctuations undergo a confinement effect resulting in the localization of the segmental dynamics. To our knowledge, this is the first report on the molecular dynamics of an adsorbed layer in thin films.
Die vorliegende Untersuchung befasst sich mit der Frage, inwieweit mit Füllstoff angereicherte Klebstoffe für die Restaurierung von Flachgläsern mit größeren Defekten oder als Ergänzungsmaterial geeignet sind. Hierzu werden verschiedene silikatische Füllstoffe untersucht und in ausgewählte Glasklebstoffe eingearbeitet. Die Zugabe der Füllstoffe ermöglicht eine gezielte Eigenschaftssteuerung von z.B. Viskosität oder Härte. Die eingesetzten Füllstoffe werden hinsichtlich ihrer Zusammensetzung und Korngröße charakterisiert und mikroskopisch betrachtet. Die optimale Dispergierung der Füllstoffe in die Klebstoffe wird ermittelt und in Testreihen überprüft.
Die angefertigten gefüllten Klebstoffe werden durch Farb- und UV-VIS Messungen charakterisiert. REM-Aufnahmen geben Aufschluss über die Verteilung der Füllstoffe im Klebstoff. Tests zur Biegefestigkeit sowie die Durchführung dynamisch-mechanischer Analysen (DMA) ermöglichen Aussagen zum Alterungsverhalten der Klebstoffe. Dazu werden die Prüfkörper vor und nach der Alterung im Klimaprüfschrank untersucht.
Die Ergebnisse zeigen, dass sich durch die Beimischung von Füllstoffen Eigenschaften wie Festigkeit, Elastizität und auch Vergilbungsbeständigkeit beeinflussen lassen. Im Praxisbetrieb in den Restaurierungswerkstätten ist es jedoch schwierig, eine optimale Mischung der Komponenten zu erreichen. Dies begrenzt die Verwendung der getesteten Füllstoffe als transparentes Ergänzungsmaterial. Im Versuchsverlauf konnten dennoch vielversprechende gefüllte Klebstoffe entwickelt und auch die Transparenz verbessert werden. Die Testergebnisse werden vorgestellt und erläutert.
Die mittelalterlichen Glasmalereien der Johanniskirche in Thorn und der Kathedrale von Leslau sind Belastungen durch Industrieabgase und im Winterhalbjahr auch durch Emissionen aus Heizungsanlagen ausgesetzt. Im Rahmen des Projektes wurden Glasproben beider Bauwerke analysiert und ihre chemische Zusammensetzung bestimmt. Die Analysen tragen zur Bestandscharakterisierung bei. Restaurierungsmaterialien aus den 1950er Jahren und Beschichtungen auf den Gläsern aus Thorn, Leslau und auf Glasmalereien aus Kulm (Chelmno), die im Stadtmuseum in Thorn aufbewahrt werden, wurden dokumentiert, Materialproben entnommen und analysiert.
Unraveling the Dynamics of Nanoscopically Confined PVME in Thin Films of a Miscible PVME/PS Blend
(2017)
Broadband dielectric spectroscopy (BDS) was employed to investigate the glassy dynamics of thin films (7−200 nm) of a poly(vinyl methyl ether) (PVME)/polystyrene (PS) blend (50:50 wt %). For BDS measurements, nanostructured capacitors (NSCs) were employed, where films are allowed a free surface. This method was applied for film thicknesses up to 36 nm. For thicker films, samples were prepared between crossed electrode capacitors (CECs). The relaxation spectra of the films showed multiple processes. The first process was assigned to the α-relaxation of a bulklike layer. For films measured by NSCs, the rates of α-relaxation were higher compared to those of the bulk blend. This behavior was related to the PVME-rich free surface layer at the polymer/air interface. The second process was observed for all films measured by CECs (process X) and the 36 nm film measured by NSCs (process X2). This process was assigned to fluctuations of constraint PVME segments by PS. Its activation energy was found to be thickness-dependent because of the evidenced thickness dependency of the compositional heterogeneity. Finally, a third process with an activated temperature dependence was observed for all films measured by NSCs (process X1). It resembled the molecular fluctuations in an adsorbed layer found for thin films of pure PVME, and thus, it is assigned accordingly. This process undergoes an extra confinement because of frozen adsorbed PS segments at the polymer/substrate interface. To our knowledge, this is the first example where confinement-induced changes were observed by BDS for blend thin films
Specific heat spectroscopy (SHS) employing AC nanochip calorimetry was used to investigate the glassy dynamics of ultra-thin films (thicknesses: 10 nm–340 nm) of a polymer blend, which is miscible in the bulk. In detail, a Poly(vinyl methyl ether) (PVME)/Polystyrene (PS) blend with the composition of 25/75 wt. % was studied. The film thickness was controlled by ellipsometry while the film topography was checked by atomic force microscopy. The results are discussed in the framework of the balance between an adsorbed and a free surface layer on the glassy dynamics. By a self-assembling process, a layer with a reduced mobility is irreversibly adsorbed at the polymer/substrate interface. This layer is discussed employing two different scenarios. In the first approach, it is assumed that a PS-rich layer is adsorbed at the substrate. Whereas in the second approach, a PVME-rich layer is suggested to be formed at the SiO2 substrate. Further, due to the lower surface tension of PVME, with respect to air, a nanometer thick PVME-rich surface layer, with higher molecular mobility, is formed at the polymer/air interface. By measuring the glassy dynamics of the thin films of PVME/PS in dependence on the film thickness, it was shown that down to 30 nm thicknesses, the dynamic Tg of the whole film was strongly influenced by the adsorbed layer yielding a systematic increase in the dynamic Tg with decreasing the film thickness. However, at a thickness of ca. 30 nm, the influence of the mobile surface layer becomes more pronounced. This results in a systematic decrease in Tg with the further decrease of the film thickness, below 30 nm. These results were discussed with respect to thin films of PVME/PS blend with a composition of 50/50 wt.%as well as literature results.
We combined two completely different methods measuring the frequency-dependent electrical properties of moist porous materials in order to receive an extraordinary large frequency spectrum. In the low-frequency (LF) range, complex electrical resistivity between 1 mHz and 45 kHz was measured for three different soils and sandstone, using the spectral induced polarization (SIP) method with a four electrode cell. In the high-frequency (HF) radio to microwave range, complex dielectric permittivity was measured between 1MHz and 10 GHz for the same samples using dielectric spectroscopy by means of the coaxial transmission line technique. The combined data sets cover 13 orders of magnitude and were transferred into their equivalent expressions: the complex effective dielectric permittivity and the complex effective electrical conductivity.We applied the Kramers-Kronig relation in order to justify the validity of the data combination. A new phenomenological model that consists of both dielectric permittivity and electrical conductivity terms in a Debye- and Cole–Cole-type manner was fitted to the spectra. The combined permittivity and conductivity model accounts for the most common representations of the physical quantities with respect to the individual measuring method. A maximum number of four relaxation processes was identified in the analysed frequency range. Among these are the free water and different interfacial relaxation processes, the Maxwell-Wagner effect, the counterion relaxation in the electrical double layer and the direct-current electrical conductivity. There is evidence that free water relaxation does not affect the electrical response in the SIP range. Moreover, direct current conductivity contribution (bulk and interface) dominates the losses in the HF range. Interfacial relaxation processes with relaxations in the HF range are broadly distributed down to the LF range. The slowest observed process in the LF range has a minor contribution to the HF response.
Recently, we suggested an unconventional approach [the so-called Internal-Field-Guarded-Active-Region Design (IFGARD)] for the elimination of the crystal polarization field induced quantum confined Stark effect (QCSE) in polar semiconductor heterostructures. And in this work, we demonstrate by means of micro-photoluminescence techniques the successful tuning as well as the elimination of the QCSE in strongly polar [000-1] wurtzite GaN/AlN nanodiscs while reducing the exciton life times by more than two orders of magnitude. The IFGARD based elimination of the QCSE is independent of any specific crystal growth procedures. Furthermore, the cone-shaped geometry of the utilized nanowires (which embeds the investigated IFGARD nanodiscs) facilitates the experimental differentiation between quantum confinement- and QCSE-induced emission energy shifts. Due to the IFGARD, both effects become independently adaptable.
The electrospray ionization (ESI) method was used for deposition of thin films of poly(acrylic acid) (PAA) onto ZSM-5, Cu/ZSM-5 and Ag-Cu/ZSM-5 zeolites. This method allowed the formation of uniform polymer films of controlled thickness on conductive substrates.
The zeolites were prepared home-made. The effect of incorporation of Cu (5 wt.%) and Ag-Cu (1+4 wt.%) onto ZSM-5 on its particle size, unit cell parameters and crystallinity was investigated.
The deposited PAA layer acts as a common dispersing agent with its ionic COOH (COO-) groups. The antibacterial activity towards the bacterial strains such as Staphylococcus pneumonia (S. Pneumonia), Bacillus subtilis (B. subtilis), Escherichia coli (E. coli) and Pseudomonas aeruginosa (P. aeruginosa) as Gram positive and Gram negative bacteria, respectively, and Aspergillus fumigatus (A. fumigatus), Candida albicans (C. albicans) as Fungi was evaluated. The chemical and physical modifications of ZSM-5, Cu/ZSM-5 and Ag-Cu/ZSM-5 surfaces were characterized by X-ray photoelectron spectroscopy, Fourier-transform infrared spectroscopy, atomic force microscopy and X-ray diffraction.
The Cu/ZSM-5 and Ag-Cu/ZSM-5 nanocomposites coated with a 10 nm thick PAA layer exhibit significant antibacterial activity. The carboxyl (¬-COOH) or the corresponding carboxylate groups (¬-COO-) interact with Cu2+ and Ag+ ions by formation of ionic bonds (¬-COO-Ag+ or 2 ¬-COO->Cu2+). Moreover, short exposure to light and temperature has reduced Cu2+ and Ag+ to Cu0 and Ag0.
Core-shell (CS) particles with a polymeric core and a silica shell play an important role in the materials and (bio)analytical sciences. Besides the establishment of reliable synthesis procedures, comprehensive particle characterization is essential for batch-to-batch reproducibility and objective performance assessment across architectures, protocols, and laboratories. Particle characterization with respect to size, size distribution, shell thickness and texture, surface area and roughness or materials composition is commonly conducted with different analytical methods, often on different samples. Our approach uses a dual-mode TSEM/SEM set-up with an EDX detector to obtain a complementary data set with sufficient statistical confidence of one and the same sample on a single instrument. Our protocol reveals information about size, size distribution and shell thickness of the various particles employed from overview images, while an increased field of view (FOV) and high-resolution EDX analysis yields detailed information on shell texture and elemental composition. An image analysis tool was developed to derive and quantify the profile roughness of CS particles from individual beads. Comparison with surface roughness data from AFM showed a similar trend in roughness across the series of particles. Reliable classification into smooth and rough is proposed and roughness changes within different particle batches were tracked systematically.
We report on a novel and simple approach to surface ligand design of CdSe-based nanocrystals (NCs) with biocompatible, heterobifunctional polyethylene glycol (PEG) molecules. This method provides high transfer yields of the NCs into aqueous media with preservation of the narrow and symmetric emission bands of the initial organic-capped NCs regardless of their interior crystal structure and surface chemistry. The PEG-functionalized NCs show small sizes, high photoluminescence quantum yields of up to 75%, as well as impressive optical and colloidal stability. This universal approach is applied to different fluorescent nanomaterials (CdSe/CdS, CdSe/CdSCdxZn1-xS, and CdSe/CdS/ZnS), extending the great potential of organic-capped NCs for biological applications.
The synthesis of TiO2 nanoplatelets with fluorine-containing reactants is carried out using titanium (IV) butoxide as precursor and concentrated HF as shape controller, the final product requires a working up in order to eliminate or at least to reduce the amount of residual fluorides, which is realized here by well-defined thermal treatment of the samples. Bulk and surface sensitive methods namely scanning electron microscopy with energydispersive X-ray spectroscopy (SEM-EDX), Auger electron spectroscopy (AES) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) have been applied to trace the presence of any fluorides in dependence on different information depths and measurement sensitivities of these methods.
Topical issue: Geopolymers
(2017)
Geopolymers have gained very much momentum in recent years, in science and in industry. These highly promising and versatile materials have been researched with a view to applications as diverse as fire-resistant/refractory materials, as precursors for ceramics, in waste stabilization/immobilization, and as novel building materials. The great interest in these materials is reflected, inter alia, by the installment of a session on geopolymers at the 92nd Annual Meeting of the Deutsche Keramische Gesellschaft (DKG; German Ceramic Society) in March 2017. Therefore this Special Issue is dedicated to disseminating some of the recent findings on these materials. In addition, it contains reviews by highly experienced researchers in the field, highlighting very different aspects such as fiber reinforcement and synchrotron-based characterization methods.
Partly due to the interest from very different fields, the term „geopolymer“ is used with two different meanings. Sometimes it is used in the sense to denote the ceramic-like materials produced by activation of metakaolin with alkali silicate solutions, and closely related materials. On the other hand, sometimes it is used in a much broader sense to refer to any material that is produced by alkali-activation of many different aluminosilicate precursors, such as fly ash and granulated blast furnace slag waste materials, often serving as a cementitious binder. The present issue focusses on applications and materials that may be classified as ceramic, but also contains a review on the use of alkali-activated materials as construction materials to make the reader familiar with this approach too. Additionally, some of the materials described in this issue may be regarded as being „on the borderline“ between ceramics and cements, which is something that can be said about many studies in the geopolymer field.
The editors are very grateful to each of the authors of the articles in the present issue, as all of them have contributed high quality research based on their extensive experience. In particular, the historial perpectives on the origins and developments of geopolymers and of alkali activated materials have been authoritatively documented in contributions, by Joseph Davidovits and Pavel Krivenko. Dr. Krivenko was the Ph.D. student of Viktor D. Glukhovsky who first introduced alkali activated cements in 1957. It is hoped that the readers of this issue will enjoy reading it as much as the editors enjoyed putting it together, and that the issue will stimulate more high quality studies of geopolymers, perhaps even from research groups that have not yet been active in this area.
Nanoscale building blocks impart added functionalities to microelectromechanical systems (MEMS). The integration of silicon nanowires with MEMS-based sensors leading to miniaturization with improved sensitivity and higher noise immunity is one example highlighting the advantages of this multiscale approach. The accelerated pace of research in this area gives rise to an urgent need for batch-compatible solutions for scaling to nano. To address this challenge, a monolithic fabrication approach of silicon nanowires with 10-lm-thick silicon-on-insulator (SOI) MEMS is developed in this work. A two-step Si etching approach is adopted, where the first step creates a shallow surface protrusion and the second step releases it in the form of a nanowire. It is during this second deep etching step that MEMS—with at least a 2-order-of-magnitude scale difference - is formed as well. The technique provides a pathway for preserving the lithographic resolution and transforming it into a very high mechanical precision in the assembly of micro- and nanoscales with an extreme topography. Validation of the success of integration is carried out via in situ actuation of MEMS inside an electron microscope loading the nanowire up to its fracture. The technique yields nanowires on the top surface of MEMS, thereby providing ease of access for the purposes of carrying out surface processes such as doping and contact formation as well as in situ observation. As the first study demonstrating such monolithic integration in thick SOI, the work presents a pathway for scaling down to nano for future MEMS combining multiple scales.
The use of duplex stainless steels (DSS) in energy related applications is well known. Nowadays, DSS steels become more favorable than austenitic steels due to the outstanding mechanical properties, the good corrosion resistance and the lower nickel content. However, the use of the duplex grade in acidic environments such as seawater often leads to severe degradation of the structural integrity of the steel by hydrogen-induced/assisted cracking (HAC) phenomena, which can eventually result in premature failure. Hydrogen assisted degradation and cracking of steels are active fields of research even though this topic is intensively studied for more than a century. A bottleneck is the analytical validation of the theoretical models proposed ion the literature at the sub-micron scale.
Industrial and the research communities see a need for an accurate analytical method by which it is possible to image the distribution of hydrogen in the microstructure of a steels or and other alloys. Among the very few available methods hydrogen imaging methods, Time-of-Flight secondary ion mass spectrometry (ToF-SIMS) has the principal capability for mapping of hydrogen in a steel’s microstructure. The combination of ToF-SIMS with multivariate data analysis (MVA), electron microscopy (SEM) and electron-backscattered diffraction (EBSD) is a powerful approach for providing chemical and structural information. The use of data fusion techniques has been shown recently to enhance the better understanding of the hydrogen induced degradation processes in in a DSS steel.
Raman spectroscopy is becoming a powerful process analytical technology (PAT) tool. Until now Raman technology has not shown its full potential in bioprocess on-line monitoring due to several technical challenges. Because of only small? interference from water molecules, Raman-spectroscopy is in contrast to IR spectroscopy able to follow changes of metabolite concentrations in dilute aqueous solutions. Results from common CCD-based process Raman-spectrometers reveal only barely identifiable peaks with a dominating (fluorescence) background. To solve this, Raman spectroscopy needs: (A) an enhancement to increase the limit of detection (LOD), and (B) a reliable method to distinguish the Raman signal from the sample-related auto-fluorescence.
SERS (surface enhanced Raman spectroscopy) acts as an optical "nano-antenna"-effect. It causes a dipolar localized surface Plasmon resonance effect due to noble metallic nanoparticles or roughened metal and improves the limit of detection (LOD) significantly. Another new process-monitoring technique, which removes the fluorescence background in Raman-measurements is called time-gated Raman spectroscopy. It uses a picosecond pulsed Nd:YVO4-laser as emission source (exc= 532 nm) and a gated SPAD-array (Single Photon Avalanche Detector) detector instead of commonly used CCD (Charged Coupled Device)-detectors and CW (Continues Wave) laser emission. Time-Gate can measure the Raman-signal before the stronger fluorescence signal reaches the detector.
In this study we utilized both SERS (Surface Enhanced Raman Spectroscopy) and time-gated Raman spectroscopy (TG-Raman) in combination on cell-free supernatant samples of an Escherichia coli cultivation with mineral salt media and a lactic acid bacteria fermentation with complex media. As a reference method for the estimation of amino acids and other metabolites, HPLC-RID and HPLC-FLD were used to evaluate the Raman-based detection. The quantitative evaluation of Raman data was performed by multivariate data analysis such as principal component analysis (PCA) and partial least squares regression (PLSR). For the first time, we can show that both qualitative and quantitative measurements are conducted successfully with both, SERS and time-gated Raman methods in industrially relevant media, so that a fast and reliable in situ or bypassed concentration measurement becomes feasible.
Flow cytometry is a widely used method in biological research and medical diagnostics. Depending on the respective application, two opposing directions of development are currently of interest. On the one hand, there is a need for analyses of growing complexity employing more and more fluorescent labels and codes. On the other hand, cost-effective methods and portable, miniaturized, and robust instruments are desired.
Commonly performed spectral multiplexing utilizing a color code suffers from several problems, such as the sensitivity of fluorescence intensity measurements to fluctuations in excitation light intensity and dye concentration and hence, photobleaching, dye leaking for certain encoding procedures, and spectral crosstalk, limiting the achievable number of detection channels. Moreover, it typically requires several costly excitation light sources. An innovative alternative can be lifetime multiplexing and the discrimination between different encoding fluorophores and carrier beads based on their fluorescence decay kinetics. In order to examine the potential of this approach, dye encoded beads (lifetime encoded surface chemistry) were prepared using several fluorophores from different dye classes and their suitability for lifetime discrimination in a flow was tested in conjunction with a custom designed flow cytometer equipped with a pulsed light source and a fast detector.
In a first step, the spectroscopic properties of micrometer-sized dye-stained PMMA beads were studied by means of steady state and time-resolved photoluminescence measurements. For the performance of studies on the practical use of these microbeads in flow cytometry applications, a custom-built demonstrator model for a flow system was employed.
Our results demonstrated that lifetime discrimination and simultaneous readout of a ligand fluorescence signal for analyte quantification with a set of dye-stained polymer microbeads at single wavelength excitation is feasible. These studies are expected to pave the road for new applications of fluorescence lifetime multiplexing within the framework of time-domain flow cytometry and bead-based assays.
The motivation of this work is to produce thin films perovskite solar cells with constant high light conversion efficiency over time. Loss of efficiency may be caused by structural and/or chemical alterations of the complex layered system. As these changes might take place either in the bulk and/or on the surface of the stratified material, analytical tools addressing both key issues are selected and combined. SEM/EDS combined with XPS were chosen as appropriate methodical approach to characterise perovskite laboratory cells in depth and complementary on top, before and after light exposure. The layered perovskite system investigated here is based on glass covered with fluorine doped tin oxide (FTO), followed by three porous thin films of TiO2, ZrO2 and a thick monolithic carbon. The TiO2 film is subdivided into a dense layer covered by a porous one constituted of nanoparticles with a truncated bipyramidal shape. This layered system serves as the matrix for the perovskite. After infiltration of perovskite solution and annealing, EDS
spectral maps on cross-sections of the specimen have been measured. The distribution of relevant
elements – Si, Sn, Ti, Zr and C – correlates conclusively with layers visible in the acquired SEM images. Lead and iodine are distributed throughout the porous layers C, ZrO2 and TiO2. Specimens were exposed to ambient daylight for 7 weeks. In a SEM micrograph taken of the cross-section of a sample after illumination, the glass substrate and all layers FTO, TiO2, ZrO2 as well as C are clearly identified. EDS data have been acquired under the same measurement conditions as before the illumination. It was found that several weeks of ambient daylight did not change significantly the qualitative elemental composition of lead and iodine throughout the solar cell system. It was confirmed with EDS that nanoparticles identified in high-resolution SEM micrographs contain mainly Pb and I, indicating these to be the perovskite
crystals. However, a time-dependent compositional and chemical altering was observed with XPS for the near-surface region of the outermost ~10 nm after 2 months of illumination.
Background: Gas sensors are very important in several fields like gas monitoring, safety and environmental applications. In this approach, a new gas sensing concept is investigated which combines the powerful adsorption probability of metal oxide conductive sensors (MOS) with an optical ellipsometric readout. This concept Shows promising results to solve the problems of cross sensitivity of the MOS concept.
Results: Undoped tin oxide (SnOx) and iron doped tin oxide (Fe:SnOx) thin add-on films were prepared by magnetron sputtering on the top of the actual surface plasmon resonance (SPR) sensing gold layer. The films were tested for their sensitivity to several gas species in the surface plasmon resonance enhanced (SPREE) gas measurement. It was found that the undoped tin oxide (SnOx) shows higher sensitivities to propane (C3H8) then to carbon monoxide (CO). By using Fe:SnOx, this relation is inverted. This behavior was explained by a change of the amount of binding sites for CO in the layer due to this iron doping. For hydrogen (H2) no such relation was found but the sensing ability was identical for both layer materials. This observation was related to a different sensing mechanism for H2 which is driven by the Diffusion into the layer instead of adsorption on the surface.
Conclusion: The gas sensing selectivity can be enhanced by tuning the properties of the thin film overcoating. A relation of the binding sites in the doped and undoped SnOx films and the gas sensing abilities for CO and C3H8 was found. This could open the path for optimized gas sensing devices with different coated SPREE sensors.
A short overview of thin film analysis by SEM/EDX is presented. Relevant steps such as optimization of instrumnetal parameters, extraction of net peak areas, use of standards, calculation of k-values and quantification with the dedicated thin film analysis software (Stratagem) are explained. Examples of different layered aystems are given together with validation of the results.
2,6-Diaminopyridine based functional polymers poly N-(6-aminopyridin-2-yl)acrylamide) (PNAPAAm) and poly(N-(6-acetamidopyridin-2-yl)acrylamide) (PNAcAPAAm) were synthesized via free radical polymerization and in addition PNAcAPAAm was synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization for comparison. The obtained polymers displayed upper critical solution temperature (UCST)-type reversible thermoresponsiveness in water/alcohol mixtures. The UCST Phase transition behaviour of the obtained functional polymers was studied using temperature dependent turbidimetry, dynamic light scattering and 1H-NMR measurements. The phase transition temperature of the polymers was tunable by varying either the concentration of the polymer solution, the nature of the alcohol or the composition of the solvent mixture. The cloud Point temperature of PNAcAPAAm was found to decrease with increasing alcohol content (MeOH, EtOH and iPrOH) in water/alcohol mixtures.
Past a critical amount of EtOH or iPrOH in water, the cloud point temperature of PNAcAPAAm increased upon further addition of EtOH or iPrOH. Such functional polymers with tunable UCST behaviour can be applicable in drug delivery, sensing, personal care and microfluidic applications.
Formgedächtnispolymere werden durch thermomechanische Vorbehandlung, die Programmierung, in eine temporäre Form überführt. In die Ursprungsform kehren sie dann erst nach externer Stimulierung, durch Auslösen des Formgedächtniseffekts, wieder zurück. Um diesen Effekt zu optimieren, werden in dieser Arbeit thermomechanische Designoptionen analysiert und Stellschrauben der Programmierung diskutiert. Quantifiziert wird das Materialverhalten eines physikalisch vernetzten Polyurethans mit semikristalliner Polyester-Weichsegmentphase (PEU) in thermomechanischen Messungen, in denen das Polymer Dehnungen bis über 1000% fixiert.
Deformationen im breiten Schmelzübergangsbereich der Weichsegmentphase ermöglichen die präzise Kontrolle über die Temperaturen der Dehnungs- und Spannungsrückstellung, den bekannten Temperaturgedächtniseffekt (TGE). Erst durch eine neuartige Programmierung wird jedoch der Beginn der Rückstellung einstellbar. Für diesen Onset-TGE wird das PEU direkt nach dem Recken entlastet und danach unter die Kristallisationstemperatur abgekühlt. In situ Röntgenstreuung zeigt, dass durch den frühen Entlastungszeitpunkt nur der Teil der kristallinen Weichsegmentphase zur Fixierung beiträgt, der auch beim Recken kristallin ist. Die Kristallinität bietet daher eine Stellschraube, um das thermomechanische Verhalten zu veredeln. Über die Optimierungsparameter Reckrate, Temperaturhaltezeit und maximale Dehnung erzielt das PEU hohe Fixierbarkeiten und Rückstellspannungen, ohne die Rückstellung und den Onset-TGE zu beeinträchtigen. Durch die Erweiterung der Programmierung des Onset-TGEs hin zu einer zweiten Deformation und Entlastung innerhalb des Schmelzübergangs zeigt das PEU einen bisher nicht berichteten zweistufigen Spannungsanstieg während der Rückstellung. Ein Temperaturlimit für den Onset-TGE stellt die Peak-Schmelztemperatur aus der dynamischen Differenzkalorimetrie dar. Durch die verbleibende Kristallinität oberhalb dieser Temperatur führt die Deformation und Entlastung direkt zur thermoreversiblen Aktuation mit Dehnungsänderungen bis zu 28%.
Die Ergebnisse werden auf einen Miniaturisierungsansatz für schaltbare Informationsträger übertragen, mit denen eine maschinenlesbare Information von nichtlesbar nach lesbar geschaltet werden kann. In einer Machbarkeitsstudie wird der für Sensoranwendungen vielversprechende Onset-TGE genutzt, um die Lesbarkeit der Informationsträger bei einer vordefinierten Temperatur zu schalten. Das erweitert das potentielle Anwendungsfeld der Technologie vom Produkt- und Markenschutz zur Überwachung von Kühlketten.
The unparalleled excited-state potential-energy landscape of the chromium(III)-based dye [1]3+ ([Cr(ddpd)2]3+; ddpd=N,N’-dimethyl-N,N’-dipyridin-2-ylpyridin-2,6-diamine) enables a strong dual emission in the near infrared region. The temperature dependence of this dual emission allows the use of [1]3+ as an unprecedented molecular ratiometric thermometer in the 210–373 K temperature range in organic and in aqueous media. Incorporation of [1]3+ in biocompatible nanocarriers, such as 100 nm-sized polystyrene nanoparticles and solutol micelles, provides nanodimensional thermometers operating under physiological conditions.
Mandatory for the comparison of different emitter classes and the rational design of the next generation of molecular and nanoscale reporters are reliable and quantitative photoluminescence measurements. This is of special relevance for all fluorescence applications in the life and material sciences. In the following, proccedures for the determination of this spectroscopic key parameter are presented including material-specific effects related to certain emitters
The effects of reducing specimen size on the fire behavior of polymeric materials were investigated by means of the rapid mass calorimeter, a high-throughput Screening instrument. Results from the rapid mass calorimeter were compared with those from the cone calorimeter. Correlation coefficients between the different measures of each method and between the two methods are discussed to elucidate the differences and similarities in the two methods. Materials with characteristic heat release rate (HRR) curves in the cone calorimeter were evaluated in detail. The rapid mass calorimeter produces valuable and interpretable results with HRR curve characteristics similar to cone calorimeter results. Compared to cone calorimeter measurements, material savings of 96% are achieved, while maintaining the Advantages of a macroscopic fire test.
The rapid mass calorimeter based on reduced‐size specimens is proposed for accelerated fire
testing and put up for discussion, particularly for flame retarded polymeric materials. A mass loss
calorimeter is combined with a semiautomatic sample changer. Experiments on specimens of
reduced size were conducted on poly(methyl methacrylate), poly(propylene), polyamide 66,
poly(ether ether ketone), and pine sapwood square samples with edge lengths of 100, 75, 50,
25, 20, and 10 mm. Specimens of 20 × 20 mm2 were selected to achieve a crucial reduction in
specimen size and a measuring protocol developed. A total of 71 different polymeric materials
were investigated in the rapid mass calorimeter and cone calorimeter for comparison and several
materials with different heat release rate characteristics in the pyrolysis combustion flow calorimeter to test this additional screening method as well. The important fire properties obtained in the rapid mass calorimeter show reasonable correlation with the cone calorimeter results but also with the oxygen index. All in all, the rapid mass calorimeter produces reliable and meaningful results and, despite acceleration and size reduction, still allows for a certain degree of burning behavior interpretation. Material savings of 96% and time savings of around 60%‐70% are achieved compared to measure cone calorimeter.
Elemental imaging of biological samples using laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) provides spatially resolved information on element distribution in thin sections. By rastering with a laser across the sample, a two-dimensional image of the elemental distribution can be reconstructed that shows the intensities of the respective elements. Using overlapping laser shots the area ablated from single cells or thin sections (thickness 5 to 10 µm) can be reduced significantly so that the pixel size of the intensity measurement is significantly reduced. Having in mind that a laser shot ablates thin biological samples completely, we can make use of a new concept for calibration in the laser ablation method: the concept of total consumption. This calibration strategy allows production of simple matrix matched standards and provides an internal standardisation by ink jet technology, where a metal containing inks is printed on as thin layer on top of a biological sample.
Different applications will be presented where our concepts have been applied. In the first example we used nanoparticle suspension of given particle numbers to quantify the uptake of metallic nanoparticles by biological cells. In the second example antibodies have been tagged by metals to measure protein expression in prostata cancer. In this approach application of house keeping proteins are investigated additionally to compensate variations in thickness and density of the biopsy samples. In the third application different nephrotoxic behaviour of Pt containing drugs have been investigated to study the local enrichement in kidney samples of mice treated with these three different compounds. Here the internal standard is required to allow intercomparisons between different individual mouse tissues.
At the end of the lecture future trends will be discussed for elemental microscopy.
The work focuses on the potential of structural and chemical examinations by scanning electron microscopy based methods for archaeometric studies on ceramics. Achieved by a single preparation technique (polished block sections), the feasibility and benefits of electron backscatter diffraction are demonstrated as case studies using polychrome examples of pre-Columbian pottery (Wari, Moche and Cajamarca). Elemental and phase maps allow for separate consideration of clay and temper. Identification of mineral phases and intergrowths of temper particles provide information for clarifying clay procurement and firing techniques with respect to local versus non-local pottery to enlighten trade relations, technological transfer and shared heritage of pre-Columbian cultures.
Data correction is probably the least favourite activity amongst users experimenting with small-angle X-ray scattering: if it is not done sufficiently well, this may become evident only during the data analysis stage, necessitating the repetition of the data corrections from scratch. A recommended comprehensive sequence of elementary data correction steps is presented here to alleviate the difficulties associated with data correction, both in the laboratory and at the synchrotron. When applied in the proposed order to the raw signals, the resulting absolute scattering cross section will provide a high degree of accuracy for a very wide range of samples, with its values accompanied by uncertainty estimates. The method can be applied without modification to any pinhole-collimated instruments with photon-counting direct-detection area detectors.
The release of iron from iron nanoparticles (NPs) used as parenteral formulations appears to be influenced by the size and surface properties of the colloidal iron complex and the matrix. A clinically applied product Venofer® has been used as a model formulation to establish adequate analytical strategies to evaluate the fate of iron nanoparticles (NPs) in blood. First, the preparation was characterized by high resolution transmission electron microscopy (HRTEM), dynamic light scattering (DLS) and UV-vis absorption spectroscopy. This revealed the presence of monodisperse iron NPs with a hydrodynamic diameter of ∼15 nm and an iron core of ∼4 nm. Venofer® was then incubated with serum and whole blood in a quantitative study on the iron bioavailability from these NPs. Iron was speciated and quantified by using inductively coupled plasma mass spectrometry (ICP-MS). Iron solubilization levels of up to 42% were found in both fluids using isotope dilution of iron for quantification within the first hour of incubation even in the absence of the reticuloendothelial system. The monitoring of the iron-containing proteins present in serum was conducted by highperformance liquid chromatography with ICP-MS detection. It indicated that the dissolved iron ions are bound to transferrin. Quantitative speciation studies using isotope pattern deconvolution experiments concluded that the released iron saturated almost completely (up to 90%) the metal binding sites of transferrin. The remaining iron appeared also associated to albumin and, to a lesser extent, forming smaller sized particles. Thus, the methods presented here provide new insights into the fate of Venofer® nanoparticles and may be applied to other formulations.
The effectiveness of distinct fillers, from micro to nano-size scaled, on the fire behaviour of an epoxy resin and its carbon fibre reinforced composites was assessed by cone calorimetry. The performance was compared not only regarding the reaction to fire performance, but also in terms of thermal stability, glass transition temperature and microstructure. Regarding the fire reaction behaviour of nanofilled epoxy resin, anionic nanoclays and thermally oxidized carbon nanotubes showed the best results, in agreement with more compact chars formed on the surface of the burning polymer. For carbon fibre reinforced composite plates, the cone calorimeter results of modified resin samples did not show significant improvements on the heat release rate curves. Poorly dispersed fillers in the resin additionally caused reductions on the glass transition temperature of the composite materials.
Superplasticizers (SPs) have been employed in concrete technology for decades to improve the workability of concrete in its fresh state. The addition of SPs in cement-based systems affects the early properties. Although the interaction of the cement particles with various SPs has been extensively researched, there still exists limited research on the interaction of SPs with supplementary cementitious materials such as rice husk ash (RHA). This paper investigates the rheological properties and early hydration kinetics of RHA-blended systems with three types of SPs, a polycarboxylate ether (PCE) and two lignosulphonates (LS-acc and LS-ret). In rheological properties, the addition of SP causes an initial improvement of workability as the yield stress is significantly reduced. The pastes with PCE and LS-acc show a slight increase of yield stress over time whereas pastes with LS-ret tend to lower the yield stress slightly over time, further improving the workability. Without SP, pastes with RHA show a lower yield stress but an increase in plastic viscosity as cement is further replaced with RHA. The addition of the LS SPs is observed to lower the plastic viscosity but remains constant with further replacement of cement with RHA. This indicates that LS SPs further adsorbs on RHA particles and hydration products produced causing dispersion of the particles
within the system. In early hydration kinetics, pastes with PCE retard hydration and the degree of retardation is further increased with LS SPs. In the presence of RHA, the retardation of LS SP systems is significantly reduced. The pastes with PCE show more ettringite in the SEM micrographs, but is observed to be shorter needles. This indicates an initial good workability for PCE. However, C-S-H and CH were observed to be low in quantity, whereby the pastes with LS show more nucleation sites for C-S-H and CH. The ettringite needles in the LS systems were similar in quantity and more elongated in some cases but not abundant as in the PCE systems.
An extraction of silica from natural sands of Bancar has been conducted by means of alkali fusion route using NaOH and mechanical alloying using planetary ball milling. The PANI/SiO2 Composite system has been coated in steel surfaces using spraying method. This study was designed to obtain PANI/SiO2 as an anti-corrosion coating material. The filler materials in the composite System consist of micro- and nano-SiO2. The structure of synthesized SiO2 be characterized using XRD and TEM. Corrosion of PANI/SiO2 composite has been tested using immersion method in synthetic geothermal atmosphere (Nord Deutsche Becken/NDB solution). The surface morphology after corrosion was observed by using SEM/EDX. XRD-Patterns and TEM show that the size of produced SiO2 is micro and nano. The size and composition of filler have influenced to surface degradation in geothermal atmosphere significantly. The addition of nano-SiO2 in the PANI matrix influenced corrosion resistance better than micro-SiO2 filler qualitatively. The nano-SiO2 has a high potential as an anti-corrosion material in geothermal atmosphere. The product of corrosion is mainly Fe2O3 and the corrosion process is identified as a pitting corrosion.
The synthesis of hybrid inorganic/organic copolymers, using reversible deactivation radical polymerization (RDRP) techniques, has been an intensively studied research topic over recent years. A plethora of hybrid inorganic/organic copolymers were synthesized, including hybrid inorganic/organic block copolymers as well as random copolymers,[1–4] that showed great potential in fabricating hybrid (nano)materials with tailored properties [5]. Two widely employed RDRP techniques to prepare such hybrid inorganic/organic copolymers are atom transfer radical polymerization (ATRP) [1,2] and reversible addition-fragmentation chain transfer (RAFT) polymerization [3,4]. In order, to afford hybrid inorganic/organic copolymers with narrow dispersity, high conversions and precise structures, it is required to choose proper reaction conditions. Due to the importance of both ATRP and RAFT in the preparation of such hybrid polymers, we aim to compare both RDRP techniques by preparing 2-acetoxyethyl methacrylate (AcEMA) and 3-(triethoxysilyl)propyl methacrylate (TESPMA) based homopolymers. For this purpose, AcEMA and TESPMA were polymerized in 1,4-dioxane at 60 °C mediated by CuBr/N,N,N',N'-pentamethyldiethylenetriamine (PMDETA) and 2-(2-carboxylethylsulfanylthiocarbonyl-sufanyl) propionic acid (TTC) as well as cumyl dithiobenzoate (CDB) to evaluate the suitability and reliability of ATRP and RAFT to prepare such hybrid (co)polymers.
Near-field optical techniques such as nano-FTIR spectroscopy enable spectroscopic characterization of samples with a high sensitivity and a spatial resolution at the nanoscale. In this work we realized nano-FTIR spectroscopy by elastic scattering of infrared light from a probe tip of an atomic force microscope operated in tapping mode, with broadband infrared synchrotron radiation provided by the Metrology Light Source (MLS). We apply this technique to characterize the protective oxidation layers of different Silicon Carbides (SiCs) treated by chlorine gas. The process using chlorine-donors has been developed to separate toxic heavy metals from sewage sludge ash (SSA) and to increase the plant-availability of phosphors in the SSA in order to produce P-fertilizers. Nitrified SiC showed the highest resistant strength against chlorine corrosion at 1000 °C compared to the other SiCs. In order to discuss this behavior high resolution imaging has been performed on the interfacial layer between bulk-SiC and the protective oxidation layer on sub-micrometer scale. The formation of a SixNiyO protective layer, which might be the reason for the higher corrosion resistance, was observed using nano-FTIR spectroscopy.
Synchrotron Radiation with its high intensity and the opportunity to tune the wavelength offers unique possibilities to investigate real catalysts, even under industry-like conditions.
A good example is a XAFS study performed at supported Ni catalysts used for the dimerization of butene at elevated temperature and pressure. Another example are investigations at titania supported Pd based catalyst elucidating the role of co-components (e.g. Sb, Co, Mn and Au) which are necessary to get the desired promising performance in the gas phase acetoxylation of toluene to benzyl acetate, an environmentally benign alternative for the conventional process using chlorine.
Furthermore, investigations about the redox properties of different Cu catalysts will be presented. It could be shown that the redox properties of Cu have a great impact on the performance of such catalysts, not only in some gas phase reactions, but also in photocatalytic applications, e.g. water splitting.
One of the most significant limitations for the quantum efficiency of group III-nitride based light emitters is the spatial electron-hole separation due to the quantum-confined Stark effect (QCSE). To overcome this problem, Hönig et al. [1] proposed a novel concept, the Internal-Field-Guarded-Active-Region Design (IFGARD), which suppresses the QCSE for wurtzite crystals in the [0001] direction. Here, we show how encapsulating the active region by additional guard layers results in a strong reduction of the built-in electric field in c-plane wurtzite nanostructures. Even more importantly, we demonstrate the first experimental evidence for the successful realization of an IFGARD structure based on GaN/AlN heterostructures embedded in GaN nanowires. By means of power-dependent and time-resolved µ-photoluminescence (µ-PL) we experimentally proof the validity of the unconventional IFGARD structure. We managed to tune the emission of 4-nm-thick GaN nano-discs up to 3.32 eV at low excitation powers, which is just 150 meV below the bulk GaN bandgap. Our results demonstrate an almost complete elimination of the QCSE in comparison to conventional structures which show approximately 1 eV red-shifted emission. The suppression of the QCSE results in a significant increase of the radiative exciton decay rates by orders of magnitude and demonstrates the potential of IFGARD structures for future light sources based on polar heterostructures.
[1] Hönig et al., Phys. Rev. Applied 7, 024004 (2017)
Silica nanowires spanning 10 μm-deep trenches are fabricated from different types of silsesquioxane-based precursors by direct e-beam patterning on silicon followed by release through deep reactive ion etching. Nanowire aspect ratios as large as 150 are achieved with a critical dimension of about 50 nm and nearly rectangular cross-sections. In situ bending tests are carried out inside a scanning electron microscope, where the etch depth of 10 mm provides sufficient space for deformation. Silica NWs are indeed observed to exhibit superplastic behavior without fracture with deflections reaching the full etch depth, about two orders of magnitude larger than the nanowire thickness. A large-deformation elastic bending model is utilized for predicting the deviation from the elastic behavior. The results of forty different tests indicate a critical stress level of 0.1–0.4 GPa for the onset of plasticity. The study hints at the possibility of fabricating silica nanowires in a monolithic Fashion through direct e-beam patterning of silsesquioxane-based resins. The fabrication technology is compatible with semiconductor manufacturing and provides silica nanowires with a very good structural integrity.
Nanoparticles (NPs) have potential applications in medical diagnostics, imaging, drug delivery and other kinds of therapy. Furthermore, studies concerning nanoparticle uptake by cells are important for risk assessment. Size, shape and surface modification of the NPs determine the uptake rate and pathway into the cells, and therefore impact specific cell components and processes. Understanding the different uptake mechanisms and involved processes require sub-cellular resolution to determine, for example, whether the nanoparticles are reaching the nucleus. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) is an established quantitative multi-elemental analysis and mapping technique. However, sub-cellular imaging has traditionally been challenging to achieve due to a lack of sensitivity at small laser spots. But now novel laser ablation systems with improved sensitivity and washout time allow imaging at high lateral resolution with spot sizes down to 1 µm.
Here LA-ICP-MS was applied for the imaging of individual fibroblast cells to study the uptake and intracellular processing of metal-containing NPs. To indicate cell morphology the local distribution of naturally occurring elements in cells like P and Zn was measured, too. Our results show that LA-ICP-MS can be used to localise nanoparticle aggregates within cellular compartments. The studied NPs accumulate in the perinuclear region in the course of intracellular processing, but do not enter the cell nucleus. The uptake efficiency depends strongly on the physico-chemical properties of the nanostructures as well as on the incubation conditions like concentration and incubation time. The potential of LA-ICP-MS for analysis at single cell level will be demonstrated.
In this study, series of coatings with the goal of sensitising gold SPR sensors towards CO, NH4, etc. were prepared. To better understand the mechanism behind the sensitizing effect and to enable the targeted production of optimized layers, the wide range of coatings was studied by multiple methods from spectroscopic ellipsometry for their dielectric function, by XPS for chemical composition and SEM, TEM to determine their microscopic structure. The coatings were deposited at inert Ar gas and reactive Ar/O2 gas mixture by RF magnetron sputtering or DC pulsed magnetron sputtering with settable RF bias on the substrates. The plasma processes were monitors by mass spectrometry.
The metal oxide coatings in SPR sensors have to be prepared reproducible with thickness about 5 nm therefore lower deposition rate conditions were advantages.
In this study, series of coatings with the goal of sensitising gold SPR sensors towards CO, NH4, etc. were prepared. To better understand the mechanism behind the sensitizing effect and to enable the targeted production of optimized layers, the wide range of coatings was studied by multiple methods from spectroscopic ellipsometry for their dielectric function, by XPS for chemical composition and SEM, TEM to determine their microscopic structure. The coatings were deposited at inert Ar gas and reactive Ar/O2 gas mixture by RF magnetron sputtering or DC pulsed magnetron sputtering with settable RF bias on the substrates. The plasma processes were monitors by mass spectrometry.
The metal oxide coatings in SPR sensors have to be prepared reproducible with thickness about 5 nm therefore lower deposition rate conditions were advantages.
The application of inorganic nanoparticles as reinforcement agent for polymer composites is constantly growing. Improving the performance of the material with desirable properties requires understanding of the interaction between polymer chains and nanoparticles and the properties of the interphase as well. Boehmite, a mineral of aluminum with basic unit of AlO(OH), is a novel and promising nanofiller which leads to enhanced performance of polymer composites. It has been recently reported that boehmite nanoparticles have reinforcing effect on epoxy matrix in carbon-fiber composites. It was primarily assumed that these improvements are due to very high Young’s modulus of boehmite particles. However, in our latest study we presented new values for the Young’s modulus of boehmite much lower than those reported earlier. This brings up the importance of interphase properties, e.g. the crosslink density, which can have the dominant role in the overall material property. Nevertheless, due to resolution limitations of conventional nanoprobing approaches, characterization of the interphase between individual particles and matrix is a challenge.
In this study, the main goal is to investigate the interphase of the epoxy/boehmite nanocomposites using AFM-based methods. We simplify the three-dimensional nanocomposite system to a two-dimensional horizontally layered sample with a large and easy to access interphase area. For this purpose, 1µm coatings of hydrothermally synthesized boehmite are prepared as the substrate on which the epoxy is later molded and cured. AFM surface potential and force maps were obtained on the cross-sectional cut of epoxy/ boehmite sample. The results show unexpectedly a large interphase area (approx. 1 µm) with different electrical and mechanical properties comparing to bulk epoxy. The average force-distance curves from this region showed more elastic behavior compared to bulk. The underlying mechanism of this influence is not fully understood yet. Thus, further investigation on the interphase region using the novel Nano-IR approach provides more information about the chemical characteristics. Numerical simulation will give complementary information to understand the effect of nanoparticles on the crosslinking density of the interphase. This can be different to bulk epoxy due to either different local temperature gradients or due to a surface selectivity of boehmite towards the monomer molecules.
Nanocomposites based on poly(L-lactide) (PLA) and organically modified Ni/Al layered double hydroxides (NiAl/LDHs) are prepared by melt blending and investigated by a combination of size exclusion chromatography, differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS), wide-angle X-ray scattering, and broadband dielectric spectroscopy. A detailed comparison to the behavior of the corresponding MgAl/LDH–PLA nanocomposites is made. SAXS investigations show that the morphology of the NiAl/LDH–PLA nanocomposites is more intercalated compared to the MgAl/LDH based PLA nanocomposite, which is more exfoliated. The DSC investigation gives a different dependence of the degree of crystallization on the concentration of LDH for NiAl/LDH–PLA than for MgAl/LDH–PLA nanocomposite system. These differences are discussed taking the differences of the morphologies of both systems into account. Broadband dielectric spectroscopy reveals information about the molecular dynamics where essential differences are observed for all relaxation processes taking place in both systems which were related to the different morphologies.
Polymer-based nanocomposites attracted recently a lot of attention from both the applicative and fundamental point of research. While the former point of view is due to the properties improvement compared to the corresponding matrix polymers the latter aspect is related to interaction of polymers with solid surfaces and confinement effects.
Here, nanocomposites based on poly(L-lactide) (PLA), which is a semi-crystalline polymer, and organically modified Layered Double Hydroxides (LDH) were prepared by melt blending, and investigated by a combination of Differential Scanning Calorimetry (DSC), Small- and Wide-Angle X-ray Scattering (SAXS, WAXS), and dielectric spectroscopy (BDS). Two different LDH materials were considered, which results in different morphologies of the nanocomposites. The influence of these different morphologies on the properties of the nanocomposites especially on the molecular mobility is discussed in detail.
In general the structure of semi-crystalline polymers has to be described by a three phase model, consisting of a mobile amorphous (MAF), a crystalline (CF), and a rigid amorphous fraction (RAF). For nanocomposites based on semi-crystalline polymers the RAF is due to both the crystallites (RAFcrystal) and the filler (RAFfiller). The considered nanocomposites were further investigated by hyper and temperature modulated differential scanning calorimetry. For the first time the different phase fractions CF, MAF, RAFcrystal, and RAFfiller could be estimated independently from each other.
In this study, the molecular dynamics of two linear-shaped tetramethylated guanidinium triflates ionic liquid crystals were investigated by a combination of Broadband Dielectric Spectroscopy (BDS) and Specific Heat Spectroscopy (SHS). Three processes were detected by BDS; at low temperature γ-process, at higher temperatures α-process and at even higher temperatures conductivity. The γ-process indicates localized fluctuations, and the α-process designates cooperative fluctuations. Slightly different restrictions were found for conductivity processes of LC536 and LC537 due to the slightly different lengths of alky chains. Furthermore, the cooperative dynamics were also probed by SHS. The cooperative dynamics probed by the different techniques (BDS and SHS) compared, and assigned to the different restrictions on the cooperativity due to the difference in the sensitivity of the techniques.
The interest in porous anodic aluminum oxide (AAO) has been rapidly growing due to its numerous applications in separation, catalysis, energy generation and storage, electronics, and sensors. From the scientific point of view, AAO is a topical interest in soft matter fields. Spatial confinement of soft matter in nanoporous media influences its structure, thermodynamics, and mobility. Embedding polymers and liquid crystals into nanopores of AAO results in a 2D nanoconfinement of these materials. This confinement affects their properties, compared to the bulk, such as phase transition temperatures and enthalpies, molecular mobility, and architecture of the crystallization. On the other hand, discotic liquid crystals (DLCs) are a promising class of soft matter for electronic applications. This is due to their ability to organize and stack themselves into columns in a hexagonal columnar mesophase, a mesophase in between the plastic crystalline and isotropic phase, driven by the overlap of the π orbitals of their aromatic core. This leads to a high charge-carrier mobility along the column axis. Further, these columns could then be considered as “molecular nanowires”. In this study, 2,3,6,7,10,11 hexakis[hexyloxy] triphenylene (HAT6), a triphenylene based DLC, was confined into nanoporous AAO membranes. The structure, dynamics and the phase behavior of the confined HAT6 were investigated by broadband dielectric spectroscopy (BDS) and differential scanning calorimetry (DSC). HAT6 was embedded into nanoporous AAO membranes by melt infiltration in the isotropic phase under argon atmosphere. The membranes have parallel aligned cylindrical nanopores, with pore diameter of 10, 20, 25, 40, 80, 120 and 180 nm. The filling degree for each sample was checked by thermogravimetric analysis (TGA) in order to ensure complete filling. Bulk HAT6 forms a hexagonal columnar phase; in between the isotropic phase above 371 K and the plastic crystalline phase below 340 K. Unlike the bulk, the confined HAT6 split the plastic crystalline-to-hexagonal columnar phase transition in two, which might be interpret as two different phase structures; close to the wall and at the pore center. Moreover, the isotropic-to-columnar transition of the confined HAT6 shifted, with decreasing pore diameter, to lower temperatures. Furthermore, pore surfaces of a series of membranes were chemically modified, resulting in a more hydrophobic pore surface than the unmodified ones. HAT6 was embedded into the modified membranes by the same aforementioned preparation. The influence of the changed host-guest-interaction, on the structure, dynamics, and the phase behavior of HAT6 confined in the modified membranes, was also investigated by BDS and DSC.
Discotic liquid crystals (DLCs) are a promising class of soft matter for electronic applications. This is due to their ability to organize and stack themselves into columns in a hexagonal columnar mesophase, driven by the overlapping of the π orbitals of their aromatic core. This leads to a high charge-carrier mobility along the column axis. Previous studies on DLCs showed that their properties, such as phase transition temperatures and enthalpies, are susceptible to nanoconfinement. In this study, 2,3,6,7,10,11 hexakis[hexyloxy] triphenylene (HAT6), a triphenylene based DLC, was confined into parallel aligned cylindrical nanopores of anodic aluminum oxide (AAO) membranes by melt infiltration in the isotropic phase under an argon atmosphere. Furthermore, the pore surfaces of a series of membranes were chemically modified, resulting in a more hydrophobic pore surface than the unmodified ones. The structure, dynamics, and the phase behavior of HAT6 confined into modified and unmodfied nanopores of AAO were investigated by broadband dielectric spectroscopy and differential scanning calorimetry. Results will be discussed in detail.
Discotic liquid crystals (DLCs) are a promising class of soft matter for electronic applications. This is due to their ability to organize and stack themselves into columns in a hexagonal columnar mesophase, a mesophase in between the plastic crystalline and isotropic phase, driven by the overlap of the π orbitals of their aromatic core. This leads to a high charge-carrier mobility along the column axis. Further, these columns could then be considered as “molecular nanowires”.
Spatial confinement of soft matter in nanoporous media influences its structure, thermodynamic properties, and mobility. Embedding liquid crystals and polymers into nanopores of anodic aluminum oxide (AAO) results in a 2D nanoconfinement of these materials. This confinement affects their properties, compared to the bulk, such as phase transition temperatures and enthalpies, molecular mobility, and architecture of the crystallization.
In this study, 2,3,6,7,10,11 hexakis[hexyloxy] triphenylene (HAT6), a triphenylene-based DLC, was confined into nanoporous AAO membranes. The structure, dynamics and the phase behavior of the confined HAT6 were investigated by broadband dielectric spectroscopy (BDS) and differential scanning calorimetry (DSC). HAT6 was embedded into nanoporous AAO membranes by melt infiltration in the isotropic phase under argon atmosphere. The membranes have parallel aligned cylindrical nanopores, with different pore diameters in the range of 10-180 nm. Bulk HAT6 forms a hexagonal columnar phase; in between the isotropic phase above 371 K and the plastic crystalline phase below 340 K. Unlike the bulk, the confined HAT6 split the phase transitions in two or more, which might be interpret as different phase structures; close to the wall and at the pore center. Moreover, the phase transitions of the confined HAT6 shifted, with decreasing pore diameter, to lower temperatures. The dependencies of the phase transition temperatures on the pore size was well-described by the Landau-de Gennes model. Furthermore, pore surfaces of a series of membranes were chemically modified, resulting in a more hydrophobic pore surface than the unmodified ones. HAT6 was embedded into the modified membranes by the same aforementioned preparation. The influence of the changed host-guest-interaction, on the structure, dynamics, and the phase behavior of HAT6 confined in the modified membranes, was also investigated by BDS and DSC.
The structural and magnetic properties of magnetic multi-core particles were determined by numerical inversion of small angle scattering and isothermal magnetisation data. The investigated particles consist of iron oxide nanoparticle cores (9 nm) embedded in poly(styrene) spheres (160 nm). A thorough physical characterisation of the particles included transmission electron microscopy, X-ray diffraction and asymmetrical flow field-flow fractionation. Their structure was ultimately disclosed by an indirect Fourier transform of static light scattering, small angle X-ray scattering and small angle neutron scattering data of the colloidal dispersion. The extracted pair distance distribution functions clearly indicated that the cores were mostly accumulated in the outer surface layers of the poly(styrene) spheres. To investigate the magnetic properties, the isothermal magnetisation curves of the multi-core particles (immobilised and dispersed in water) were analysed. The study stands out by applying the same numerical approach to extract the apparent moment distributions of the particles as for the indirect Fourier transform. It could be shown that the main peak of the apparent moment distributions correlated to the expected intrinsic moment distribution of the cores. Additional peaks were observed which signaled deviations of the isothermal magnetisation behavior from the non-interacting case, indicating weak dipolar interactions.
This paper deals with uncertainty considerations in damage diagnosis using the stochastic subspace-based damage detection technique. With this method, a model is estimated from data in a (healthy) reference state and confronted to measurement data from the possibly damaged state in a hypothesis test. Previously, only the uncertainty related to the measurement data was considered in this test, whereas the uncertainty in the estimation of the reference model has not been considered. We derive a new test framework, which takes into account both the uncertainties in the estimation of the reference model as well as the uncertainties related to the measurement data. Perturbation theory is applied to obtain the relevant covariances. In a numerical study the effect of the new computation is shown, when the reference model is estimated with different accuracies, and the performance of the hypothesis tests is evaluated for small damages. Using the derived covariance scheme increases the probability of detection when the reference model estimate is subject to high uncertainty, leading to a more reliable test.
Multiparametric analyses involving optical techniques like flow cytometry are at the core of studying complex systems in biological research and diagnostic applications. However, for fluorescence-based techniques, the number of reporters distinguishable in spectral multiplexing is limited by spectral overlap and requires a multitude of excitation light sources and detection Systems. Intensity encoding often used for bead assays suffers from problems regarding dye concentration control and excitation light intensity fluctuations. An alternative is luminescence lifetime encoding, particularly to minimize instrument costs.
Here, we report on dye-stained polymer microparticles for lifetime encoding in flow cytometry with different organic dyes. This ranges from studies of the impact of parameters like dye loading concentration and particle diameter on fluorescence decay behavior to the demonstration of lifetime code reading and simultaneous ligand fluorescence signal detection with single-wavelength excitation in a flow.
8-Bromoadenine (8BrA) is a potential DNA radiosensitizer for cancer radiation therapy due to its efficient interaction with low-energy electrons (LEEs). LEEs are a short-living species generated during the radiation damage of DNA by high-energy radiation as it is applied in cancer radiation therapy. Electron attachment to 8BrA in the gas phase results in a stable parent anion below 3 eV electron energy in addition to fragmentation products formed by resonant exocyclic bond cleavages. Density functional theory (DFT) calculations of the 8BrA– anion reveal an exotic bond between the bromine and the C8 atom with a bond length of 2.6 Å, where the majority of the charge is located on bromine and the spin is mainly located on the C8 atom. The detailed understanding of such long-lived anionic states of nucleobase analogues supports the rational development of new therapeutic agents, in which the enhancement of dissociative electron transfer to the DNA backbone is critical to induce DNA strand breaks in cancerous tissue.
Periodic self-organization of matter beyond the diffraction limit is a puzzling phenomenon, typical both for surface and bulk ultrashort laser processing. Here we compare the mechanisms of periodic nanostructure formation on the surface and in the bulk of fused silica. We show that volume nanogratings and surface nanoripples having subwavelength periodicity and oriented perpendicular to the laser polarization share the same electromagnetic origin. The nanostructure orientation is defined by the near-field local enhancement in the vicinity of the inhomogeneous scattering centers. The periodicity is attributed to the coherent superposition of the waves scattered at inhomogeneities. Numerical calculations also support the multipulse accumulation nature of nanogratings formation on the surface and inside fused silica. Laser surface processing by multiple laser pulses promotes the transition from the high spatial frequency perpendicularly oriented nanoripples to the low spatial frequency ripples, parallel or perpendicular to the laser polarization. The latter structures also share the electromagnetic origin, but are related to the incident field interference with the scattered far-field of rough non-metallic or transiently metallic surfaces. The characteristic ripple appearances are predicted by combined electromagnetic and thermo-mechanical approaches and supported by SEM images of the final surface morphology and by time-resolved pump-probe diffraction measurements.
Currently great effort is made to find materials and technologies for the recycling of phosphate from wastewater.
Herein, we present an in-depth study of the Phosphate adsorption mechanism of a promising adsorber material, a Zn−Fe−Zr oxyhydroxide-based nanostructured precipitate. The behavior of the multicomponent nanomaterial, consisting of both crystalline and amorphous parts, is investigated via X-ray absorption fine structure spectroscopy and Mössbauer spectroscopy, revealing the importance of the nanostructured composition for the phosphate adsorption. We found evidence that adsorption takes place especially in the vicinity of iron sites in the amorphous part of the material.
The presentation focuses on the current state of the optical spectroscopic studies on plasmon enhanced upconversion luminescent processes of silica-metal core-shell nanocomposites. A general introduction of the upconversion process, the theoretical basis of plasmonic enhancement, the theoretical requirements in regard to NP architecture for plasmon enhanced UC will be outlined. The first proof-of-concept measurements show the difficulty in realization the theoretical measurement parameters in laboratory conditions and underline the need for shifting the experiments to single particle level.“
Lanthanide-doped up-converting nanoparticles (UCNPs) are promising reporters for medical diagnostics and bioimaging. Current limitations present their relative low absorption cross sections and low fluorescence efficiencies, with the latter being affected by particle size, surface chemistry, and microenvironment, particularly water.
Here, we present results from systematic studies of the excitation power density dependent upconversion luminescence spectra, intensities/intensity ratios of the individual emission bands, slope factors, and quantum yields of UCNPs of varying size, dopant concentration, and surface chemistry in different microenvironments as well as the up- and downconversion luminescence decay kinetics of the different emission bands. Moreover, first studies of the energy transfer from UCNPs to surface-bound organic dyes acting as fluorescence acceptors are shown. Based upon these measurements, fluorescence deactivation channels are identified and spectroscopic parameters for the screening of material performance are derived.
Components in the Aerospace, Power and Automotive engineering sectors are frequently subjected to cyclic stresses induced by thermal fluctuations and mechanical loads. For the design of such components, reliable material property data are required which need to be acquired using well accepted and reproducible test procedures for thermo-mechanical fatigue (TMF) loading. There is limited availability of proven TMF data indicating there is need for further research and testing. The TMF behaviour of materials is often desired to be simulated in models which describe the cyclic stress-strain behaviour, the fatigue life and the cyclic crack growth behaviour. There is a continuous need for the development and amendment of such models. Models can be validated by using materials in industrial applications which are subjected to TMF loading.
The 3rd Workshop on Thermo-Mechanical Fatigue was held on 27–29 April 2016 at BAM, Berlin, Germany. The workshop was attended by 90 attendees coming from 17 countries in the world. 38 presentations including five poster presentations were held.
The following topics were covered by the workshop:
– TMF of materials coated with Thermal Barrier Coatings.
– Thermal Gradient Mechanical Fatigue.
– TMF crack growth.
– TMF + High Cycle Fatigue.
– TMF Modelling and Lifetime Prediction.
– TMF Properties of steels, cast iron, Al-, Mg- and Ni-alloys
– Advanced TMF Testing Techniques.
– Industrial Applications.
A panel discussion was held regarding the present state of TMF testing standards (ISO and ASTM) and their potential for improvement. The discussion and contributions were summarized and forwarded to the standard committees. The 3rd TMF-Workshop ensured the continuation of international exchange of knowledge providing a forum to present and discuss all recent developments in the field of thermo-mechanical fatigue.
The current special issue publishes eleven selected papers of the 3rd TMF-Workshop 2016. The papers were peer reviewed by a number of experts in the Thermo-Mechanical Fatigue sector. I hope you will enjoy reading papers of this special issue.
Sol-Gel wood preservation
(2017)
The sol–gel-based modification of wood introduces chemical substances into wood in order to improve its characteristics and impart new properties. It stabilizes dimensions of wood (timber) components, increases its strength and resistance to water, and reduces cracking. Many sol–gel-based impregnations aim to protect against wood rot and fire. In most cases, the treatments are performed with alkoxysilanes, polysiloxanes, colloidal silica, or organically modified silica. In addition further substances such as titania, copper, and boron compounds have been applied on different types of wood. The precursor solutions were introduced by immersion, painting, or spray coating of wood followed by a drying and heat treatment process. The structure of the impregnated wood was investigated by SEM, EDX, TEM, FT-IR, NMR, and XRD. Frequently, test procedures according to standards were applied in order to assess the improvement in properties. Investigations demonstrate that silica and titania impregnations change properties first of all with increasing the amount of absorbed inorganic material (WPG), which is determined by the concentration of precursors, amount and size of particles in the sol, and the impregnation method. Sol–gel impregnation can be considered as an environmentally friendly approach of wood preservation. Various improvements in wood properties can be achieved such as reduced water uptake and volume swelling, improved weather stability, resistance against biodegradation, and fire retardancy.
The influence of temperature and counter body material on the tribological properties of a-C:H coatings deposited on Cronidur 30 steel has been investigated in a lubricated ball on disk contact siutation with an oil temperature up to 250°C. The results show, that the wear volumes of the system increase exponentially with increasing temperature.
In addition to the acid source, charring agent, and blowing agent, the binder is a crucial part of an intumescent coating. Its primary task is to bind all compounds, but it also acts as a carbon source and influences the foaming process. A series of intumescent coatings based on five different binders was investigated in terms of insulation, foaming, mechanical impact resistance, and residue morphology. The Standard Time-Temperature modified Muffle Furnace (STT MuFu+ ) was used for the bench-scale fire resistance tests and provided data on temperature and residue thickness as well as well-defined residues. The residue morphology was analyzed by nondestructive m-computed tomography and scanning electron microscopy. A moderate influence of the binder on insulation performance was detected in the set of coatings investigated, whereas the foaming dynamics and thickness achieved were affected strongly. In addition, the inner structure of the residues showed a rich variety. High expansion alone did not guarantee good insulation. Furthermore, attention was paid to the relation between the microstructure transition induced by carbon loss due to thermo-oxidation of the char and the development of the thermal conductivity and thickness of the coatings during the fire test.
Polycrystalline Ni materials with grain sizes less than 100 nm (nano crystalline NC) and with grain sizes in the micrometer range (micro crystalline MC) in form of thin films have become important in many technologies due to their improved physical, chemical and mechanical properties. Usual the mechanical properties of such coatings are described by a Hardness value and a Young´s modulus measured by Instrumented Indentation Testing (IIT).The behavior of such coatings during indentation test is influenced by different size effects having their representative length scale – grain size, coating thickness, length that characterizes the depth dependence of the hardness (Indentation Size Effect ISE). To estimate realistic values for the intrinsic coating Hardness and Young´s modulus all size effects have to be considered.
For this work thin nano crystalline Ni – coatings (average grain size 30 nm) with thickness from 1 μm to 5 μm were electrodeposited on brass substrates. Indentation tests in the continuous stiffness measurement (CSM) mode were provided on as prepared Ni – coatings using a G200 Nanoindentation system (Fa. Keysight). For estimation of the intrinsic hardness of the coatings from composite hardness values calculated from the measured force –displacement curve using the Oliver & Pharr method, the model described by Z.S. Ma [1] was used.
It was found that the experimental data can be well described by the model. The fitted values for the intrinsic hardness and the fitting parameters will be given. The different values of intrinsic hardness and of length characterizing depth dependence of the hardness for different coating thickness are discussed as results of changes in the coating structure because of changes in deposition parameters.
[1] Z.S. Ma, Y.C. Zhou, S.G. Long, C. Lu: On the intrinsic hardness of a metallic film/substrate system: Indentation size and substrate effects. International Journal of Plasticity 34 (2012) 1-11.
This work is supported by European Metrology Program for Innovation and Research (EMPIR)
(JRP 14IND03 Strength – ABLE)
The primary crystallite size of titania powder relates to its properties in a number of applications. Transmission electron microscopy was used in this interlaboratory comparison (ILC) to measure primary crystallite size and shape distributions for a commercial aggregated titania powder. Data of four size descriptors and two shape descriptors were evaluated across nine laboratories. Data repeatability and reproducibility was evaluated by analysis of variance. One-third of the laboratory pairs had similar size descriptor data, but 83% of the pairs had similar aspect ratio data. Scale descriptor distributions were generally unimodal and were well-described by lognormal reference models. Shape descriptor distributions were multi-modal but data visualization plots demonstrated that the Weibull distribution was preferred to the normal distribution. For the equivalent circular diameter size descriptor, measurement uncertainties of the lognormal distribution scale and width parameters were 9.5% and 22%, respectively. For the aspect ratio shape descriptor, the measurement uncertainties of the Weibull distribution scale and width parameters were 7.0% and 26%, respectively. Both measurement uncertainty estimates and data visualizations should be used to analyze size and shape distributions of particles on the nanoscale.
Magnetic iron oxide nanoparticle clusters (mnpc) coated with organic stabilizers were investigated using scanning transmission x-ray microscopy (STXM). Simultaneous surface and bulk sensitive Fe L3 edge absorption spectra, obtained using a photomultiplier tube and a channeltron, were used to detect subtle changes in the oxidation state in the surface and bulk of Iron Oxide mnpc.
The effectiveness of this mode of STXM operation is demonstrated for These nanoparticle clusters.
Magnetic iron oxide nanoparticle clusters (mnpc) coated with organic stabilizers were investigated using scanning transmission x-ray microscopy (STXM). Simultaneous surface and bulk sensitive Fe L₃ edge absorption spectra, obtained using a photomultiplier tube and a channeltron, were used to detect subtle changes in the oxidation state in the surface and bulk of Iron Oxide mnpc. The effectiveness of this mode of STXM operation is demonstrated for these nanoparticle clusters.
Diese Doktorarbeit ist das Resultat einer intensiven und fruchtbaren Zusammenarbeit zwischen dem Fachbereich 6.1 (Oberflächenanalytik und Grenzflächenchemie) der Bundesanstalt für Materialforschung und -prüfung (BAM) sowie der Arbeitsgruppe Theoretische Chemie von Professor Saalfrank an der Universität Potsdam. Zusammen haben wir die Strukturaufklärung von Systemen in kondensierter Phase unter Verwendung der Röntgenabsorptionsspektroskopie betrieben. Von Seiten der BAM wurden experimentelle Röntgenabsorptionsspektren hoher Auflösung an modernen Synchrotroneinrichtungen (BESSY II, Berlin) aufgenommen. Die Theoretische Chemie liefert, unter Verwendung quantenchemischer Methoden, die Möglichkeit die Spektren zu simulieren. Bei der Röntgenabsorption wird ein Photon hoher Energie von einem molekularen System absorbiert und in einen angeregten Zustand versetzt. Die Intensität der Absorption ist stark abhängig von der eingestrahlten Photonenenergie. Das resultierende Absorptionsspektrum enthält eine Vielzahl von Informationen. Meine Aufgabe bestand darin, die untersuchten Systeme am Computer zu modellieren.
Short course on ICP-MS
(2017)
ICP-MS is a well-established analytical method which excels by high accuracy, high dynamic range and extremely low limits of detection for most metals. Furthermore ICP-MS offers a very high multi-element coverage so that many elements of the periodic table can be detected simultaneously. In this series of lectures, we want to focus on the historical developments, fundamentals, instrumentation and novel applications of ICP-MS in the life and material sciences.
Polar semiconductor materials enable a variety of classic and quantum-light sources, which are optimized continuously. However, one key problem—the inherent electric crystal polarization of such materials—remains unsolved and deteriorates the radiative exciton decay rate. We suggest a sequence of reverse interfaces to compensate these polarization effects, while the polar, natural crystal growth direction is maintained. Former research approaches, like growth on less-polar crystal planes or even the stabilization of unnatural phases, never reached industrial maturity. In contrast, our concept provides a way for the development of ultrafast devices based on established growth processes for polar materials, while the electric potential landscape becomes adjustable.
At the core of luminescence color and lifetime Tuning of rare earth doped upconverting nanoparticles (UCNPs), is the understanding of the Impact of the particle architecture for commonly used sensitizer (S) and activator (A) Ions. In this respect, a series of core@Shell NaYF4 UCNPs doped with Yb3+ and Ho3+ ions are presented here, where the same dopant concentrations are distributed in different particle architectures following the scheme: YbHo core and YbHo@..., ...@YbHo, Yb@Ho, Ho@Yb, YbHo@Yb, and Yb@YbHo core-Shell NPs. As refealed by quantitative steady-state and time-resolved luminescence studies, the relative spatial Distribution of the A and S ions in the UCNPs and their protection from surface quenching has a critical Impact on ther luminescence characteristics. Although the increased amount of Yb3+ Ions boosts UCNP Performance by amplifying the Absorption, the Yb3+ ions can also efficiently dissipate the energy stored in the material through energy Migration to the surface, thereby reducing the Overall energy Transfer Efficiency to the activator ions. The results provide yet another proof that UC Phosphor chemistry combined with materials Engineering through intentional core@shell structures may help to fine-tune the luminescence Features of UCNPs for their specific future applications in biosensing, bioimaging, photovoltaics, and Display technologies.
Sensing of intracellular pH is of particular interest in biomedical research since structure and function of biomolecules strongly depend on the concentration of protons in their environment. We have functionalized photon upconversion nano-particles (UCNPs) with pH responsive dyes to achieve nanoprobes for intracellular pH determination. The sensing mechanism is based on a resonance energy transfer (UC-RET) from the 550 nm emission of hexagonal nanocrystals of NaYF4: Yb3+,Er3+ to the pH-sensitive fluorophore pHrodoTM Red. The nanocrystals were coated with thin shells of aminosilane or highly branched polyethylenimine (PEI) with several nanometer layer thickness for coupling of the pH indicator.
The nanoprobes are calibrated by ratiometric dual wavelength readout at 550 nm (reference signal) and 590 nm (sensor signal) and visualized using a scanning confocal fluorescence microscope with 980 nm excitation wavelength. It was found that PEI coating enables a higher coupling of indicator molecules on the particle surface, better signal to reference ratios in ratiometric readout and an improved cellular uptake compared to the aminosilane coated particles due to a more positive zeta potential. We studied the cellular uptake efficacy of the nanoprobes and determined to which type of compartment, lysosomes, endosomes or cytosol, the probes are targeted to by measuring the pH of their microenvironment. An in situ control was performed in live cells by a treatment with nigericin, whereby the pH of all intracellular compartments is set at extracellular level.
Finally, we will show new strategies for the preparation of UCNP-dye conjugates with improved UC-RET efficiency to achieve higher acceptor (sensor) emission.
Scanning Electron Microscopy (SEM) or Transmission Electron Microscopy (TEM) ? This is a question, nowadays discussed in EM labs of research and industry involved in the characterization and metrology of nanoparticles. The Scanning principle is adapted to TEM, the Transmission mode is adapted to Ultra High Resolution SEM. Can modern SEM replace TEM, reach atomic resolution even without Cs corrector or nm lateral resolution for energydispersive X-ray spectroscopy (EDX)?
Due to the development of a New Cold Field Emission (NCFE) electron source Hitachi SEMs SU9000 and SU8200 can deliver routinely sub-nm image resolution and EDX mappings at very high count rates and a lateral EDX resolution of a few nm. A TiO2 sample provided by BAM was analysed at 30kV using low kV STEM – simultaneously with the Through-the-lens (TTL) SE detector, the Bright Field transmitted and Dark Field transmitted signals. By this method a pixel precise information of the particles surface using SE, its chemical nature using DF-STEM and its crystalline structure using Bright Field signal is given in one 40sec scan. The advantage of this observation mode compared to Ultra Low Voltage imaging is outlined.
Several restoration projects of stained-glass windows have been performed in Poland since 2010.Chemical analysis of glass samples was performed with SEM/EDX on a FEI ESEM-XL 30, (EDX-EDAX) and with Micro-XRF (M4 Tornado, Bruker).The chemical composition of medieval glass samples and of glass samples of the 19th Century have been determined.
The investigation of physical properties and chemical composition generates data important for answering art-historical questions. Due to technological developments, technical diagnostics in art and culture are in ever-greater demand in such fields of transdisciplinary research. Based on one example, a collar drawing from the Berlin Diez albums, the present paper aims to give some insights into the multi-instrumental approach in the material analysis of cultural artefacts. The same methods were also applied to other drawings from the Diez Albums.
SAXS for the determination of the size distribution of nanoparticles: Application in catalysis
(2017)
The open source software packages SASfit1 and McSAS2 are widely used to determine the size distribution of nanoparticles. SASfit is based on classical curve fitting. The type of size distribution needs to be provided as constraint for analysis. Very often the lognormal size distribution is useful as shown for the characterization of single- and multimodal magnetic iron oxide particles. The use of SASfit is part of efforts to standardize analyzing methods for magnetic nanoparticles within the EU project NanoMag (www.nanomag-project.eu). In contrast to SASfit, it is not necessary to provide the type of size distribution when using the program McSAS. Both programs provide tools that allow the user to estimate uncertainties of the derived size distributions. Such is helpful in the development of nanoscale reference materials for environmental, health and safety measurements. As an example, a detailed study on using SAXS in the characterization of ultra-small-silver nanoparticles is presented. These particles are useful in the catalytic reduction of 4-nitrophenol and display an adjustable activity (see Figure).
Figure. Core-shell silver nanoparticles catalyze the reduction of 4-nitrophenol and display an increasing catalytic activity when stabilized with different ligands in the line bovine serum albumin (BSA), glutathione (GSH) and polyacrylic acid (PAA).5
This article reports on the characterization of four superparamagnetic iron oxide nanoparticles stabilized with dimercaptosuccinic acid, which are suitable candidates for reference materials for magnetic properties. Particles p1 and p2 are single-core particles, while p3 and p4 are multi-core particles. Small-angle X-ray scattering analysis reveals a lognormal type of size distribution for the iron oxide cores of the particles. Their mean radii are 6.9 nm (p1), 10.6 nm (p2), 5.5 nm (p3) and 4.1 nm (p4), with narrow relative distribution widths of 0.08, 0.13, 0.08 and 0.12. The cores are arranged as a clustered network in the form of dense mass fractals with a fractal dimension of 2.9 in the multi-core particles p3 and p4, but the cores are well separated from each other by a protecting organic shell. The radii of gyration of the mass fractals are 48 and 44 nm, and each network contains 117 and 186 primary particles, respectively. The radius distributions of the primary particle were confirmed with transmission electron microscopy. All particles contain purely maghemite, as shown by X-ray absorption fine structure spectroscopy
Naturwissenschaftliche Verfahren sind inzwischen fester Bestandteil bei der materialwissenschaftlichen Untersuchung von Kunst- und Kulturgut und bei der Entwicklung von Konservierungskonzepten zum Erhalt des kulturellen Erbes. Insbesondere werden zunehmend bildgebenden Verfahren wie die Computertomographie, die Radiographie oder die Multispektralanalyse verwendet, um die für das menschliche Auge nicht sichtbare Inhalte wie Vorzeichnungen, Pentimenti oder innere Strukturen zu visualisieren. Die entstehenden „neuen Bilder“ verändern jedoch die Sichtweise auf das kulturelle Artefakt, da sie tiefere Einblicke in den Herstellungsprozess, den Aufbau oder den Erhaltungszustand geben können. Weiterhin dokumentieren sie Veränderungen, denen ein Objekt unterworfen wurde. Anhand der Untersuchung von zwei Objekten mit dem Röntgenfluoreszenzportalscanner Jet Stream soll das Verhältnis Original – Digitalisat – Rekonstruktion diskutiert werden.
In this lecture the VSSA concept is explained, and VSSA as measured by BET. Results of the NanoDefine evaluation based on selected examples on real-world materials are presented. Recommendations for consideration of the VSSA concept for the implementation of the EC definition of nanomaterial for powder materials are given.
Role of metal cations in plasmon-catalyzed oxidation: A case study of p-aminothiophenol dimerization
(2017)
The mechanism of the plasmon-catalyzed reaction of p-aminothiophenol (PATP) to 4,4′-dimercaptoazobenzene (DMAB) on the surface of metal nanoparticles has been discussed using data from surface-enhanced Raman scattering of DMAB. Oxides and hydroxides formed in a plasmon-catalyzed process were proposed to play a central role in the reaction. Here, we report DMAB formation on gold nanoparticles occurring in the presence of the metal cations Ag+, Au3+, Pt4+, and Hg2+. The experiments were carried out under conditions where formation of gold oxide or hydroxide from the nanoparticles can be excluded and at high pH where the formation of the corresponding oxidic species from the metal ions is favored. On the basis of our results, we conclude that, under these conditions, the selective oxidation of PATP to DMAB takes place via formation of a metal oxide from the ionic species in a plasmon-catalyzed process. By evidencing the necessity of the presence of the metal cations, the reported results underpin the importance of metal oxides in the reaction.
Role of materials data
(2017)
In a general sense, data are the output of experimental research work. In this workshop we will present some basic ideas concerning the reliability of experimental data; this is a central issue both for individuals or labs producing results as well as for scientists working on theoretical models and engineers designing a machine. Digitalization accelerates enormously the data exchange between these communities; however, the required level of confidence on experimental results increases in the same way. We invite all the participants to reflect upon the value of materials data for their own work.
In der Krebs-Strahlentherapie werden halogenierte Nukleinbasen als Radiosensibilisatoren eingesetzt, um die Reaktivität der DNA gegenüber niederenergetischen Elektro-
nen (NEEs) zu erhöhen. NEEs erzeugen DNA-Strangbrüche bei spezifischen Energien (Resonanzen) durch dissoziative Elektronenanlagerung (DEA). Obwohl halogenierte Nukle-
inbasen intensive DEA-Resonanzen bei verschiedenen Elek-tronenenergien in der Gasphase aufweisen, kann der Einfluss der halogenierten Nukleinbasen auf tatsächliche DNA-Strangbrüche grundsätzlich nur schwer über den Energiebereich, in dem DEA stattfindet (< 12 eV), untersucht werden.
Mithilfe von DNA-Origami-Nanostrukturen haben wir die Energieabhängigkeit der Wirkungsquerschnitte für DNA-Strangbrüche von Oligonukleotiden bestimmt, die mit 8-
Bromadenin (8BrA) modifiziert wurden. Diese Ergebnisse wurden mit DEA-Messungen an isoliertem 8BrA in der Gas-phase verglichen. Entgegen der Erwartungen wird der Großteil der Strangbrüche durch Resonanzen um 7 eV hervorgerufen, wohingegen der Einfluss von Resonanzen bei sehr niedrigen Energien (< 2eV) auf die Strangbrüche gering ist.
Halogenated nucleobases are used as radiosensitizers in cancer radiation therapy, enhancing the reactivity of DNA to secondary low-energy electrons (LEEs). LEEs induce DNA strand breaks at specific energies (resonances) by dissociative electron attachment (DEA). Although halogenated nucleobases show intense DEA resonances at various electron energies in the gas phase, it is inherently difficult to investigate the influence of halogenated nucleobases on the actual DNA strand breakage over the broad range of electron energies at which DEA can take place (<12 eV). By using DNA origami nanostructures, we determined the energy dependence of the strand break cross-section for oligonucleotides modified with 8-bromoadenine ((8Br)A). These results were evaluated against DEA measurements with isolated (8Br)A in the gas phase. Contrary to expectations, the major contribution to strand breaks is from resonances at around 7 eV while resonances at very low energy (<2 eV) have little influence on strand breaks.
Reliable nanomaterial classification of powders using the volume-specific surface area method
(2017)
The volume-specific surface area (VSSA) of a particulate material is one of two apparently very different metrics recommended by the European Commission for a definition of "nanomaterial" for regulatory purposes: specifically, the VSSA metric may classify nanomaterials and non-nanomaterials differently than the median size in number metrics, depending on the chemical composition, size, polydispersity, shape, porosity, and aggregation of the particles in the powder.
Here we evaluate the extent of agreement between classification by electron microscopy (EM) and classification by VSSA on a large set of diverse particulate substances that represent all the anticipated challenges except mixtures of different substances. EM and VSSA are determined in multiple labs to assess also the level of reproducibility. Based on the results obtained on highly characterized benchmark materials from the
NanoDefine EU FP7 project, we derive a tiered screening strategy for the purpose of implementing the definition of nanomaterials. We finally apply the Screening strategy to further industrial materials, which were classified correctly and left only borderline cases for EM.
On platelet-shaped nanomaterials, VSSA is essential to prevent false-negative classification by EM. On porous materials, approaches involving extended Adsorption isotherms prevent false positive classification by VSSA. We find no false negatives by VSSA, neither in Tier 1 nor in Tier 2, despite real-world industrial polydispersity and diverse composition, shape, and coatings. The VSSA screening strategy is recommended for inclusion in a technical guidance for the implementation of the definition.
In October 2011 the European Commission (EC) published a "Recommendation on the definition of na-nomaterial" (2011/696/EU), to promote consistency in the interpretation of the term "nanomaterial" for legislative and policy purposes in the EU. The EC NM Definition includes a commitment to its review in the light of experience and of scientific and technological developments. This review is ongoing in 2017 and as a contribution to the review the Joint Research Centre of the European Commission (JRC) has already developed a series of three scientific-technical reports with the title: “Towards a review of the EC Recommendation for a definition of the term nanomaterial” which provides to the EC policy services sci-ence-based options on how the definition could be revised or supported with additional guidance.
The overarching nature and wide scope of the EC NM Definition, as it does not exclude a priori any particulate material regardless the state, form and size, creates many analytical challenges in its imple-mentation for all stakeholders, including enterprises and regulators.
The NanoDefine project has as core objective to support the implementation of the EC NM Definition. In an earlier report1 key aspects of the EC NM Definition were addressed, with the goal to improve the implementability of the EC NM Definition. Based on further developments and results obtained in NanoDefine project that first report was updated and is presented here. The key aspects are discussed based on the results of four years of research performed within the framework of the project. As a result this report assesses how well the requirements of the EC NM Definition can be fulfilled with currently available analytical possibilities. It presents recommendations and options on a revision of the EC NM Definition to improve the implementability of the definition based on currently available analytical possi-bilities, according to the state of the art in 2017. Of the technical issues considered in this report, the following seem to deserve the most attention in terms of clarification of the definition and/or provision of additional implementation guidance: 'external dimension', ‘number based particle size distribution‘, ‘polydispersity‘ and ‘upper size limit‘, the term ‘particle’, the ‘means to prove that a material is not a nanomaterial‘ and ‘the role of the volume specific sur-face area (VSSA)‘, and "particulate materials'.
Lanthanide-doped up-converting nanoparticles (UCNPs) are promising reporters for medical diagnostics and bioimaging, which are excited in the near infrared (NIR) by multiphoton absorption processes, and show multiple narrow emission bands in the visible (vis) and NIR, long luminescence lifetimes in the μs range, and excellent photostability. Current limitations present their relative low absorption cross sections and low fluorescence efficiencies, with the latter being affected by particle size, surface chemistry, and microenvironment, particularly water.
Here, we present results from systematic studies of the excitation power density dependent upconversion luminescence spectra, intensities/intensity ratios of the individual emission bands, slope factors, and quantum yields of UCNPs of varying size, dopant concentration, and surface chemistry in different microenvironments as well as the up- and downconversion luminescence decay kinetics of the different emission bands. Moreover, first studies of the energy transfer from UCNPs to surface-bound organic dyes acting as fluorescence acceptors are shown. Based upon these measurements, fluorescence deactivation channels are identified and spectroscopic parameters for the screening of material performance are derived.