Anomalous X-ray Research Articles

Crystal Growth and the Structure of a New Quaternary Adamantine Cu□GaGeS4

Single crystals of quaternary adamantine-type Cu□GaGeS4 were grown using the chemical vapor transport technique, with iodine as the transport agent. Dark red transparent crystals were grown in a temperature gradient of DT = 900–750 °C. Chemical characterization by X-ray fluorescence showed the off-stoichiometric composition of Cu□GaGeS4 crystals—in particular, a slight Ge deficiency was observed. By X-ray diffraction, Cu□GaGeS4 was found to adopt the chalcopyrite-type structure with the space group . Cation distribution in this structure was analyzed by multiple energy anomalous synchrotron X-ray diffraction, and it was found that Cu and vacancies occupied the 4a site, whereas Ga and Ge occupied the 4b site. The band gap energies of several off-stoichiometric Cu□GaGeS4 crystals were determined by UV-Vis spectroscopy and ranged from 2.1 to 2.4 eV. A non-linear correlation of the band gap energy with the Ge content of the compound was shown to follow the usual bowing behavior of semiconductor alloys, with a bowing parameter of = −1.45 (0.08).

Direct Experimental Observations of Ion Distributions during Overcharging at the Muscovite-Water Interface by Adsorption of Rb+ and Halides (Cl- , Br- , I- ) at High Salinity.

Classical electric double layer (EDL) models have been widely used to describe ion distributions at charged solid-water interfaces in dilute electrolytes. However, the chemistry of EDLs remains poorly constrained at high ionic strength where ion-ion correlations control non-classical behavior such as overcharging, i. e., the accumulation of counter-ions in amounts exceeding the substrate's surface charge. Here, we provide direct experimental observations of correlated cation and anion distributions adsorbed at the muscovite (001)-aqueous electrolyte interface as a function of dissolved RbBr concentration ([RbBr]=0.01-5.8 M) using resonant anomalous X-ray reflectivity. Our results show alternating cation-anion layers in the EDL when [RbBr]≳100 mM, whose spatial extension (i. e., ~20 Å from the surface) far exceeds the dimension of the classical Stern layer. Comparison to RbCl and RbI electrolytes indicates that these behaviors are sensitive to the choice of co-ion. This new in-depth molecular-scale understanding of the EDL structure during transition from classical to non-classical regimes supports the development of realistic EDL models for technologies operating at high salinity such as water purification applications or modern electrochemical storage.

Mechanism for enhanced precipitation strengthening due to the addition of copper to Al-Zn-Mg alloys with high Zn/Mg ratio

The mechanism for enhanced precipitation strengthening due to the addition of copper to Al-9.0Zn-1.5Mg (wt.%) alloys has been investigated by means of tensile test, transmission electron microscopy, anomalous small-angle X-ray scattering and three-dimensional atom probe. With the addition of copper increasing from 0% to 1.0%, and then 2.6%, the strength increment of peak-aged alloys due to precipitation strengthening increases from 274.8 MPa to 329.3 MPa, and then 343.0 MPa. Based on the copper-induced change of the parameters of clusters, GPI zones and η′ precipitates coexisting in the aged alloys, the enhanced precipitation strengthening has been discussed in detail by considering their coherent, modulus and short-order strengthening. In the alloy without copper, the coherent strengthening from η′ precipitates play a main role in precipitation strengthening. In copper-containing alloys, the contribution of clusters to strengthening become significant. The addition of copper decreases coherent strengthening and modulus strengthening from η′ precipitates, but increases modulus strengthening from GPI zones and clusters, and short-range order strengthening from clusters more apparently, and consequently enhances strength of the alloys after aging.

IXPE and XMM-Newton Observations of the Soft Gamma Repeater SGR 1806–20

Recent observations with the Imaging X-ray Polarimetry Explorer (IXPE) of two anomalous X-ray pulsars provided evidence that X-ray emission from magnetar sources is strongly polarized. Here we report on the joint IXPE and XMM-Newton observations of the soft γ-repeater SGR 1806–20. The spectral and timing properties of SGR 1806–20 derived from XMM-Newton data are in broad agreement with previous measurements; however, we found the source at an all-time low persistent flux level. No significant polarization was measured apart from the 4–5 keV energy range, where a probable detection with PD = 31.6% ± 10.5% and was obtained. The resulting polarization signal, together with the upper limits we derive at lower and higher energies (2–4 and 5–8 keV, respectively), is compatible with a picture in which thermal radiation from the condensed star surface is reprocessed by resonant Compton scattering in the magnetosphere, similar to what was proposed for the bright magnetar 4U 0142+61.

Transition metal elements in coloured beryl: application of anomalous X-ray scattering

Transition metal elements in coloured beryl: application of anomalous X-ray scattering

Intrinsic Magnetic Proximity Effect at the Atomically Sharp Interface of CoxFe3-xO4/Pt Grown by Molecular Beam Epitaxy.

CoxFe3-xO4(CFO)/Pt bilayers prepared by molecular beam epitaxy were investigated for the anomalous Hall effect and X-ray magnetic circular dichroism (XMCD). We found that the anomalous Hall effect originates from a magnetic proximity effect at the CFO/Pt interface. The XMCD signal in the Pt L-edge was obtained only for the sample deposited at 600 °C, indicating that the magnetic proximity effect is sensitive to the interface structure. Transmission electron microscopy images of the CFO/Pt interface and XMCD measurements of Co and Fe L-edges do not provide direct evidence for interfacial atomic diffusion or alloying. In summary, these results suggest that the magnetic proximity effect is robust for transport properties, such as the anomalous Hall effect, while the induced magnetic moment depends on slight differences in the interfacial structure, such as the presence or absence of interfacial oxygen ions.

Atomic structure of ZrO2-doped Li2O–SiO2-based multi-component glasses revealed by molecular dynamics–reverse Monte Carlo modeling

Structural model of ZrO2-doped Li2O–SiO2-based multi-component glass, which is developed as a mother material for high-strength glass-ceramics, is constructed by the molecular dynamics–reverse Monte Carlo (MD–RMC) method based on anomalous X-ray and neutron scattering data. In particular, we have succeeded in extracting reliable local structural information around Zr from the MD–RMC model. It was found that a significant fraction of edge-sharing structural units was formed around Zr–O and Li–O polyhedra, resulting in a densely packed configuration of O atoms. This configuration was manifested by a very sharp principal peak in the neutron scattering data. Our model suggested that both the Zr and Li ions are incorporated in the glass as distorted ZrO6 octahedra and distorted LiO4 tetrahedra, respectively. These structural features are discussed in terms of the crystallization behavior of this material.

Mechanistic Characterisation of the Bacterial Sesterviridene Synthase from Kitasatospora viridis.

A gene coding for a terpene synthase homolog from Kitasatospora viridis was cloned and expressed in Escherichia coli. The purified recombinant protein possessed sesterterpene synthase activity and efficiently converted geranylfarnesyl diphosphate (GFPP) with 19 % yield into the sesterterpene hydrocarbon sesterviridene A. Large scale enzymatic conversions also allowed for the isolation of two side products that are generated with very low yields of ca. 0.1 %. Several derivatives of sesterviridene A were obtained by chemical transformations, securing the NMR-based structural assignments. The absolute configuration of sesterviridene A was determined by chemical correlation using stereoselectively deuterated precursors and by anomalous dispersion X-ray crystallography. The cyclisation mechanism from GFPP to sesterviridene A was extensively studied through isotopic labelling experiments and DFT calculations.

Inhibition of Strontium Adsorption and Desorption by Ethylenediaminetetraacetic Acid at the Barite (001)–Water Interface

Understanding the sorption behavior of ions at the mineral–water interface is important to determine the fate of elements in the environment. Here, we used barite to understand metal and organic molecule interactions with ionic crystals as organic molecules are used to remove scale that can form during oil recovery in sulfate-rich settings. The sorption behavior of strontium (Sr) on the (001) surface in the presence of ethylenediaminetetraacetic acid (EDTA) was measured using in situ specular X-ray reflectivity (XR) and resonant anomalous X-ray reflectivity (RAXR). Based on the XR results, the presence of EDTA disrupts the barite surface structure, particularly that of the top two monolayers. A maximum of 0.7 (±0.2) EDTA molecules per surface unit cell are adsorbed, though the exact amount cannot be distinguished from that of other adsorbed species, such as Ba2+ and H2O. Based on the RAXR results, the presence of EDTA inhibits Sr incorporation into the barite surface and binds with Sr in solution to limit the amount of Sr2+ in solution. The Sr-EDTA2– complex then binds with barium ions at the barite surface, presumably in a bi-nuclear, bi-dentate state. Desorption of the Sr was also measured in the presence of EDTA. The desorption experiments show that ∼75% of the sorbed strontium was removed following extended reactions with EDTA and deionized water. There were minimal changes in the surface structure following desorption measurements implying that changes following Sr sorption in the presence of EDTA may be irreversible.

Anomalous Small-Angle X-ray Scattering and Its Application in the Dynamic Reconstruction of Electrochemical CO2 Reduction Catalysts

The electrochemical CO2 reduction reaction (CO2RR) is a promising approach for mitigating the greenhouse effect arising from anthropogenic CO2 emission. Nonetheless, poor product selectivity associated with electrochemical catalysts is the main technical problem for the application of CO2RR technology. The catalytic performance of nano-catalysts is strongly dependent on their microstructural features. Anomalous small-angle X-ray scattering (ASAXS) is one of the most effective techniques for studying nanostructural change in an operando way, especially for complex systems and mixed-element catalyst situations. Furthermore, based on the research results of ASAXS, appropriate catalyst components and nanostructures can be designed to achieve stable catalytic performance of the catalyst, promote catalytic reaction rate, or improve catalytic reaction selectivity. In this paper, the basic concept, principle, and applications in different systems of ASAXS are reviewed thoroughly. Finally, the development prospect of ASAXS in the field of electrocatalysis is prospected. It is hoped that this review will further promote ASAXS technology to play a more far-reaching impact in the field of electrocatalytic CO2RR.

Structural origins of the unusual thermal stability of amorphous Cu x Ge50−x Te50 (0 x 33.3)

We have investigated the local atomic structures of several compositions of the amorphous phase of the system Cu x GeTe50 (), based on extended x-ray absorption fine-structure as well as anomalous x-ray scattering experiments, and discuss the unusual trend regarding their thermal stability as a function of the Cu content. At low concentrations (), Cu atoms tend to agglomerate in flat nanoclusters reminiscent of the crystalline phase of metallic Cu, leading to a more and more Ge-deficient Ge–Te host network structure with growing Cu content and an increasing thermal stability. At higher Cu concentrations (), Cu is incorporated into the network, leading to an overall weaker bonding situation which is associated with a decreasing thermal stability.

IXPE detection of polarized X-rays from magnetars and photon mode conversion at QED vacuum resonance

The recent observations of the anomalous X-ray pulsars 4U 0142+61 and 1RXS J170849.0-400910 by the Imaging X-ray Polarimetry Explorer (IXPE) opened up a new avenue to study magnetars, neutron stars endowed with superstrong magnetic fields (B ≳ 1014 G). The detected polarized X-rays from 4U 0142+61 exhibit a 90° linear polarization swing from low photon energies (E ≲ 4 keV) to high energies (E ≳ 5.5 keV). We show that this swing can be explained by photon polarization mode conversion at the vacuum resonance in the magnetar atmosphere; the resonance arises from the combined effects of plasma-induced birefringence and Quantum electrodynamics (QED)-induced vacuum birefringence in strong magnetic fields. This explanation suggests that the atmosphere of 4U 0142 is composed of partially ionized heavy elements and that the surface magnetic field is comparable to or less than 1014 G, consistent with the dipole field inferred from the measured spindown. It also implies that the spin axis of 4U 0142+61 is aligned with its velocity direction. The polarized X-rays from 1RXS J170849.0-400910 do not show such 90° swing, consistent with magnetar atmospheric emission with B ≳ 5 × 1014 G.

Evolutionary Deformation toward the Elastic Limit by a Magnetic Field Confined in the Neutron-star Crust

Occasional energetic outbursts and anomalous X-ray luminosities are expected to be powered by the strong magnetic field in a neutron star. For a very strong magnetic field, elastic deformation becomes excessively large such that it leads to crustal failure. We studied the evolutionary process driven by the Hall drift for a magnetic field confined inside the crust. Assuming that the elastic force acts against the Lorentz force, we examined the duration of the elastic regime and maximum elastic energy stored before the critical state. The breakup time was longer than that required for extending the field to the exterior, because the tangential components of the Lorentz force vanished in the fragile surface region. The conversion of large magnetic energy, confined to the interior, into Joule heat is considered to explain the power for central compact objects. This process can function without reaching its elastic limit, unless the magnetic energy exceeds 2 × 1047 erg, which requires an average field strength of 2 × 1015 G. Thus, the strong magnetic field hidden in the crust is unlikely to cause outbursts. Furthermore, the magnetic field configuration can discriminate between central compact objects and magnetars.

Atomic Structures and Glass-Forming Ability of Pd-Based Bulk Metallic Glasses

To understand the relation of the glass-forming ability (GFA) to the atomic configurations of Pd42.5Ni7.5Cu30P20 (PNCP) metallic glass having the best GFA at present, the local structures were investigated by combining data obtained anomalous x-ray scattering, x-ray and neutron diffraction and applying reverse Monte Carlo modeling. By comparing the results of PNCP with Pd40Ni40P20 and Pd40Cu40P20 having a slightly and much worse GFAs, respectively, characteristic features were observed in the hyper-ordered atomic structures around the secondary metals of Ni and Cu, such as the concentration inhomogeneity, the fraction of pure and slightly distorted icosahedra, and the existence of large persistent homology rings. The structural heterogeneity for the excellent GFA of PNCP would be considered by an incompatible mixture of covalent-like Pd-P configurations and icosahedral clusters around the secondary metals.

Anomalous small-angle X-ray scattering analyses on hierarchical structures of rubber-filler systems.

The hierarchical structures of poly(styrene-ran-butadiene) (SBR) rubber/carbon black (CB) systems vulcanized with sulfur and ZnO have been clarified using anomalous small-angle X-ray scattering (ASAXS) near the Zn absorption edge. In the case of SBR/CB systems vulcanized with peroxide, it has been found previously that the hierarchical structures formed by CB consist of aggregates of primary particles and agglomerates of those aggregates with mass-fractal dimensions. However, to date the hierarchical structures in SBR/CB systems vulcanized with sulfur and ZnO have not been well investigated, despite being commonly used. This is because the strong scattering contrast of Zn prevents the quantitative analyses of the hierarchical structures of CB using X-ray scattering. In this study, the effects of Zn on the scattering intensity were eliminated and the structure factors of CB in SBR/CB systems were obtained using the ASAXS method. By extrapolating to the zero volume fraction of CB, the particle structure factor of the CB aggregates was estimated and it was found that the CB aggregates consist of closely packed CB primary particles. The presence of large particles of ZnO and particles of ZnS on the order of 10 nm in size is confirmed.

Short- and medium-range ordering in Al3Mn amorphous alloy prepared by magnetron sputtering

The structure of the Al3Mn amorphous alloy synthesized by magnetron sputtering was investigated using a combination of anomalous X-ray scattering and reverse Monte Carlo simulations. The geometrical features in the short- and medium-range regions around Mn were significantly different from those inferred by the dense random packing of the hard-sphere model, suggesting that the environmental structure around Mn is influenced by chemical interactions similar to those realized in the crystalline Al3Mn structure. The present advanced analysis also indicated that the medium-range ordering structure corresponding to a pre-peak signal in the X-ray diffraction profiles was because of the Al-Mn and Mn-Mn correlations accompanied by the modulation of number density and non-Bernal-type coordination geometry.

The 100-month Swift catalogue of supergiant fast X–ray transients

Supergiant fast X-ray transients (SFXTs) are high mass X-ray binaries (HMXBs) displaying X-ray outbursts that can reach peak luminosities up to 1038 erg s−1 and spend most of their lives in more quiescent states with luminosities as low as 1032−1033 erg s−1. During the quiescent states, less luminous flares are also frequently observed with luminosities of 1034−1035 erg s−1. The main goal of the comprehensive and uniform analysis of the SFXT Swift triggers presented in this paper is to provide tools to predict whether a transient that has no known X-ray counterpart may be an SFXT candidate. These tools can be exploited for the development of future missions exploring the variable X-ray sky through large field-of-view instruments. We examined all available data on outbursts of SFXTs that triggered the Swift/Burst Alert Telescope (BAT) collected between 2005 August 30 and 2014 December 31, in particular those for which broad-band data, including the Swift/X-ray Telescope (XRT) data, are also available. This work complements and extends our previous catalogue of SFXT flares detected by BAT from 2005 February 12 to 2013 May 31, since we now include the additional BAT triggers recorded until the end of 2014 (i.e. beyond the formal first 100 months of the Swift mission). Due to a change in the mission’s observational strategy, virtually no SFXT triggers obtained a broad-band response after 2014. We processed all BAT and XRT data uniformly by using the Swift Burst Analyser to produce spectral evolution dependent flux light curves for each outburst in the sample. The BAT data allowed us to infer useful diagnostics to set SFXT triggers apart from the general γ-ray burst population, showing that SFXTs uniquely give rise to image triggers and are simultaneously very long, faint, and ‘soft’ hard-X-ray transients. We find that the BAT data alone can discriminate very well the SFXTs from other classes of fast transients, such as anomalous X-ray pulsars and soft gamma repeaters. On the contrary, the XRT data collected around the time of the BAT triggers are shown to be decisive for distinguishing SFXTs from, for instance, accreting millisecond X-ray pulsars and jetted tidal disruption events. The XRT observations of 35 (out of 52 in total) SFXT BAT triggers show that in the soft X-ray energy band, SFXTs display a decay in flux from the peak of the outburst of at least three orders of magnitude within a day and rarely undergo large re-brightening episodes, favouring in most cases a rapid decay down to the quiescent level within three to five days (at most).

Are fast radio bursts produced by large glitches of anomalous x-ray pulsars?

Phase transitions within anomalous X-ray pulsars (AXPs) and soft γ-ray repeaters (SGRs) can lead to mini contractions. Such contractions produce pulsar gliches and shock break outs from their surface accompanied by thermal X/γ -ray emission. Highly relativistic dipolar e+e− bunches launched from the pulsar polar caps emit fast radio bursts (FRBs) of narrowly beamed coherent curvature radiation, visible from cosmic distances if they point in the direction of Earth. Although the associated bursts of surface X/γ -rays are nearly isotropic, and many orders of magnitude more energetic than the FRBs, they are detectable by the current all sky X-ray and γ-ray monitors only from our galaxy and nearby galaxies.

Long-exposure NuSTAR constraints on decaying dark matter in the Galactic halo

We present two complementary NuSTAR x-ray searches for keV-scale dark matter decaying to mono-energetic photons in the Milky Way halo. In the first, we utilize the known intensity pattern of unfocused stray light across the detector planes -- the dominant source of photons from diffuse sources -- to separate astrophysical emission from internal instrument backgrounds using ${\sim}$7-Ms/detector deep blank-sky exposures. In the second, we present an updated parametric model of the full NuSTAR instrument background, allowing us to leverage the statistical power of an independent ${\sim}$20-Ms/detector stacked exposures spread across the sky. Finding no evidence of anomalous x-ray lines using either method, we set limits on the active-sterile mixing angle $\sin^2(2\theta)$ for sterile-neutrino masses 6--40 keV. The first key result is that we strongly disfavor a ${\sim}$7-keV sterile neutrino decaying into a 3.5-keV photon. The second is that we derive leading limits on sterile neutrinos with masses ${\sim}$15--18 keV and ${\sim}$25--40 keV, reaching or extending below the Big Bang Nucleosynthesis limit. In combination with previous results, the parameter space for the Neutrino Minimal Standard Model ($\nu$MSM) is now nearly closed.

Boron migration during amorphous to crystalline transformation in CoFeB/MgO multilayers: A reflectivity study

Migration of boron in CoFeB/MgO multilayer during amorphous to crystalline transformation in CoFeB has been studied using Polarized Neutron Reflectivity (PNR) and anomalous Soft X-ray Reflectivity (SXR). PNR gives information about the possible redistribution of B in the multilayer during thermal annealing, as well as about the variation in the average magnetic moment. Sensitivity of the soft X-ray reflectivity to the movement of boron is enhanced by doing a series of measurements with X-ray energy spanning across the K absorption edge of B. Both the PNR and anomalous SXR results clearly suggest that upon thermal annealing, boron prefers to move away from the MgO/CoFeB interfaces, and forms a layer of boride in the middle of the magnetic layer. These results are important in view of the existing ambiguity regarding the role of boron in CoFeB/MgO based magnetic tunnel junctions.