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We report the results of a Versailles Project on Advanced Materials and Standards (VAMAS) interlaboratory study on the measurement of the shell thickness and chemistry of nanoparticle coatings. Peptide-coated gold particles were supplied to laboratories in two forms: a colloidal suspension in pure water and particles dried onto a silicon wafer. Participants prepared and analyzed these samples using either X-ray photoelectron spectroscopy (XPS) or low energy ion scattering (LEIS). Careful data analysis revealed some significant sources of discrepancy, particularly for XPS. Degradation during transportation, storage, or sample preparation resulted in a variability in thickness of 53%. The calculation method chosen by XPS participants contributed a variability of 67%. However, variability of 12% was achieved for the samples deposited using a single method and by choosing photoelectron peaks that were not adversely affected by instrumental transmission effects. The study identified a need for more consistency in instrumental transmission functions and relative sensitivity factors since this contributed a variability of 33%. The results from the LEIS participants were more consistent, with variability of less than 10% in thickness, and this is mostly due to a common method of data analysis. The calculation was performed using a model developed for uniform, flat films, and some participants employed a correction factor to account for the sample geometry, which appears warranted based upon a simulation of LEIS data from one of the participants and comparison to the XPS results.
Results are reported from a pilot study under the Consultative Committee for Amount of Substance (CCQM) to compare measurements of and resolve any relevant measurement issues in, the amount of thermal SiO2 oxide on (100) and (111) orientation Si wafer substrates in the thickness range 1.5 - 8 nm. As a result of the invitation to participate in this activity, 45 sets of measurements have been made in different laboratories using 10 analytical methods: medium-energy ion scattering spectrometry (MEIS), nuclear reaction analysis (NRA), RBS, elastic backscattering spectrometry (EBS), XPS, SIMS, ellipsometry, grazing-incidence x-ray reflectrometry (GIXRR), neutron reflectometry and transmission electron microscopy (TEM). The measurements are made on separate sets of 10 carefully prepared samples, all of which have been characterised by a combination of ellipsometry and XPS using carefully established reference conditions and reference parameters.
The results have been assessed against the National Physical Laboratory (NPL) data and all show excellent linearity. The remaining data sets correlate with the NPL data with average root-mean-square scatters of 0.15 nm, half being better than 0.1 nm and a few at or better than 0.05 nm. Each set of data allows a relative scaling constant and a zero thickness offset to be determined. Each method has an inherent zero thickness offset between 0 nm and 1 nm and it is these offsets, measured here for the first time, that have caused many problems in the past. There are three basic classes of offset: water and carbonadeous contamination equivalent to ~1 nm as seen by ellipsometry; adsorbed oxygen mainly from water at an equivalent thickness of 0.5 nm as seen by MEIS, NRA, RBS and possibly GIXRR; and no offset as seen by XPS using the Si 2p peaks. Each technique has a different uncertainty for the scaling constant and consistent results have been achieved. X-Ray photoelectron spectroscopy has large uncertainties for the scaling constant but a high precision and, critically, if used correctly, has zero offset. Thus, a combination of XPS and the other methods allows the XPS scaling constant to be determined with low uncertainty, traceable via the other methods. XPS laboratories returning results early were invited to test a new reference procedure. All showed very significant improvements. The reference attenuation lengths thus need scaling by 0.986 ± 0.009 (at an expansion factor of 2) deduced from the data for the other methods. Several other methods have small offsets and, to the extent that these can be shown to be constant or measurable, then these methods will also show low uncertainty. Recommendations are provided for parameters for XPS, MEIS, RBS and NRA to improve their accuracy.
Redox behaviour of La-Cr compounds formed in CrOX/La2O3 mixed oxides and CrOX/La2O3/ZrO2 catalysts
(2003)
The redox behaviour of chromium oxide in CrOx/La2O3, CrOx/La2O3/ZrO2 and CrOx/ZrO2 mixed oxide systems has been investigated by temperature-programmed reduction (TPR), photoelectron spectroscopy (XPS) and Raman spectroscopy (RS). The formation of La-Cr compounds such as La2CrO6, LaCrO4 was shown to occur by calcination of CrOx/La2O3 and CrOx/La2O3/ZrO2 at 600 °C. With a Cr content of ca. 4 wt.%, it was revealed that, having been reduced to Cr3+-containing compounds, La2CrO6 and/or LaCrO4 in both systems may be restored by reoxidation at 600 °C. In the case of CrOx/La2O3/ZrO2 catalysts, it is suggested that these compounds were real surface species anchored as an overlayer on zirconia. Such a structure may stabilise, on the one hand, the tetragonal modification of zirconia and, on the other hand, highly dispersed state of Cr species in calcined as well as in reduced catalysts.
Nanocrystalline particles of high temperature pretreated titania, zirconia or hafnium oxide, embedded in a carbon matrix, have been found to catalyze the aromatization of n-octane into ethylbenzene (EB) and o-xylene (OX) with high selectivity. The carbon matrix itself is catalytically not active, but seems to co-operate with the transition metal oxides in such a way that the various metal oxide/carbon composite materials exhibit equal selectivity patterns. In detail, the carbon component stabilizes a high dispersion of the oxides during the high temperature pretreatment procedure. This thermal treatment results in a destruction of surface acidity of the oxides, which would otherwise be responsible for undesirable consecutive and parallel reactions. Moreover, the carbon component is involved in the deep dehydrogenation of alkanes to multiple unsaturated alkenes. This is explained by the ability of surface carbon atoms to interact with hydrogen. The bulk and surface structure of the catalysts have been characterized by XRD, specific surface area measurements, XPS, UPS, Raman spectroscopy, in situ ESR and DRIFT spectroscopy.
The formation of a third body layer on a conventional friction material during braking tests was studied in some detail using TEM, SEM, and X-ray photoelectron spectroscopy (XPS) techniques. Plate shaped micro-contact areas representing a compositional mix of all components of the tribocouple and exhibiting a nanocry stalline microstructure were identified after a run-in period.
CrOx/La2O3 mixed oxides, prepared by impregnating La2O3 with appropriate aqueous solutions of (NH4)2CrO4 and calcining at 600 °C for 4 h, have been investigated by means of XRD, TPR, XPS, DRIFTS, and Raman spectroscopy (RS). The formation of the compounds La2CrO6, La(OH)CrO4 and LaCrO4 under these conditions was evidenced. Strong peaks at 864, 884, 913, and 921 cm-1, as well as weak peaks at 136, 180, 354, 370, and 388 cm-1 in the RS spectrum of CrOx/La2O3 have been assigned to La2CrO6.
Pyrrolovesamicols - synthesis, structure and VAChT binding of two 4-fluorobenzoyl regioisomers
(2012)
This Letter describes the synthesis of two regioisomers of a new class of vesamicol analogs as possible
ligands for imaging the vesicular acetylcholine transporter in future PET studies. The two pyrrolovesamicols
(±)-6a and (±)-6b were synthesized by nucleophilic ring opening reaction of a tetrahydroindole epoxide
precursor with 4-phenylpiperidine. The reaction mechanism of the synthesis was studied by HPLC
and the molecular structures were determined by X-ray structure analysis. Unexpected low binding affinities
to VAChT (Κi = 312 ± 73 nM for (±)-6a and Κi = 7320 ± 1840 nM for (±)-6b) were determined by competitive
binding analysis using a cell line stably transfected with ratVAChT and (–)-[3H]vesamicol.
To properly understand and assess the long-term behaviour of geosynthetic materials it is necessary to investigate the various types of possible degradation mechanims. This includes both chemical and mechanical behaviour, and sometimes even their interactions with one another. Clearly, chemical degradation of geosynthetics depends on the polymer type. For example, polyolefins are vulnerable to oxidation; polyesters are susceptible to hydrolysis; and plasticizers can leach from polyvinyl chloride. This paper describes the concept of these three types of degradation, but focuses on the oxidation of polyolefins since the majority of the geosynthetics is made from this type of polymer. The methods used to predict the lifetime of antioxidants and service life of the geosynthetic material will be illustrated. Furthermore, the influence of temperature, pressure, and ultraviolet light on the service life are also demonstrated. Finally, the current specifications targeting the longevity of different geosynthetics are presented.
Regarding mechanical degradation, the paper mainly focuses upon the creep deformation of geogrids and stress crack resistance (SCR) of polyethylene geomembranes and geopipe. The method to assess stress crack resistance is described, and the microscopic mechanisms that lead to such failure are explained. For creep evaluation, different acceleration tests are presented and their applicability with respect to the different types of polymers is illustrated. In addition, the long-term shear behaviour of geocomposites and geosynthetic clay liners is presented.
A new type of test sample for the determination of lateral resolution in surface analysis is presented. The certified reference material BAM-L002 Nanoscale strip pattern for length calibration and testing of lateral resolution is an embedded cross-section of epitaxially grown layers of AlxGa1-xAs and InxGa1-xAs on GaAs substrate. The surface of the sample provides a flat pattern with strip widths of 0.4-500 nm. The combination of gratings, isolated narrow strips and sharp edges of wide strips offers improved possibilities for the calibration of a length scale, the determination of lateral resolution and the optimization of instrument settings. The feasibility of the reference material for an analysis of lateral resolution is demonstrated for SIMS.
Different, partly complementary and partly redundant characterization methods were applied to study the transition of magnetite, graphite and MoS2 powders to mechanically alloyed nanostructures. The applied methods were: Transmission electron microscopy (TEM), Mössbauer spectroscopy (MS), Raman spectroscopy (RS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The main objective was to prepare a model material providing the essential features of a typical tribofilm forming during automotive braking, and to assess the impact of different constituents on sliding behaviour and friction level. Irrespective of the initial grain size, the raw materials were transferred to a nanocrystalline structure and mixed on a nanoscopic scale during high energy ball milling. Whereas magnetite remained almost unchanged, graphite and molybdenum disulphide were transformed to a nanocrystalline and highly disordered structure. The observed increase of the coefficient of friction was attributed to a loss of lubricity of the latter ingredient due to this transformation and subsequent oxidation.
Ausgehend von den verstärkt auftretenden AKR-Schäden an den vor 2005 hergestellten BAB-Abschnitten verfolgte das Forschungsvorhaben zwei Ziele. So sollte einerseits die Ursache für die mit der AKR-Schadensentwicklung einhergehende Dunkelfärbung der Oberfläche der Betonfahrbahndecke im Fugenbereich ermittelt werden. Andererseits galt es, ausgehend von der Zustands- und Schadenserfassung das AKR-Restschädigungspotenzial der Prüfkörper aus je drei ein- und zweischichtig ausgeführten, unterschiedlich stark AKR-geschädigten BAB-Abschnitten vergleichend zu bewerten. Folgende Ergebnisse wurden u. a. erzielt:
1. Dunkelfärbung Experimenteller Nachweis mit kombinierter insitu-
Feuchtemessung mit Radar (integral) und NMR (tiefenaufgelöst), dass Dunkelfärbung der Oberfläche der Betonfahrbahndecke im Fugenbereich auf eine erhöhte Durchfeuchtung der Betonrandzone zurückzuführen ist; erfolgreiche Validierung der ZfP-Ergebnisse mit Darr-Wäge-Versuch.
2. Zustand beprobter BAB-Abschnitte und schadenskategoriespezifische
Bewertung der AKR-Prüfverfahren:
• Auffinden von Horizontalrissen im Bereich der Querscheinfuge bei allen AKR-geschädigten BAB-Abschnitten,
• Ermittlung mittlerer Eindringtiefen bei Natrium von maximal 20 bis 45 mm und bei Chlorid von maximal 15 bis 60 mm im Entnahmezustand;
keine Korrelation mit der AKR-Schadenskategorie des jeweiligen BAB-Abschnitts,
• Nachweis gleichzeitig auftretender SEB bei allen AKR-geschädigten BAB-Abschnitten im Entnahmezustand,
• keine signifikante Verminderung der Spaltzugfestigkeit durch die verstärkte AKR am Plattenrand,
• Ermittlung eines erhöhten AKR-Restschädigungspotenzials bei vier der sechs beprobten BAB-Abschnitte primär mittels AKR-erformanceprüfungen,
• Ermittlung höherer Dehnungen bei Performanceprüfungen aus Ober- und Unterbeton bestehenden Halbschalen, als an separat aus Ober- und Unterbeton gewonnenen Prismen,
• Unauffälliges Verhalten nahezu aller bei der Performanceprüfung auffälligen Bestandsbetone im 40°C- und 60°C-Betonversuch; vermutete Ursache: mit LIBS nachgewiesene hohe und tiefreichende Auslaugung der Alkalien.
Directing nanoparticles to the nucleus by attachment of nuclear localization sequences (NLS) is an aim in many applications. Gold nanoparticles modified with two different NLS were studied while crossing barriers of intact cells, including uptake, endosomal escape, and nuclear translocation. By imaging of the nanoparticles and by characterization of their molecular interactions with surface-enhanced Raman scattering (SERS), it is shown that nuclear translocation strongly depends on the particular incubation conditions. After an 1 h of incubation followed by a 24 h chase time, 14 nm gold particles carrying an adenoviral NLS are localized in endosomes, in the cytoplasm, and in the nucleus of fibroblast cells. In contrast, the cells display no nanoparticles in the cytoplasm or nucleus when continuously incubated with the nanoparticles for 24 h. The ultrastructural and spectroscopic data indicate different processing of NLS-functionalized particles in endosomes compared to unmodified particles. NLS functionalized nanoparticles form larger intraendosomal aggregates than unmodified gold nanoparticles. SERS spectra of cells with NLS-functionalized gold nanoparticles contain bands assigned to DNA and were clearly different from those with unmodified gold nanoparticles. The different processing in the presence of an NLS is influenced by a continuous exposure of the cells to nanoparticles and an ongoing nanoparticle uptake. This is supported by mass-spectrometry-based quantification that indicates enhanced uptake of NLS-functionalized nanoparticles compared to unmodified particles under the same conditions. The results contribute to the optimization of nanoparticle analysis in cells in a variety of applications, e.g., in theranostics, biotechnology, and bioanalytics.
Multifunctional composite nanoprobes consisting of iron oxide nanoparticles linked to silver and gold nanoparticles, Ag–Magnetite and Au–Magnetite, respectively, were introduced by endocytic uptake into cultured fibroblast cells. The cells containing the non-toxic nanoprobes were shown to be displaceable in an external magnetic field and can be manipulated in microfluidic channels. The distribution of the composite nanostructures that are contained in the endosomal system is discussed on the basis of surfaceenhanced Raman scattering (SERS) mapping, quantitative laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) micromapping, and cryo soft X-ray tomography (cryo soft-XRT). Cryo soft-XRT of intact, vitrified cells reveals that the composite nanoprobes form intra-endosomal aggregates. The nanoprobes provide SERS signals from the biomolecular composition of their surface in the endosomal environment. The SERS data indicate the high stability of the nanoprobes and of their plasmonic properties in the harsh environment of endosomes and lysosomes. The spectra point at the molecular composition at the surface of the Ag–Magnetite and Au–Magnetite nanostructures that is very similar to that of other Composite structures, but different from the composition of pure silver and gold SERS nanoprobes used for intracellular investigations. As shown by the LA-ICP-MS data, the uptake efficiency of the magnetite composites is approximately two to three times higher than that of the pure gold and silver nanoparticles.
Linear sensor for areal subsurface gas monitoring - calibration routine and validation experiments
(2014)
Membrane based linear gas sensors and fiber optical sensors feature similar geometries and complement each other in quantities to be measured. To the author's best knowledge, it is the first time that these sensors are combined to a multifunctional sensor for distributed measuring of gas concentrations, temperature, and strain. Objective is a comprehensive monitoring of underground gas storage areas. In the presented project a 400 m² test site and a corresponding laboratory system were just built up to characterize, validate, and optimize the combined sensor. Application of the sensor lines in a grid structure should enable spatial resolution of the measurement data and early detection of relevant events, as gas leakage, temperature change, or mechanical impact. A Calibration routine was developed which can be applied subsequent to underground installation. First measurement results indicate the potential of the method, with regard to highly topical energy transport and storage issues.
One of the main unsolved issues of under-ground storages for, e.g., CO2, H2, and natural gas is the comprehensive surveillance of these areas with reasonable effort and costs. Conventional sensors (e.g., soil air probes or borehole probes), however, can only be used for punctual or locally limited measurements; further their application can cause structural influences (invasive application).
In this paper, we describe in detail the setup of a CO2 injection soil test field. This test field will be used to enhance and validate an innovative ap-proach for distributed subsurface monitoring of gas storage areas. To the author’s knowledge, this is the first time that, for this purpose, a test field is built in an application relevant scale.
A 400 m² soil test field with gas injection system was built up for the purpose of large-scale validation, optimization, and characterization of a novel comprehensive monitoring method for underground gas storage areas. The method combines gas sensing technology with linear form factor for in-situ monitoring of gases in soil with the mapping capabilities of Computed Tomography (CT) to reconstruct time-series of gas distribution maps based on samples of orthogonally-aligned linear gas sensors. Several injection experiments with carbon dioxide (CO2) at different days with varying boundary conditions indicates the potential of the method for, e.g., rapid leakage detection with respect to Carbon Capture and Storage (CCS) issues.