Additional Sharp Peaks Research Articles

A New Hydrometallurgical Process for Metal Extraction from Electric Arc Furnace Dust Using Ionic Liquids

This research proposes a new hydrometallurgical method for Zn, In, and Ga extraction, along with Fe as a common impurity, from electric arc furnace dust (EAFD), using ionic liquids. EAFD is a metal-containing waste fraction generated in significant amounts during the process of steelmaking from scrap material in an electric arc furnace. With valuable metal recovery as the main goal, two ionic liquids, [Bmim+HSO4-] and [Bmim+Cl-], were studied in conjunction with three oxidants: Fe2(SO4)3, KMnO4, and H2O2. The results indicated that the best combination was [Bmim+HSO4-] with [Fe2(SO4)3]. An experimental series subsequently demonstrated that the combination of 30% v/v [Bmim+HSO4-], 1 g of [Fe2(SO4)3], S/L ratio = 1/20, a 240 min leaching time, and a temperature of 85 °C was optimal, resulting in maximum extractions of 92.7% Zn, 97.4% In, and 17.03% Ga. In addition, 80.2% of the impurity metal Fe was dissolved. The dissolution kinetics of these four elements over a temperature range of 55-85 °C was found to be diffusion controlled. The remaining phases present in the leached residue were low amounts of ZnO, Fe3O4, ZnFe2O4, and traces of Ca(OH)2 and MnO2, and additional sharp peaks indicative of PbSO4 and CaSO4 appeared within the XRD pattern. The intensity of the peaks related to ZnO and Fe3O4 were observed to have decreased considerably during leaching, whereas some of the refractory ZnFe2O4 phase remained. SEM-EDS analysis revealed that the initial EAFD morphology was composed of spherical-shaped fine-grained particle agglomerates, whereas the leached residue was dominated by calcium sulphate (Ca(SO4))-rich needle-shaped crystals. The results clearly demonstrate that [Bmim+HSO4-] is able to extract the target metals due to its acidic properties.

Evidence for Participation of 4f and 5d Orbitals in Lanthanide Metal–Ligand Bonding and That Y(III) Has Less of This Complex-Stabilizing Ability. A Thermodynamic, Spectroscopic, and DFT Study of Their Complexation by the Nitrogen Donor Ligand TPEN

The formation constants (log K1) of lanthanide(III) (Ln) ions [except for Pm(III)] and the Y(III) cation have been measured with the ligand TPEN (N,N,N',N'-tetra-2-picolylethylenediamine). These log K1 values show a typical variation with ionic radius, with a local maximum at Sm(III) and a local minimum at Gd(III), with an overall increase in log K1 from La(III) to Lu(III) as the ionic radius decreases. The log K1 for the Y(III)/TPEN complex is much lower than expected from its ionic radius, while the literature log K1 for Am(III) is much higher. The latter effect is thought to be due to greater covalence in the M-L (metal-ligand) bond than for Ln(III) ions: the low log K1 for Y(III) is interpreted as being due to lower covalence. The f → f transitions in the Nd(III) and Pr(III) complexes were examined for effects that might indicate the participation of f orbitals in M-L bonding. The intensity of the f → f transitions in the Nd(III)/TPEN complex was greatly increased compared to that of the Nd3+ aqua ion, which appeared to be due to additional sharp peaks, possibly parity forbidden transitions where parity rules were broken by covalence in the M-L bond. The Pr(III)/TPEN complex showed that all of the f → f transitions shifted to longer wavelengths by some 5 nm, with modest increases in intensity. The effects seen in the f → f transitions of Nd(III) and Pr(III) with TPEN with its six nitrogen donors were present to a much smaller extent in the EDTA and other complexes with fewer nitrogen donors. The changes in the f → f transitions of the TPEN complexes of Er(III) and Ho(III) were small, suggesting a smaller contribution of f orbitals to M-L bonding in these heavier Ln(III) ions. The intense Laporte allowed f → d transitions in Ce(III) complexes show large shifts to longer wavelengths as complexes of, for example, EDTA with increasing numbers of nitrogen donors, suggesting the participation of both f and d orbitals, or either, in M-L bonding. The nature of M-L bonding in M(III)/TPEN complexes was further investigated via density functional theory calculations.

Crossover behavior of the localized to itinerant transition of 5f electrons in the antiferromagnetic Kondo lattice USb2

In Uranium-based heavy fermion system, the 5f electrons display an intermediate character between partial localization and partial itinerancy, which makes the Kondo problem more complicated. Here we use scanning tunneling microscopy/spectroscopy to investigate the (001) surface of the Kondo lattice antiferromagnet USb2. Temperature-dependent dI/dV spectra from 4.7 K up to 140 K reveal several peak structures around the Fermi level. Two pronounced peaks are originated from the hybridization between the conduction and 5f electrons. We did not observe the mysteriously abrupt change of the electronic state at 45 K, which is previously reported by another STM group and attributed to a novel first-order like transition. Instead, we only observe continuous evolution of the dI/dV spectra with temperature. Furthermore, in some scanning regions, we find significant Sb atoms missing from the top layer, which gives us the opportunity to investigate the electronic structure of the U-terminated surface. For the U-terminated surface, an additional sharp peak emerges, which is closely related to the magnetic order.

Insertion loss of periodic cylindrical shells with helical slit

We propose periodic shells with helical slit to overcome the lacuna in periodic C scatterers, where the first Bragg band is considerably reduced on increasing width of the slit. The key discovery of this research indicates that, by changing the upright slit of the C scatterers to helical slits, larger insertion loss (IL) is achieved around the first Bragg band without compromising the local resonance band. Comparing the performance of periodic shells without slit or cylindrical scatterers, it is found that IL becomes larger at first Bragg band. The pitch, thickness of the shell and width of helical slit can be altered to adjust the resonance of the proposed shells. On decreasing the pitch or increasing the slit width, the resonance band shifts toward high frequencies without much alteration in acoustic attenuation of bandwidth. Additionally, below threshold pitch, the said peak merges with first Bragg band and broadens with prominent IL. The calculated band structure authenticates the bandwidth of the first Bragg band, and the additional sharp peak in IL can be attributed to local resonance of the periodic scatterers.

Mobility of Radiogenic Helium in Amphibole

Recently experiments on He extraction from an amphibole by the incremental heating unexpectedly revealed that the He release pattern depends on the heating rate. During slow heating (~4 K·min−1) of the amphibole grains, one smooth peak of the He flux from the mineral was observed; in contrast, during fast heating (~40 K·min−1) an additional sharp peak appeared at a temperature about 750 °C. In order to explain these observations, we developed a model of He diffusion from the amphibole, which allowed the calculated He fluxes from the mineral to be reconciled with those observed. From the modelling we derived: (i) the helium diffusion domain size distribution, and evolution of the distribution in the course of incremental heating; (ii) occurrence of the tensile stresses, operating under enhanced temperatures above 700 °C. The stresses are different in sites with the different local thermal expansion of the crystalline lattice and they increase the He diffusion flux. The model can be applied to other minerals (materials).

Phonon-Induced Optical Dephasing in Single Organic Molecules.

We present a joint experiment-theory analysis of the temperature-dependent emission spectra, zero-phonon linewidth, and second-order correlation function of light emitted from a single organic molecule. We observe spectra with a zero-phonon line together with several additional sharp peaks, broad phonon sidebands, and a strongly temperature dependent homogeneous broadening. Our model includes both localized vibrational modes of the molecule and a thermal phonon bath, which we include nonperturbatively, and is able to capture all observed features. For resonant driving we measure Rabi oscillations that become increasingly damped with temperature, which our model naturally reproduces. Our results constitute an essential characterization of the photon coherence of molecules, paving the way to their use in future quantum information applications.

Effect of HOD parameters on gain and bandwidth of parametric amplifiers for near-zero ultra-flat dispersion profile

Higher order dispersion (HOD) parameters play an important role in the overall performance of fiber optic parametric amplifier (FOPA). Effect of HOD parameters on gain spectrum and bandwidth for an engineered dispersion profile has been investigated revealing some interesting outcomes. Here, we have optimized a near-zero ultra flat dispersion profile around the communication wavelength based on selective liquid infiltration technique. The performance of FOPA in terms of gain and bandwidth based on the optimized dispersion profile is thoroughly investigated incorporating different HOD parameters. Considering upto 6th order of HOD terms, we could observe one additional sharp gain peak (on both sides of the central gain maxima) which otherwise is absent when considering other lesser values of HOD parameters. The spectral shift and width of the additional peaks are found to vary significantly due to the incorporation of these different HOD terms. The effect of HOD parameters are found to be extremely significant for the generation of new frequencies as well as modification of the peak widths for the communication band application.

Study of the effect of V-doping on the opto-electrical properties of spray-pyrolized SnS thin films

SnS is an earth-abundant material that is a potentially suitable candidate for the absorber layer in solar cells. Here spray-pyrolized SnS thin films doped with vanadium were studied using structural and opto-electrical methods. The thin films have an orthorhombic structure with a preferential (111) crystallographic direction. SnS has an indirect bandgap of around 1.05 eV, whereas doping with vanadium changes the band edge and shifts the absorption threshold to around 1.2 eV. The photoluminescence study revealed a broad peak related to the band-to-band transition of energy at around 1.2 eV and an additional sharp peak positioned at 1.17 eV related to vanadium. Additionally, a non-radiative recombination mechanism followed by hopping through band fluctuation barriers has been proposed for photoluminescence quenching at increased temperatures. The conductivity measurements reveal that conductivity weakly increases with V-doping, whereas its activation energy decreases from around 0.38 eV to 0.35 eV.

Optical, thermal and microstructural studies of epoxy-CoSO4.7H2O hybrid material

Organic–inorganic polymer hybrid films of epoxy polymer were prepared, using Cobaltous sulfate heptahydrate (CoSO4.7H2O) as a filler component, by physical blending method. UV–Vis optical absorption spectra were analyzed to determine optical band gaps (Eg) of the hybrid material. FTIR studies revealed the interaction of inorganic component with molecules of the polymer matrix. Glass transition temperature (Tg) and degradation temperature were determined by DSC. TG analysis showed the improvement in thermal stability of prepared hybrid films. XRD patterns revealed the amorphous nature of the pure epoxy polymer. Additional sharp peaks were seen for higher filler levels (FLs), indicating self formed nanostructures in the material, which was also evident from SEM analysis.

Protective Carbon Overlayers from 2,3-Naphthalenediol Pyrolysis on Mesoporous SiO₂ and Al₂O₃ Analyzed by Solid-State NMR.

Hydrothermally stable carbon overlayers can protect mesoporous oxides (SiO2 and Al2O3) from hydrolysis during aqueous-phase catalysis. Overlayers made at 800 °C by pyrolysis of 2,3-naphthalenediol deposited out of acetone solution were analyzed by solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Power absorption due to sample conductivity was prevented by diluting the sample in nonconductive and background-free tricalcium phosphate. While pyrolysis on SiO2 produced a predominantly aromatic carbon film, at least 15% of nonaromatic carbon (sp3-hybridized C as well as C=O) was observed on γ-Al2O3. These species were not derived from residual solvent, according to spectra of the same material treated at 400 °C. The sp3-hybridized C exhibited weak couplings to hydrogen, short spin-lattice relaxation times, and unusually large shift anisotropies, which are characteristics of tetrahedral carbon with high concentrations of unpaired electrons. Moderate heat treatment at 400 °C on SiO2 and Al2O3 resulted in yellow-brown and nearly black samples, respectively, but the darker color on Al2O3 did not correspond to more extensive carbonization. Aromatic carbon bonded to hydrogen remained predominant and the peaks of naphthalenediol were still recognizable; however, some of the chemical shifts differed by up to 5 ppm, indicating significant differences in local structure. On SiO2, additional sharp peaks were detected and attributed to 1/3 of the 2,3-naphthalene molecules undergoing fast, nearly isotropic motions.

Structural, optical and waveguiding properties improvement of SiO2/TiO2 Bragg reflectors processed by the sol–gel method under the effect of Ni-doped TiO2 and annealing duration

We investigated the nickel doped TiO2 layer and annealing duration effects on SiO2/TiO2 Bragg reflectors. The films crystallize in pure anatase phase whatever is the Ni content and the annealing duration. In UV–vis-NIR analyses, variations of width, position and transmission coefficient of the stop-band were observed. The PL spectra red-shifted when the Ni content and annealing duration increased. As the annealing duration increases, an additional sharp emission peak appears around 867nm, indicating a reduced number of defects. As Ni content increased, the M-lines spectroscopy shows two transverse electric polarization guided modes TE0 and TE1, which indicates a decreased refractive index and an increased film thickness.

Nanoscopic observations of stress-induced formation of graphitic nanocrystallites at amorphous carbon surfaces

The formation of graphitic nanocrystallites at the surface of amorphous carbon under large mechanical stresses was examined by using micro-Raman spectrometry, transmission electron microscopy and in-situ compressions. In the Raman analyses of severely deformed (above a strain energy density criterion of 5.9J/m2) surface regions of nanoscratched and nanoindented amorphous carbon films, two additional sharp and narrow peaks, DGr and GGr at 1330 and 1580cm−1, appeared from the main unchanged broad spectra, revealing the transformation of some small-range amorphous carbon to nanocrystalline graphite. Transmission electron microscopic images presented the formation of surface shear layer within which dispersed graphitic nanocrystallites (a size of about 3nm) were formed in the remaining amorphous matrix. The in-situ nanoscopic observation of amorphous carbon nanopillars under compressions confirmed the formation of graphitic nanocrystallites at pillar edge surfaces. The formed graphite (001) and (100) lattices were well oriented along maximum resolved shear stresses, being an evidence of lattice reconstruction and suggesting a possibility of stress-induced graphitization of amorphous carbon in the absence of heat.

Characterization of silk sponge in the wet state using13C solid state NMR for development of a porous silk vascular graft with small diameter

The 13C solid state NMR spectra of the sponge prepared from Bombyx mori silk fibroin with different 13C labeling sites, [3-13C]Ser, [3-13C]Tyr and [3-13C]Ala were observed in dry and wet states. Here the silk fibroin sponge was prepared using poly(ethylene) glycol diglycidyl ether (PGDE) as porogen. Two broad peaks assigned to β-sheet and random coil were observed for each 13C-labeled site in the dry state. Moreover, in the wet state, one additional sharp peak assigned to random coil with high mobility due to the presence of water was observed. When the silk fibroin aqueous solution and PGDE was mixed in the sponge preparation process, the slow structural change from random coil to β-sheet structure occurs together with decrease in the motion of the silk fibroin backbone chain. The silk fibroin graft with small diameter was prepared with a knitted silk fiber tube coated with this silk fibroin sponge. The high porosity and suture retention strength which are comparable to an ePTFE vascular graft were attained. The excellent results, high patency and high tissue ingrowth, were obtained with the porous silk fibroin graft with small diameter by a rat abdominal aorta implantation experiment.

Coexistence of quantum-confined Stark effect and localized states in an (In,Ga)N/GaN nanowire heterostructure

We analyze the emission of single GaN nanowires with (In,Ga)N insertions using both micro-photoluminescence and cathodoluminescence spectroscopy. The emission spectra are dominated by a green luminescence band that is strongly blueshifted with increasing excitation density. In conjunction with finite-element simulations of the structure to obtain the piezoelectric polarization, these results demonstrate that our (In,Ga)N/GaN nanowire heterostructures are subject to the quantum-confined Stark effect. Additional sharp peaks in the spectra, which do not shift with excitation density, are attributed to emission from localized states created by compositional fluctuations in the ternary (In,Ga)N alloy.

Quick single-step mechanosynthesis of ZnO nanorods and their optical characterization: milling time dependence

We report on the growth of ZnO nanorods (NRs) by a quick single-step mechanochemical process and investigated the milling time dependence on the structural and optical properties of the ZnO NRs. Mechanochemical reactions are carried out in a planetary ball mill for the time durations ranging from 30 min to 5 h. XRD and TEM studies revealed wurtzite structure of the as-grown ZnO NRs with length of several hundreds of nanometers to few micrometers after 30 min of reaction. Average diameter of the as-grown ZnO NRs decreases from 40 to 15 nm with increasing reaction time. Micro-Raman spectra show red- shift in the characteristic Raman modes, indicating pres- ence of milling induced strain. As-grown NRs show blueshift in the excitonic absorption peak with increasing milling time due to decrease in size and induced strain. Room temperature photoluminescence (PL) spectra show strong band-edge related UV emission and other three major emission peaks, two in the UV-blue region and one at the visible region. Post-growth annealing of the as- grown ZnO NRs completely eliminates the defect related visible PL band. Low-temperature PL studies show an additional sharp peak related to donor-bound excitonic transition, revealing the n-type nature of the as-grown NRs.

Sulfur K-edge XANES analysis of natural and synthetic basaltic glasses: Implications for S speciation and S content as function of oxygen fugacity

XANES analyses at the sulfur K-edge were used to determine the oxidation state of S species in natural and synthetic basaltic glasses and to constrain the fO 2 conditions for the transition from sulfide (S 2−) to sulfate (S 6+) in silicate melts. XANES spectra of basaltic samples from the Galapagos spreading center, the Juan de Fuca ridge and the Lau Basin showed a dominant broad peak at 2476.8 eV, similar to the spectra obtained from synthetic sulfide-saturated basalts and pyrrhotite. An additional sharp peak at 2469.8 eV, similar to that of crystalline sulfides, was present in synthetic glasses quenched from hydrous melts but absent in anhydrous glasses and may indicate differences in sulfide species with hydration or presence of minute sulfide inclusions exsolved during quenching. The XANES spectra of a basalt from the 1991 eruption of Mount Pinatubo, Philippines, and absarokitic basalts from the Cascades Range, Oregon, USA, showed a sharp peak at 2482.8 eV, characteristic of synthetic sulfate-saturated basaltic glasses and crystalline sulfate-bearing minerals such as hauyne. Basaltic samples from the Lamont Seamount, the early submarine phase of Kilauea volcano and the Loihi Seamount showed unequivocal evidence of the coexistence of S 2− and S 6+ species, emphasizing the relevance of S 6+ to these systems. XANES spectra of basaltic glasses synthesized in internally-heated pressure vessels and equilibrated at fO 2 ranging from FMQ − 1.4 to FMQ + 2.7 showed systematic changes in the features related to S 2− and S 6+ with changes in fO 2. No significant features related to sulfite (S 4+) species were observed. These results were used to construct a function that allows estimates of S 6+/ΣS from XANES data. Comparison of S 6+/ΣS data obtained by S Kα shifts measured with electron probe microanalysis (EPMA), S 6+/ΣS obtained from XANES spectra, and theoretical considerations show that data obtained from EPMA measurements underestimate S 6+/ΣS in samples that are sulfate-dominated (most likely because of photo-reduction effects during analysis) whereas S 6+/ΣS from XANES provide a close match to the expected theoretical values. The XANES-derived relationship for S 6+/ΣS as a function of fO 2 indicates that the transition from S 2− to S 6− with increasing fO 2 occurs over a narrower interval than what is predicted by the EPMA-derived relationship. The implications for natural systems is that small variation of fO 2 above FMQ + 1 will have a large effect on S behavior in basaltic systems, in particular regarding the amount of S that can be transported by basaltic melts before sulfide saturation can occur.

Bound Excitons inSr2CuO3

We investigated temperature dependent optical spectra of the one-dimensional chain compound Sr2CuO3. The charge transfer transition polarized along the chain direction shows a strongly asymmetric line shape as expected in one-dimensional extended Hubbard model. At low temperature, the charge transfer peak shows a large blueshift and reveals additional sharp peaks at the gap. Even though many spectroscopic studies suggest that this material cannot have a bound exciton based on the one-dimensional extended Hubbard model, we attribute the additional sharp peaks to excitons, which come to exist due to the long-range Coulomb interaction.

Synchronized Firing among Retinal Ganglion Cells Signals Motion Reversal

We show that when a moving object suddenly reverses direction, there is a brief, synchronous burst of firing within a population of retinal ganglion cells. This burst can be driven by either the leading or trailing edge of the object. The latency is constant for movement at different speeds, objects of different size, and bright versus dark contrasts. The same ganglion cells that signal a motion reversal also respond to smooth motion. We show that the brain can build a pure reversal detector using only a linear filter that reads out synchrony from a group of ganglion cells. These results indicate that not only can the retina anticipate the location of a smoothly moving object, but that it can also signal violations in its own prediction. We show that the reversal response cannot be explained by models of the classical receptive field and suggest that nonlinear receptive field subunits may be responsible.

Surface hydration states of commercial high purity α-Al2O3 powders evaluated by temperature programmed desorption mass spectrometry and diffuse reflectance infrared Fourier transform spectroscopy

The surface of three different grades of commercial high-purity α-Al2O3 powders produced by hydrolysis of aluminum alkoxide, which differ each other in SSA are evaluated by temperature programmed desorption mass spectrometry (TPDMS) and diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. For the DRIFT evaluation the powders were heated in situ under vacuum from 25 to 700 8C. The TPDMS spectra of desorbed H2O were obtained by heating the samples under ultra high vacuum at a rate of 20 K minK1 up to 1200 8C.The presence of hydrogen bonded water molecules, amorphous Al(OH)3 and AlOOH structures, as well as associated and isolated hydroxyl groups on the surface of all the a-Al2O3 powders investigated is demonstrated. On the surface of one of the powders the presence of crystalline Al(OH)3 structures, as evidenced by an additional sharp peak in the H2O TPDMS spectrum, is confirmed.

Excitons and multi-excitons in single CdTe quantum dots probed by near-field spectroscopy

A near-field optical spectroscopy study of a single CdTe/ZnTe quantum dot at low temperatures is presented. While the photoluminescence spectrum at low excitation power reveals only one single sharp peak due to the radiative recombination of excitons (X) in the single dot, several additional sharp peaks appear with increasing excitation density. The dominant features are ascribed to exciton complexes and charged exciton complexes such as negatively charged excitons (X −), neutral (2X and 3X) and negative (2X − and 3X −) biexcitons and triexcitons. Exciton charging arises due to efficient hole trapping by residual acceptors in the barrier material. This partly inhibits the formation of biexcitons and triexcitons. A spectral feature appearing close to the X − peak is tentatively assigned to X 2− negative excitons. This feature is found to shift to the red with increasing power: two possible explanations for this unexpected behaviour are proposed.