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Structure and dielectric properties of Ba{sub 5}NdCu{sub 1.5}Nb{sub 8.5}O{sub 30−δ} tungsten bronze ceramics

Highlights: ► Tetragonal tungsten bronze ceramic Ba{sub 5}NdCu{sub 1.5}Nb{sub 8.5}O{sub 30−δ} was prepared. ► Titanium was replaced by copper in M{sub 5}RTi{sub 3}Nb{sub 7}O{sub 30} for the first time. ► Detailed structural information was retrieved by Rietveld refinement. ► An obvious relaxor-like dielectric behavior was observed in this ceramic, ion disorders in A1 and B sites contribute to this behavior. - Abstract: A new type of tungsten bronze ceramic Ba{sub 5}NdCu{sub 1.5}Nb{sub 8.5}O{sub 30−δ} has been prepared by a conventional solid-state reaction technique. Its structural, dielectric properties were investigated. Rietveld analysis shows that Ba{sub 5}NdCu{sub 1.5}Nb{sub 8.5}O{sub 30−δ} has a single-phase tetragonal (space group P4bm and lattice constants a = b = 12.4961(4) Å, c = 3.9426(8) Å, V = 615.66(4) Å{sup 3}) tungsten bronze structure. The occupations of sites A and B are quite interesting. A1 sites are fully disordered occupied by Ba ions and Nd ions and A2 sites for Ba ions only, while B-sites are equal for both Cu and Nb ions to occupy. This material exhibits an obvious relaxation behavior in the 213–573 K temperature range. The dielectric constants have been fitted by the modified Curie–Weiss law and all the estimated γ values are close to 2, confirming the typical relaxor ferroelectric behavior. The disorders of Ba{sup 2+} or Nd{sup 3+} in A1 sites and Nb{sup 5+}, Cu{sup 2+} in B sites induced by the oxygen vacancies may contribute to this dielectric behavior.

36 MATERIALS SCIENCE↗

Structural and magnetic study of Al{sup 3+} doped Ni{sub 0.75}Zn{sub 0.25}Fe{sub 2−x}Al{sub x}O{sub 4} nanoferrites

Graphical abstract: Hyperfine field of individual sites (inset) and weighted average hyperfine field as a function of Al{sup 3+} content for Ni{sub 0.75}Zn{sub 0.25}Fe{sub 2−x}Al{sub x}O{sub 4}. - Highlights: • Grain size reduction with Al{sup 3+} substitution. • Preferred occupancy of Al{sup 3+} at B site for higher Al{sup 3+} content. • Reduction in Ms, Tc, and hyperfine field with increasing Al{sup 3+} content. • Size dependent variation in coercivity. • Changes in isomer shift due to competing effect of volume and substitution. - Abstract: Nanostructured Al{sup 3+} doped Ni{sub 0.75}Zn{sub 0.25}Fe{sub 2−x}Al{sub x}O{sub 4} (x = 0.0, 0.2, 0.4, 0.6, 0.8, and 1.0) ferrites were synthesized via the wet chemical method. X-ray diffraction, transmission electron microscopy, and magnetization measurements have been used to investigate the structural and magnetic properties of spinel ferrites calcined at 950 °C. With the doping of Al{sup 3+}, the particle size of Ni{sub 0.75}Zn{sub 0.25}Fe{sub 2−x}Al{sub x}O{sub 4} first increased to 47 nm at x = 0.4 and then decreased down to 37 nm at x = 1. The main two absorption bands in IR spectra were observed around 600 cm{sup −1} and 400 cm{sup −1} corresponding to stretching vibration of tetrahedral and octahedral group Fe{sup 3+}–O{sup 2−}. Saturation magnetization and hyperfine field values decreased linearly with Al{sup 3+} due to magnetic dilution and the relative strengths of Fe–O–Me (Me = Fe, Ni, Zn, and Al) superexchanges. The coercive field showed an inverse dependence on ferrite particle size with minimum value of 82 Oe for x = 0.4. A continuous drop in Curie temperature was observed with the Al{sup 3+} substitution. From the Moessbauer spectral analysis and X-ray diffraction analysis, it is deduced that Al{sup 3+} for x < 0.4 has no obvious preference for either tetrahedral or octahedral site but has a greater preference for the B site for x > 0.4. In nutshell the study presents detailed structural and magnetic, and Moessbauer analysis of Ni{sub 0.75}Zn{sub 0.25}Fe{sub 2−x}Al{sub x}O{sub 4} ferrites.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Structural, magnetic, and Mössbauer spectroscopy of Cu substituted M-type hexaferrites

Highlights: • Single BaM hexaferrite structural phases with Cu substations were prepared. • The magnetocrystalline anisotropy decreased with Cu substitution. • The coercivity was significantly modified while the magnetization remained high. • Hexaferrites with 0.2–0.4 Cu possess properties suitable for magnetic recording. • Ionic distributions from structural refinement agreed with Mössbauer spectroscopy. - Abstract: BaFe{sub 12−x}Cu{sub x}O{sub 19} hexaferrites were prepared using ball milling and sintering at 1100 °C. Refinement of the X-ray diffraction patterns was carried out to determine the structural parameters and the ionic distribution over the crystallographic sites. The preferential site occupation and valence state of Cu was consistent with the results obtained from the analysis of Mössbauer spectra. Further, the magnetic parameters of the samples were discussed in light of the structural and Mössbauer analyses. The magnetic phase transition temperature was found to decrease with the level of Cu substitution, in accordance with the reduction of the superexchange interactions. Further, the magnetic softening of the hexaferrite and the significant reduction in magnetocrystalline anisotropy with Cu substitution was consistent with the ionic distribution in the lattice. This study clearly demonstrated the feasibility of using a simple method to fabricate hexaferrites with a modified coercivity, while maintain the saturation magnetization high enough for practical applications.

36 MATERIALS SCIENCE↗

Microstructure, magnetic and microwave absorptive behavior of doped W-type hexaferrite nanoparticles prepared by co-precipitation method

Highlights: • High frequency properties of substituted W-type Sr-hexaferrite. • Saturation magnetization of samples is decreased with increasing of dopants content. • The ferrite sample covers about 6 GHz of bandwidth in K{sub u} band. • The optimum substituted samples can be used as a potential magnetic loss material. • Sample contain x = 0.4 of dopants have shown greater than 90% of reflection loss. - Abstract: Substituted W-type hexaferrite nanoparticles of SrZn{sub 2−x}Co{sub x/2}Ni{sub x/2}Fe{sub 16}O{sub 27} were synthesized by a chemical co-precipitation method. The X-ray diffraction results confirmed that W-type ferrite was identified as the main phase in whole samples in the range of x = 0–0.4. According to magnetic hysteresis loops, with increasing of substituted cations, saturation of magnetization increased and coercivity decreased due to crystalline site occupation of Zn with Ni and Co cations. The microwave reflection loss analysis results in the K{sub u} band (12–18 GHz) show that the highest value of reflection loss of samples was −29.11 dB at frequency of 14.57 GHz with an absorption bandwidth of more than 6 GHz by choosing reflection loss value of −10 dB as a reference. The results indicate that, the sample with appropriate amount of substituted cations hold great promise for microwave device applications.

36 MATERIALS SCIENCE↗

Synthesis and structural characterization of the vividly colored first row transition metal-containing oxyfluoride antiperovskites Sr3-xMnxMO4F and Sr3-xMnxMO4-αF1-δ (M = Al, Ga)

Highlights: • Substitution of Mn{sup 2+} demonstrates Sr{sub 3-x}A{sub x}MO{sub 4}F can tolerate divalent first row transition metals. • The colors of these materials vary from green to purple depending on anion stoichiometry. • Intense colors are likely due to small amounts of Mn{sup 3+} on the tetrahedral Al site. • Structural data is consistent with preferential occupation of eight-coordinate Sr(2) site by Mn{sup 2+}. • Large off-center displacements are observed on the underbonded ten-coordinate Sr(1) site. - Abstract: Incorporation of dopant amounts of the divalent transition metal cation Mn{sup 2+} into the oxyfluoride material Sr{sub 3-x}Mn{sub x}MO{sub 4}F (M = Al, Ga; 0 ≤ x ≤ 0.1) yields green powders which vary in hue depending on the identity of M. Treatment of these phases with post-synthesis annealing under reducing conditions produces anion deficient phases according to Sr{sub 3-x}Mn{sub x}MO{sub 4-α}F{sub 1-δ} displaying vivid purple coloration. Intense colors are likely due to small amounts of Mn{sup 3+} on the tetrahedral M site. Full structural characterization based upon powder X-ray diffraction (PXRD), neutron powder diffraction (NPD), and thermogravimetric analysis (TGA) data are presented herein, demonstrating that the Sr{sub 3-x}A{sub x}MO{sub 4}F (A = Ca, Sr, Ba; M = Al, Ga) anti-perovskite structure can readily accommodate first row transition metals.

36 MATERIALS SCIENCE↗

Structure, site-occpancy and luminescent properties of a novel blue phosphor Na3ZrMgP3O12: Eu2+

Highlights: • Na{sub 3}ZrMgP{sub 3}O{sub 12}: Eu{sup 2+} blue phosphor was synthesized via high-temperature solid-state reaction. • Eu{sup 2+} site occupancy in Na{sub 3}ZrMgP{sub 3}O{sub 12} was studied in details. • Luminescence, concentration quenching and thermal stability of Na{sub 3}ZrMgP{sub 3}O{sub 12}: Eu{sup 2+} were investigated. - Abstract: Single-phase Na{sub 3}ZrMgP{sub 3}O{sub 12}: Eu{sup 2+} (NZMP: Eu{sup 2+}) phosphor was prepared via high-temperature solid-state reaction. The crystal structure, lattice parameters and occupied sites of Eu{sup 2+}-doped Na{sub 3}ZrMgP{sub 3}O{sub 12} are elucidated by powder X-ray diffraction and Rietveld refinement. It is found that majority of Eu{sup 2+} ions occupy 8-coordianted Na2 site while minority of Eu{sup 2+} are in 6-coordianted Na1 site of NZMP host. NZMP: Eu{sup 2+} shows a strong blue emission broadband with peak at 450 nm under UV excitation, which can be decomposed into two sub-bands peaking at 446 and 474 nm based on the substitution of two kinds of Na{sup +} sites by Eu{sup 2+} ions. Luminescence properties of NZMP: Eu{sup 2+} phosphors were investigated in detail, including excitation and emission spectra, decay lifetime, concentration quenching and temperature-dependent emission spectra.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Blue and red up-conversion light emission in TM-doped A 2 B 2 O 7 oxides

The crystal structure and light emission property of Yb/Tm doped gadolinium titanate and gadolinium zirconate with chemical composition of A 2 B 2 O 7 were studied by x-ray diffraction (XRD) and optical spectroscopy measurements, respectively. XRD results suggest that the rare earth titanates have an ordered pyrochlore structure and a defect-fluorite structure for the zirconates. Photoluminescence activated with 1064 nm infrared laser light shows different light emission behaviors for the titanate and zirconate samples, which is related to the different site occupancy of Tm 3+ in the lattice of the samples. Only a weak near-infrared (NIR) (~800 nm) light emission was observed in the titanate samples while a strong blue and red up-conversion emission was detected in the Tm 3+ -doped zirconate samples. As a result, the strong blue and red emission is due to the 7-fold coordinated Tm 3+ in the structure.

36 MATERIALS SCIENCE↗

Neutron diffraction probing hydrogen in monoclinic H 2 VOPO 4

Light hydrogen atoms are resolvable with neutrons; however, the massive incoherent background inhibits the diffraction quality. To improve the signal, isotope treatment by deuteration becomes a prerequisite for a successful crystallographic understanding of hydrogen-containing materials by neutron diffraction. Thanks to the low-background and high-resolution time-of-flight neutron diffractometer, this work demonstrates a direct and successful measurement of high-quality neutron diffraction patterns of H 2 VOPO 4 powders, a precursor of a high-capacity alkali-ion battery cathode. The Rietveld refinement identifies the hydrogen coordinates, occupancy, and thermal parameters in the H 2 VOPO 4 lattice. Finally, the result highlights the unique capability of neutron diffraction for the structure characterization of hydrogen-containing materials, potentially without requiring costly and possibly artifact-inducing deuteration for neutron diffraction.

36 MATERIALS SCIENCE↗

Selectivity mechanisms of ion intercalation in Prussian blue analogs

Prussian blue analogs (PBAs) are a family of materials with facile, reversible, and selective ion transport capability for various ions via electrochemical intercalation, owing to their vacancy structure. The large tunable compositional space of PBAs allows for manipulation of intercalation behavior and selectivity by controlling structural vacancy level through choice of transition metal centers and modifications to the synthesis process. However, a lack of understanding of the mechanisms of ion selectivity hinders the material’s design process. Here, for this work, we investigated the origins of ion selectivity using a model PBA, copper hexacyanoferrate, and focused on eight technologically and biologically prominent ions, for which we determined a sequence of selectivity: Rb + > K + > Na + > Ba 2+ > Sr 2+ ≈ Ca 2+ > Mg 2+ > Li + . We provide electrochemical, structural, and redox evidence of strong correlation between the ion identity, the dominant charge-compensating redox, and preferred occupancy site. Specifically, using synchrotron anomalous X-ray diffraction (AXRD), we reveal that monovalent ions exhibit significant association with the corner sites of the unit cell and iron redox, whereas divalent ions display affinity toward the center site with higher ratios of copper redox. Informed by selectivity results, we applied CuHCFe to Li purification and achieved 99.9% purity. Our findings demonstrate an approach to elucidating ion intercalation behavior in order to distinguish and manipulate material properties to optimize separation performance.

Prussian blue analog↗

Establishing an optimized patient-specific verification program for volumetric modulated arc therapy

Quality assurance (QA) of volumetric modulated arc therapy (VMAT) increases the workload significantly. We compared the results from 4 verification methods to establish an efficient VMAT QA. Planning for VMAT treatments was carried out for 40 consecutive patients. Pretreatment verifications were carried out with ion chamber array Physikalish-Technische Werkstätten (PTW729), electronic portal dosimetry (EPID), ion chamber measurements, and independent dose calculation with Diamond program. 2D analyses were made using the gamma analysis (3 mm distance to agreement and 3% dose difference relative to maximum, 10% dose threshold). Average point dose difference calculated by Eclipse relative to ion chamber measurements and Diamond were 0.1%±0.9% and 0.6%±2.2%, respectively. Average pass rate for PTW729 was 99.2%±1.9% and 98.3%±1.3% for EPID. The total required time (linac occupancy time given in parentheses) for each QA method was: PTW729 43.5 minutes (26.5 minutes), EPID 14.5 minutes (2.5 minutes), ion chamber 34.5 minutes (26.5 minutes), and Diamond 12.0 minutes (0 minute). The results were consistent and allowed us to establish an optimized protocol, considering safety and accuracy as well as workload, consisting of 2 verification methods: EPID 2D analysis and independent dose calculation.

61 RADIATION PROTECTION AND DOSIMETRY↗

Evaluation of a high-throughput method for processing sponge-stick samples to detect viable, non-spore-forming biothreat agents

After a bioterrorism incident, surface sampling is often used to determine the extent of contamination and exposure, guiding decontamination efforts and decisions for re-occupancy of affected sites. The sponge-stick (SS) is a preferred and commonly used device for sample collection to detect both spore-forming and non-spore-forming biothreat agents from non-porous surfaces. Here, in this study, a recently developed high-throughput method (HTM) for processing SS samples to detect viable Bacillus anthracis spores was adapted for detection of non-spore-forming biothreat agents, Yersinia pestis and Francisella tularensis. The scalable HTM was used to process up to 20 SS samples simultaneously, compared to the current stomacher-based method which processes one SS at a time. Comparisons of the HTM and the stomacher-based method were statistically indistinguishable for most experiments (P > 0.05) with HTM recoveries of 37–60 % for Y. pestis inoculated at 102–103 cells/SS and held 48 h at 4 °C to mimic sample transport/storage. The HTM was integrated with Rapid Viability-Polymerase Chain Reaction (RV-PCR) analysis to detect viable Y. pestis in the presence of particulate contamination (Arizona Test Dust, ATD). This approach detected Y. pestis inoculated at 20 cells/SS and ATD did not impact detection (P > 0.05). F. tularensis showed significantly lower recoveries between no-hold time and 48-h hold time (4 °C, P < 0.05) using the HTM, which further testing showed could be due to toxicity of the neutralizing buffer used for SS pre-wetting. With modifications, this method could enhance throughput capacity while maintaining similar recovery efficiencies to current methods for other non-spore-forming bacterial pathogens.

Biological and medical sciences↗

Effects of niobium and tantalum on the microstructure and strength of ferritic-martensitic steels

Herein, detailed investigations of two ferritic-martensitic steels, i.e., Nb- and Ta-steel, indicate that the higher Nb diffusivity and the lower nucleation driving force of Nb-carbide promote preferential nucleation of Nb-carbides at grain boundaries and thus a higher boundary occupancy than Ta-carbides, which favored greater creep resistance of Nb-steel than that of Ta-steel despite their similar yield strength.

36 MATERIALS SCIENCE↗

Anomalous behavior of the quasi-one-dimensional quantum material Na 2 OsO 4 at high pressure

Na 2 OsO 4 is an unusual quantum material that, in contrast to the common 5d 2 oxides with spins = 1, owns a magnetically silent ground state with spin = 0 and a band gap at Fermi level attributed to a distortion in the OsO 6 octahedral sites. In this semiconductor, our low-temperature electrical transport measurements indicate an anomaly at 6.3 K with a power-law behavior inclining through the semiconductor-to-metal transition observed at 23 GPa. Even more peculiarly, we discover that before this transition, the material becomes more insulating instead of merely turning into a metal according to the conventional wisdom. Furthermore, to investigate the underlying mechanisms, we applied experimental and theoretical methods to examine the electronic and crystal structures comprehensively, and conclude that the enhanced insulating state at high pressure originates from the enlarged distortion of the OsO 6 . It is such a distortion that widens the band gap and decreases the electron occupancy in Os’s t 2 g orbital through an interplay of the lattice, charge, and orbital in the material, which is responsible for the changes observed in our experiments.

36 MATERIALS SCIENCE↗

Cations controlled growth of β-MnO 2 crystals with tunable facets for electrochemical energy storage

Engineering crystal facets to enhance their functionalities often require complex processing routes to suppress the growth of surfaces with the lowest thermodynamic energies. Herein, we report a unique method to control the morphologies of β-MnO 2 crystals with different occupancy of {100}/{111} facets through the effect of K + cations. Combining aberration-corrected scanning transmission electron microscopy (STEM), ultramicrotomy, and dynamic functional theory (DFT) simulation, we clarified that the β-MnO 2 crystals were formed through a direct solid-state phase transition process. Increasing the concentration of K + cations in the precursor gradually changed the morphology of β-MnO 2 from bipyramid prism ({100}+{111} facets) to an octahedron structure ({111} facets). The K + cations controlled the morphology of β-MnO 2 by affecting the formation of α-K 0.5 Mn 4 O 8 intermediate phase and the subsequent phase transition. Utilizing the β-MnO 2 crystals as the cathode for Li-ion batteries showed that highly exposed {111} facets offered β-MnO 2 crystal better rate performance, with ~70% capacity retention when the charge-discharge rate increased from 20 mA/g to 200 mA/g. Furthermore, our work revealed a new mechanism to tune the morphology of this earth-abundant metal oxide crystal, which could be used to adjust its electrochemical performance for different applications, such as supercapacitors and catalysts for metal-air batteries and fuel cells.

25 ENERGY STORAGE↗

Heteroatom anchoring to enhance electrochemical reversibility for high-voltage P2-type oxide cathodes of sodium-ion batteries

P2-type cathode has received extensive attention due to its faster Na+ diffusion and a high theoretical capacity in sodium-ion batteries (SIBs). However, undesirable phase transformations have induced dramatic capacity decay of SIBs during the cycling process. In this study, heteroatom anchoring through Cu/Mg dual doping is introduced into P2-type Na 0.67 Ni 0.33 Mn 0.67 O 2 cathode to enhance high-voltage electrochemical reversibility and modulate interfacial Na + kinetics. Further, the as-prepared Na 0.67 Ni 0.23 Mg 0.05 Cu 0.05 Mn 0.67 O 2 exhibits an outstanding capacity retention (83.4% after 2000 cycles at 10C) and rate performance (73 mAh g -1 at 10C, accounting for 58.7% of that at 0.1 C) over the voltage range of 2.5–4.4 V. Intensive explorations further manifest that the modified mechanism of dual-ion doping strategy is attributed to the synergistic coupling effect of a substantial change in Na occupancy distribution and an increase in oxygen vacancy buffer. Thus, the optimized cathode expedites Na + diffusion and reduces detrimental phase transformation, which favors high-rate performance and long-term cycling stability. This study develops a route to rationally design high-voltage cathode materials for SIBs.

25 ENERGY STORAGE↗

Nuclear Data Sheets for A = 75

The experimental nuclear spectroscopic data for known nuclides of mass number 75 (Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Kr, Rb, Sr) have been evaluated and presented together with Adopted properties for levels and γ rays. New high-spin data are available for {sup 75}Ga, and {sup 75}Rb; and lifetime data for high-spin states in {sup 75}Br and {sup 75}Kr. For ΔJ =1, M1+E2 transitions in two rotational bands in {sup 75}Kr, several B(E2)(W.u.) values are anomalously high, deviating by 2–3 σ values from currently accepted RUL(E2) = 300. In the opinion of the evaluators, there is need to remeasure level lifetimes and multipole mixing ratios in {sup 75}Kr to resolve this serious discrepancy. New precise single-particle transfer cross section data are available for {sup 75}Ga, {sup 75}Ge, {sup 75}As and {sup 75}Se from several different reactions (2009Ka06,2008Sc03); these data give information for occupancy of valence neutron orbitals in the ground states of target nuclides: {sup 76}Ge, {sup 76}Se and {sup 78}Se. No significant new data since the 1999 NDS for A = 75 have been reported for {sup 75}As and {sup 75}Se. No data are yet available for excited states in {sup 75}Co, {sup 75}Ni and {sup 75}Sr. For {sup 75}Fe, only the isotopic identification is made with one observed event. The radioactive decay schemes of {sup 75}Co and {sup 75}Ni are unknown while those for {sup 75}Rb and {sup 75}Sr are incomplete. This work supersedes the data presented in the previous NDS evaluation of A = 75 published by 1999Fa05.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Transcriptional Regulation of Enhancers Active in Protodomains of the Developing Cerebral Cortex

Elucidating the genetic control of cerebral cortical (pallial) development is essential for understanding function, evolution, and disorders of the brain. Transcription factors (TFs) that embryonically regulate pallial regionalization are expressed in gradients, raising the question of how discrete domains are generated. Here, we provide evidence that small enhancer elements active in protodomains integrate broad transcriptional information. CreER T2 and GFP expression from 14 different enhancer elements in stable transgenic mice allowed us to define a comprehensive regional fate map of the pallium. We explored transcriptional mechanisms that control the activity of the enhancers using informatics, in vivo occupancy by TFs that regulate cortical patterning ( CoupTFI, Pax6 , and Pbx1 ), and analysis of enhancer activity in Pax6 mutants. Overall, the results provide insights into how broadly expressed patterning TFs regulate the activity of small enhancer elements that drive gene expression in pallial protodomains that fate map to distinct cortical regions.

59 BASIC BIOLOGICAL SCIENCES↗

The Performance and Long Term Stability of the D0 Run II Forward Muon Scintillation Counters

The performance of the D0 experiment forward muon scintillation counters system during Run II of the Tevatron from 2001 to 2011 is described. The system consists of 4214 scintillation counters in six layers. The long term stability of the counters amplitude response determined using LED calibration system and muons produced in proton-antiproton collisions is presented. The average signal amplitude for counters of all layers has gradually decreased over ten years by 11%. The reference timing, determined using LED calibration, was stable within 0.26 ns. Average value of muon timing peak position was used for periodic D0 clock signal adjustments to compensate seasonal drift caused by temperature variations. Counters occupancy for different triggers in physics data collection runs and for minimum bias triggers are presented. The single muon yields versus time and the luminosity dependence of yields were stable for the forward muon system within 1% over 10 years.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

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