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- EXAFS (3)
- Dielectric spectroscopy (2)
- Disorganized bone (2)
- Electrochromism (2)
- Local structure (2)
- Metallo-supramolecular polyelectrolytes (2)
- Micro-computed tomography (2)
- Rhodium (2)
- Silicon nitride (2)
- X-ray topography (2)
Organisationseinheit der BAM
For the first time, an international comparison was conducted on the determination of the purity of a high purity element. Participants were free to choose any analytical approach appropriate for their institute’s applications and services. The material tested was a high purity zinc, which had earlier been assessed for homogeneity and previously used in CCQM-K72 for the determination of six defined metallic impurities. Either a direct metal assay of the Zn mass fraction was undertaken by EDTA titrimetry, or an indirect approach was used wherein all impurities, or at least the major ones, were determined and their sum subtracted from ideal purity of 100 %, or 1 kg/kg. Impurity assessment techniques included glow discharge mass spectrometry, inductively coupled plasma mass spectrometry and carrier gas hot extraction/combustion analysis. Up to 91 elemental impurities covering metals, non-metals and semi-metals/metalloids were quantified. Due to the lack of internal experience or experimental capabilities, some participants contracted external laboratories for specific analytical tasks, mainly for the analysis of non-metals. The reported purity, expressed as zinc mass fraction in the high purity zinc material, showed excellent agreement for all participants, with a relative standard deviation of 0.011 %. The calculated reference value, w(Zn) = 0.999 873 kg/kg, was assigned an asymmetric combined uncertainty of + 0.000025 kg/kg and – 0.000028 kg/kg. Comparability amongst participating metrology institutes is thus demonstrated for the purity determination of high purity metals which have no particular difficulties with their decomposition / dissolution process when solution-based analytical methods are used, or which do not have specific difficulties when direct analysis approaches are used. Nevertheless, further development is required in terms of uncertainty assessment, quantification of non-metals and the determination of purity of less pure elements and/or for those elements suffering difficulties with the decomposition process.
The present study is dealing with the basic physics for a novel way to generate a free-formed ceramic body, not like common layer by layer, but directly by Selective Volume Sintering (SVS) in a compact block of ceramic powder. To penetrate with laser light into the volume of a ceramic powder compact it is necessary to investigate the light scattering properties of ceramic powders. Compared with polymers and metals, ceramic materials are unique as they offer a wide optical window of transparency. The optical window typically ranges from below 0.3 up to 5 µm wave length. In the present study thin layers of quartz glass (SiO2) particles have been prepared. As a function of layer thickness and the particle size, transmission and reflection spectra in a wave length range between 0.5 and 2.5 µm have been recorded. Depending on the respective particle size and by choosing a proper relation between particle size and wave length of the incident laser radiation, it is found that light can penetrate a powder compact up to a depth of a few millimeters. With an adjustment of the light absorption properties of the compact the initiation of sintering in the volume of the compact is possible.
Short-range order has been investigated in Zr69.5Cu12Ni11Al7.5 and Zr41.5Ti41.5Ni17 metallic glasses using X-ray absorption spectroscopy and ab initio molecular dynamics simulations. While both of these alloys are good glass formers, there is a difference in their glass-forming abilities (Zr41.5Ti41.5Ni17 > Zr69.5Cu12Ni11Al7.5). This difference is explained by inciting the relative importance of strong chemical order, icosahedral content, cluster symmetry and configuration diversity.
Within the National Metrology Institutes (NMIs) and designated laboratories, an interlaboratory comparison, CCQM-P107, was conducted to verify the degree of international comparability concerning the results of purity analysis. The mass fractions of Ag, Bi, Cd, Cr, Ni, Tl at the lower mg/kg-level in a high purity zinc material were determined, but the real measurand in metrological sense was the sum of the six mass fractions. Homogeneity was investigated by glow discharge mass spectrometry, reference values were obtained using isotope dilution mass spectrometry. Six NMIs participated, contributing eight independent data sets. The agreement amongst the results of the participants, their median and the agreement with the reference values were usually excellent and in almost all cases below the target uncertainty of 30% relative. In this manner, the accuracy of results and the comparability between the participants was demonstrated to be established.
The first hard X-ray beamline at BESSY II will be installed by BAM and PTB at a superconducting 7 T wavelength shifter. The main optical elements of the beamline are a Double-Multilayer-Monochromator and a Double-Crystal-Monochromator. The two devices can be used separately or in-line. Main applications of monochromatic radiation with photon energies up to 50 keV are X-ray fluorescence analysis, micro-computed tomography, X-ray topography, detector calibration and reflectometry. Calculable undispersed radiation up to 200 keV will be available for radiometric applications.
The impact of very high cycle fatigue (VHCF) load conditions on the microstructure of specimens consisting of nodular cast iron is analyzed by means of micro-computed tomography (µCT) utilizing both monochromatic synchrotron radiation and polychromatic X-ray tube radiation. Using 3D µCT, the microstructure in the region of the smallest cross-sections of shouldered round specimens is imaged in different stages of the VHCF loading. By digital image correlation (DIC) of these tomograms strain fields are analyzed three-dimensionally. Strain levels in the range of a few percent were detected. It is proven that a localization of strain allows to predict the site of the crack which precedes and induces the macroscopic failure of the specimens.
A new instrument for simultaneous microbeam small- and wide-angle X-ray scattering and X-ray fluorescence (SAXS/WAXS/XRF) is presented. The instrument is installed at the microfocus beamline at BESSY II and provides a beam of 10 µm size with a flux of about 109 photons s-1. A SAXS resolution up to 500 Å d-spacing and a range of scattering vectors of almost three orders of magnitude are reached by using a large-area high-resolution CCD-based detector for simultaneous SAXS/WAXS. The instrument is particularly suited for scanning SAXS/WAXS/XRF experiments on hierarchically structured biological tissues. The necessary infrastructure, such as a cryo-stream facility and an on-site preparation laboratory for biological specimens, are available.
Local structures of amorphous and quasicrystalline phases in Zr–Ti–Ni and Zr–Ti–Ni–Cu alloys have been studied by means of x-ray absorption spectroscopy. The amorphous phases show a high degree of icosahedral short-range order. In all investigated systems local order around Cu and Ni atoms was found to be nearly identical pointing to site substitution of Ni by Cu as the reason for an improved glass forming ability when Ni is partly substituted by Cu. The results strengthen an icosahedral cluster based approach for the structure of metallic glasses and indicate the importance of the medium-range order on glass formation.
The laboratory rat is one of the most frequently-used animal models for studying bone biology and skeletal diseases. Here we show that a substantial portion of the cortical bone of mature rats is primary endochondral bone, consisting of a disorganized arrangement of mineralized collagen fibers. We characterize the structure and mechanical properties of the cortical bone of the rat. We show that the cortical bone consists of two architecturally distinct regions. One region, consisting of well-organized circumferential lamellae (CLB), is located in the endosteal and/or the periosteal regions while another, disorganized region, is located in the more central region of the cortex. Unexpectedly, we found that the disorganized region contains many islands of highly mineralized cartilage.
Micro tomography showed different structural and compositional properties of the two primary structural elements; the CLB region has lower mineral density, lower porosity, larger but fewer blood vessels and fewer lacunae. However, no difference was found in the average lacunar volume. Additionally the mean indentation modulus of the CLB region was lower than that of the disorganized region. The islands of calcified cartilage were found to be extremely stiff, with an indentation modulus of 33.4 ± 3.5 GPa.
We conclude that though the cortical bone of rats is in part lamellar, its architecture is markedly different from that of the cortical bone of humans, a fact that must be borne in mind when using the rat as a model animal for studies of human bone biology and disease.
The results of analytical measurements performed with solid-sampling techniques are affected by the distribution of the analytes within the matrix. The effect becomes significant in case of determination of trace elements in small subsamples. In this framework we propose a measurement model based on Instrumental Neutron Activation Analysis to determine the relative variability of the amount of an analyte among subsamples of a material. The measurement uncertainty is evaluated and includes the counting statistics, the full-energy gamma peak efficiency and the spatial gradient of the neutron flux at the irradiation position. The data we obtained in a neutron activation experiment and showing the relative variability of As, Au, Ir, Sb and W among subsamples of a highly pure Rh foil are also presented.
Nanocomposites with a predominantly exfoliated morphology were prepared by melt blending of organically modified doubled layered hydroxide (LDH) and low density polyethylene (PE). The prepared materials were investigated by differential scanning calorimetry (DSC) and in detail by dielectric spectroscopy. The DSC experiments show that the degree of crystallinity decreases linearly with increasing content of the LDH. The extrapolation of this dependence to zero results in a limiting concentration of ca. 50 wt % LDH were the crystallization of PE is completely suppressed by the nanofiller. The dielectric response of pure polyethylene shows different weak relaxation processes. The intensity of dynamic glass transition (β-relaxation) increases with the concentration of LDH. This is attributed to the increasing concentration of the exchanged anion dodecyl benzene sulfonate (SDBS). The SDBS molecules are strongly adsorbed at the exfoliated LDH layers. Therefore, a detailed analysis of the β-relaxation provides information about the structure and the molecular dynamics in the interfacial region between the exfoliated LDH layers and the polyethylene matrix. This analysis shows that the β-relaxation region consists of two processes: both of them obey glassy dynamics. The difference in corresponding Vogel (ideal glass transition) temperatures is about 30 K. The relaxation process at lower frequency is assigned to polyethylene segments with a reduced molecular mobility close to LDH layers. The process at higher frequencies is related to polyethylene segments in a farer distance for the surface of the nanofiller. In the nanocomposite materials an additional process due to Maxwell-Wagner-Sillars (MWS) polarization was observed. The time constant of this MWS process can be correlated with characteristic length scales in nanocomposites and therefore provides additional information on dispersion and delamination/exfoliation of the LDH layers in these materials.
Gravimetrically prepared mono-elemental reference solutions having a well-known mass fraction of approximately 1 g/kg (or a mass concentration of 1 g/L) define the very basis of virtually all measurements in inorganic analysis. Serving as the starting materials of all standard/calibration solutions, they link virtually all measurements of inorganic analytes (regardless of the method applied) to the purity of the solid materials (high-purity metals or salts) they were prepared from. In case these solid materials are characterized comprehensively with respect to their purity, this link also establishes direct metrological traceability to The International System of Units (SI). This, in turn, ensures the comparability of all results on the highest level achievable. Several national metrology institutes (NMIs) and designated institutes (DIs) have been working for nearly two decades in close cooperation with commercial producers on making an increasing number of traceable reference solutions available. Besides the comprehensive characterization of the solid starting materials, dissolving them both loss-free and completely under strict gravimetric control is a challenging problem in the case of several elements like molybdenum and rhodium. Within the framework of the European Metrology Research Programme (EMRP), in the Joint Research Project (JRP) called SIB09 Primary standards for challenging elements, reference solutions of molybdenum and rhodium were prepared directly from the respective metals with a relative expanded uncertainty associated with the mass fraction of Urel(w)<0.05 %. To achieve this, a microwave-assisted digestion procedure for Rh and a hotplate digestion procedure for Mo were developed along with highly accurate and precise inductively coupled plasma optical emission spectrometry (ICP OES) and multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) methods required to assist with the preparation and as dissemination tools.
The local structure around Ni and La atoms in Al85Ni10La5 amorphous powder after ball milling was investigated by X-ray absorption spectroscopy. A continuous decrease in coordination number of Ni and La as a function of milling time was observed, while the nearest neighbour distance and the mean square atomic displacement did not change, pointing at the creation of free volume around the Ni and La atoms. These structural changes resemble those of a liquid upon temperature increase. The results are described by a shear band model in which the coordination numbers of Ni and La are different within and outside a shear band.
Background. Post-menopausal osteoporosis is a common health problem worldwide, most commonly caused by estrogen deficiency. Most of the information regarding the skeletal effects of this disease relates to trabecular bone, while cortical bone is less studied. The purpose of this study was to evaluate the influence of estrogen deficiency on the structure and mechanical properties of cortical bone.
Methods. Eight ovariectomized (OVH) and eight intact (control) Sprague Dawley rats were used. Structural features of femoral cortical bone were studied by light microscopy, scanning electron microscopy and synchrotron-based microcomputer-tomography and their mechanical properties determined by nano-indentation.
Results. Cortical bone of both study groups contains two distinct regions: organized
circumferential lamellae and disordered bone with highly mineralized cartilaginous islands. Lacunar volume was lower in the OVH group both in the lamellar and disorganized regions (182 ± 75 µm3 vs 232 ± 106 µm3 , P < 0.001 and 195 ± 86 µm3 vs. 247 ± 106 µm3 , P < 0.001, respectively). Lacunar density was also lower in both bone regions of the OVH group (40 ± 18 ×103 lacunae/mm3 vs. 47 ± 9×103 lacunae/mm3
in the lamellar region, P = 0.003 and 63 ± 18×103 lacunae/mm3
vs. 75 ± 13×103 lacunae/mm3 in the disorganized region, P < 0.001). Vascular canal volume was lower in the disorganized region of the bone in the OVH group compared to the same Region in the control group (P < 0.001). Indentation moduli were not different between the study groups in both bone regions.
Discussion. Changes to cortical bone associated with estrogen deficiency in rats require high-resolution methods for detection. Caution is required in the application of These results to humans due to major structural differences between human and rat bone.
Flexible electrochromic devices (ECDs) based on Fe(II)-metallo-supramolecular polyelectrolytes (Fe-MEPE) and vanadium oxide are studied in operando by means of x-ray absorption fine structure (XAFS) spectroscopy. The ECDs are blue-purple in the colored state at 0.0 V and become light yellow when a voltage of 1.6 V is applied. The XAFS studies at the K-edge of Fe(II) reveals that the absorption edge is shifted toward higher energies by 1.8 eV in the transparent state. Comparison of two different ECDs and different charge cycles demonstrates the reversibility and repeatability of the process. We attribute the shift to a charge transfer and a change of oxidation state of the ions from Fe2+ to Fe3+. The transition is not accompanied by a noticeable structural change of the octahedral coordination geometry as confirmed by analysis of the extended x-ray absorption fine structure (EXAFS) data. (C) 2015 Elsevier B.V. All rights reserved.
Nanocomposites based on polypropylene (PP) and organically modified ZnAl layered double hydroxides (ZnAl-LDH) were prepared by melt blending and investigated by a combination of differential scanning calorimetry (DSC), small- and wide-angle X-ray scattering (SAXS and WAXS), and dielectric relaxation spectroscopy (DRS). An average number of stack size of LDH layers is calculated by analyzing the SAXS data which is close to that of pure organically modified ZnAl-LDH. Scanning microfocus SAXS investigations show that the ZnAl-LDH is homogeneously distributed in the PP matrix as stacks of 4–5 layers with an intercalated morphology. DSC and WAXS results show that the degree of crystallinity decreases linearly with the increasing content of LDH. The extrapolation of this dependence to zero estimates a limiting concentration of ca. 40% LDH where the crystallization of PP is completely suppressed by the nanofiller. The dielectric spectra of the nanocomposites show several relaxation processes which are discussed in detail. The intensity of the dynamic glass transition (β-relaxation) increases with the concentration of LDH. This is attributed to the increasing concentration of the exchanged anion dodecylbenzenesulfonate (SDBS) which is adsorbed at the LDH layers. Therefore, a detailed analysis of the β-relaxation provides information about the structure and the molecular dynamics in the interfacial region between the LDH layers and the polypropylene matrix which is otherwise dielectrically invisible (low dipole moment). As a main result, it is found that the glass transition temperature in this interfacial region is by 30 K lower than that of pure polypropylene. This is accompanied by a drastic change of the fragility parameter deduced from the relaxation map.