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At least 1,243 records · Page 69

Tribological Behavior of Structural Materials in High Temperature Helium Gas-Cooled Reactor Environments

The High-Temperature Gas-cooled Reactor (HTGR) is a Generation IV concept designed to produce electricity and hydrogen at high efficiencies via high operating temperatures (700 °C or higher). Helium, the primary coolant for HTGRs, contains impurities (e.g., CO, H2O and CH4) that can induce corrosion reactions at high temperatures such as oxidation and (de)carburization, which in turn can affect the tribological behavior of components. Incoloy® 800HT (Ni-Fe-Cr austenitic solid-solution alloy) and Inconel® 617 (Ni-Cr-Co-Mo solid-solution alloy) are two high-temperature superalloys currently selected as candidate structural materials for the HTGR. The objective of this study is to evaluate the high-temperature tribological performance of these two candidate alloys after conditioning them in HTGR environments. Four regimes of corrosion were considered: a non-conditioned regime (Regime I), an oxidizing regime (Regime II), a carburizing and oxidizing regime (Regime III), and a carburizing regime (Regime IV). To simulate oxidation in HTGR, samples were conditioned for 22 days at elevated temperatures in a once-through helium loop with 4 ppmv H2O. Carburization of the samples was achieved by the commercial process, Kolsterising®. In addition, two surface treatments – shot peening and aluminization – were considered as potential routes of improving the alloys’ wear resistance. Surface-treated samples were tested both before and after conditioning in Regime II. Tribological testing of the samples was performed via a pin-on-disk tribometer at elevated temperatures in ambient environment – 650 and 750°C for 800HT; 850 and 900°C for 617 – with applied loads of 1N, 2N and 5N. The wear behavior of the alloys was assessed via wear volume and friction coefficient measurements, supported by morphological, structural and compositional analyses of the wear tracks. Conditioning the samples in Regime II led to the formation of a chromium oxide on both alloys. This protective scale increased the wear resistance compared to that of as-received samples (Regime I) due to the formation of a compacted ‘glaze’ oxide layer during sliding, rendering the wear track nearly undistinguishable from the unworn background and resulting in wear volumes below the detection limits of the measurement technique. The variability of the friction coefficients of the conditioned samples was also considerably reduced compared to that of the as-received samples due to the glaze layer. Additionally, the initial friction coefficients of the samples conditioned in Regime II were reduced by 45% and 54% compared to those of as-received samples for alloys 800HT and 617, respectively. Carburizing the samples (Regime IV) hardened the surfaces of both alloys and promoted the formation of an iron oxide on 800HT during tribological testing, thereby increasing the wear resistance and decreasing the initial friction coefficient by a factor of two compared to those of as-received 800HT. Alloy 617 exhibited an enhanced wear resistance but similar initial friction coefficient compared to those of as-received samples due to the increased surface hardness. The Mn-Cr oxide developed during Regime III conditioning of 800HT did not develop a glaze layer during tribotesting, even at lower loads. Thus, it was not as protective as the oxide produced during conditioning of Regime II samples, leading to lower wear resistance of 800HT in Regime III compared to that measured in the Regime II condition. 800HT benefited from the aluminization surface treatment, particularly before conditioning in Regime II, due to the promotion of a wear-resistant aluminum oxide layer during testing and the increase in surface hardness due to the presence of a FeAl intermetallic phase. The presence of this phase caused an order-of-magnitude reduction in wear volumes compared to those of as-received 800HT. Aluminization of 617 decreased its wear resistance, particularly after conditioning in Regime II, due to significant wear of the aluminum oxide via a ceramic wear mechanism. This aluminum oxide was removed during sliding, causing the wear volumes to increase by a factor of five compared to those of 617 conditioned in Regime II. Shot-peened 800HT exhibited a tribological behavior similar to that of as-received 800HT, despite an enhancement in the rate of chromium oxide formation. Shot-peened 800HT conditioned in Regime II showed lower wear resistance compared to that of 800HT conditioned in Regime II due to the poor adhesion between the oxide and the underlying metal, preventing the formation of the glaze layer during sliding. Shot peening of 617 increased its wear resistance at higher load, reducing worn volumes by 60% compared to that measured with as-received 617. Tribotesting of shot-peened 617 in Regime II revealed that the glaze-oxide layer was formed at every load, resulting in negligible wear, similar to what was observed from testing 617 after conditioning in Regime II. Overall, alloy 617 exhibited tribologically superior behavior compared to that of alloy 800HT, as demonstrated by its lower friction coefficients and its order-of-magnitude lower wear volumes when measurable.

36 MATERIALS SCIENCE↗

Efficiently enhanced photoluminescence in Eu3+-doped Lu2(MoO4)3 by Gd3+ substituting

Highlights: • The Gd{sup 3+} doped samples had been discovered to show much better luminescent properties than Lu{sub 2}(MoO{sub 4}){sub 3}:0.02Eu{sup 3+}. • The influence of Gd{sup 3+} ions on luminescence behavior was discussed. • The DFT calculation indicates that the structure of Gd{sub 2}(MoO{sub 4}){sub 3} is more propitious for luminescence than that of Lu{sub 2}(MoO{sub 4}){sub 3}. - Abstract: A series of Lu{sub 2-x}Gd{sub x}(MoO{sub 4}){sub 3}:0.02Eu{sup 3+} (x = 0–2) red-emitting phosphors have been synthesized by the standard solid-state reaction method. Interestingly, the Gd concentration plays a profound role to influence the luminescence property. A conspicuous monotonic increase could be found in the influence of Gd{sup 3+} concentration to the emission intensity, and finally Gd{sub 2}(MoO{sub 4}){sub 3}:0.02Eu{sup 3+} exhibits the strongest red light emission with the intensifying factor even reaching 3.04-fold compared to Lu{sub 2}(MoO{sub 4}){sub 3}:0.02Eu{sup 3+}. Careful structural analysis suggested that up to about 80% (x = 1.6) Lu can be substituted by Gd with the same crystal structure of Lu{sub 2}(MoO{sub 4}){sub 3} being retained, while a higher Gd concentration would lead to it crystallizing in the Gd{sub 2}(MoO{sub 4}){sub 3} structure. We believe that the variation of crystal structure is responsible for the photoluminescence enhancing process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

High coercivity sized controlled cobalt–gold core–shell nano-crystals prepared by reverse microemulsion

Graphical abstract: - Highlights: • Calculating the crystallinity percentage and percentage of phases presented in Co–Au core–shell nanoparticles. • Magnetic properties of four groups nanogarin: 5, 10, 15, 20 nm. • Single domain ferromagnetic materials with high coercivity at room temperature. • Intrinsic blocking temperature measured in zero field cooled-warmed (ZFC-W). - Abstract: Size-controlled cobalt–gold core–shell nanoparticles were synthesized via the reverse-micelle microemulsion method. In order to control the size of the nanoparticles, the nucleation and growth process were performed within a confined space by adjusting the water to surfactant ratio of reverse micelles solution during synthesis. The crystallinity percentage and percentage of phases presented in Co–Au core–shell nanoparticles were calculated using X-ray diffraction data. The results from transmission electron microscopy provide direct evidence for core–shell structure nanomaterials. Magnetic properties of the samples were investigated using a vibrating sample magnetometer. The as-prepared samples showed significant coercivity at room temperature. The intrinsic blocking temperature was experimentally deduced from zero-field-cooled warmed (ZFC-W) curves by a simple method without employing an external magnetic field. The B-field dependence temperature data of Co–Au nanoparticles exhibited an intrinsic blocking temperature at 45 K. Annealing these samples at 400 °C caused an increase in particle size, crystallinity percentage and further enhanced their magnetic properties.

36 MATERIALS SCIENCE↗

ENHANCED WARM H{sub 2} EMISSION IN THE COMPACT GROUP MID-INFRARED ''GREEN VALLEY''

We present results from a Spitzer mid-infrared spectroscopy study of a sample of 74 galaxies located in 23 Hickson Compact Groups (HCGs), chosen to be at a dynamically active stage of H I depletion. We find evidence for enhanced warm H{sub 2} emission (i.e., above that associated with UV excitation in star-forming regions) in 14 galaxies ({approx}20%), with 8 galaxies having extreme values of L(H{sub 2} S(0)-S(3))/L(7.7 {mu}m polycyclic aromatic hydrocarbon), in excess of 0.07. Such emission has been seen previously in the compact group HCG 92 (Stephan's Quintet), and was shown to be associated with the dissipation of mechanical energy associated with a large-scale shock caused when one group member collided, at high velocity, with tidal debris in the intragroup medium. Similarly, shock excitation or turbulent heating is likely responsible for the enhanced H{sub 2} emission in the compact group galaxies, since other sources of heating (UV or X-ray excitation from star formation or active galactic nuclei) are insufficient to account for the observed emission. The group galaxies fall predominantly in a region of mid-infrared color-color space identified by previous studies as being connected to rapid transformations in HCG galaxy evolution. Furthermore, the majority of H{sub 2}-enhanced galaxies lie in the optical ''green valley'' between the blue cloud and red sequence, and are primarily early-type disk systems. We suggest that H{sub 2}-enhanced systems may represent a specific phase in the evolution of galaxies in dense environments and provide new insight into mechanisms which transform galaxies onto the optical red sequence.

79 ASTRONOMY AND ASTROPHYSICS↗

Flash Mixing of the White Dwarf Cooling Curve Spectroscopic Confirmation in NGC 2808

We present new HST far-UV spectroscopy of two dozen hot evolved stars in NGC 2808, a massive globular cluster with a large population of "blue-hook" stars. The blue-hook stars are found in ultraviolet color-magnitude diagrams of the most massive globular clusters, where they fall at luminosities immediately below the hot end of the horizontal branch (HB), in a region of the HR diagram unexplained by canonical stellar evolution theory. Using new theoretical evolutionary and atmospheric models, we have shown that these subluminous HB stars are very likely the progeny of stars that undergo extensive internal mixing during a late He-core flash on the white dwarf cooling curve. This flash mixing leads to hotter temperatures and an enormous enhancement of the surface He and C abundances; the hotter temperatures and associated decrease in the hydrogen opacity shortward of the Lyman limit makes the stars brighter in the extreme UV but appear sub luminous in the UV and optical. Our far-UV spectroscopy demonstrates that, relative to normal HB stars at the same color, the blue-hook stars of NGC 2808 are hotter and greatly enhanced in He and C, thus providing unambiguous evidence of flash mixing in the subluminous population. Although the C abundance in the blue-hook stars is orders of magnitude larger than that in the normal HB stars, the atmospheric C abundance in both the blue-hook and normal HB stars appears to be affected by gravitational settling. The abundance variations seen in C, Si, and the Fe-peak elements indicate that atmospheric diffusion is at play in our sample, with all of our hot subdwarfs at 25,000 K to 50,000 K exhibiting large enhancements of the iron-peak elements. The hottest subdwarfs in our blue-hook sample may be pulsators, given that they fall in the temperature range of newly-discovered pulsating subdwarfs in omega Cen.

Brown, Thomas M.↗

MO-FG-CAMPUS-JeP2-01: 4D-MRI with 3D Radial Sampling and Self-Gating-Based K-Space Sorting: Image Quality Improvement by Slab-Selective Excitation

Purpose: A recent 4D MRI technique based on 3D radial sampling and self-gating-based K-space sorting has shown promising results in characterizing respiratory motion. However due to continuous acquisition and potentially drastic k-space undersampling resultant images could suffer from low blood-to-tissue contrast and streaking artifacts. In this study 3D radial sampling with slab-selective excitation (SS) was proposed in attempt to enhance blood-to-tissue contrast by exploiting the in-flow effect and to suppress the excess signal from the peripheral structures particularly in the superior-inferior direction. The feasibility of improving image quality by using this approach was investigated through a comparison with the previously developed non-selective excitation (NS) approach. Methods: Two excitation approaches SS and NS were compared in 5 cancer patients (1 lung 1 liver 2 pancreas and 1 esophagus) at 3Tesla. Image artifact was assessed in all patients on a 4-point scale (0: poor; 3: excellent). Signal-tonoise ratio (SNR) of the blood vessel (aorta) at the center of field-of-view and its nearby tissue were measured in 3 of the 5 patients (1 liver 2 pancreas) and blood-to-tissue contrast-to-noise ratio (CNR) were then determined. Results: Compared with NS the image quality of SS was visually improved with overall higher signal in all patients (2.6±0.55 vs. 3.4±0.55). SS showed an approximately 2-fold increase of SNR in the blood (aorta: 16.39±1.95 vs. 32.19±7.93) and slight increase in the surrounding tissue (liver/pancreas: 16.91±1.82 vs. 22.31±3.03). As a result the blood-totissue CNR was dramatically higher in the SS method (1.20±1.20 vs. 9.87±6.67). Conclusion: The proposed 3D radial sampling with slabselective excitation allows for reduced image artifact and improved blood SNR and blood-to-tissue CNR. The success of this technique could potentially benefit patients with cancerous tumors that have invaded the surrounding blood vessels where radiation therapy is needed to remove tumor from those regions prior to surgical resection. This work is partially supported by NIH R03CA173273; and CTSI core voucher award.

60 APPLIED LIFE SCIENCES↗

Enhancement of visible light activity in Ag modified SnO{sub 2}/TiO{sub 2}

Graphical abstract: - Highlights: • Ag modified SnO{sub 2}/TiO{sub 2} nanoparticles were synthesized by a modified sol–gel method. • As-prepared samples have a small and uniform particle size of about 20 nm. • As-prepared samples exhibit an excellent photo-catalytic efficiency on the degradation of MB. • As-prepared samples maintain high photo-chemical stability after 5 catalytic cycles. - Abstract: Ag modified SnO{sub 2}/TiO{sub 2} nanoparticles were successfully prepared by a modified sol–gel method, without adding any acid or alkali. The entire preparation differs from the traditional sol–gel synthesis of TiO{sub 2} that the reaction can get controlled by adjusting the flow speed of water vapor. Ultraviolet–visible diffuse reflectance spectra (UV–vis) and spin-trapping electron paramagnetic resonance (EPR) were used to forecast the photocatalytic activity of the samples, and the results were proved by the degradation of methylene blue solution under visible light. Compared with pure TiO{sub 2}, as-prepared Ag modified SnO{sub 2}/TiO{sub 2} nanoparticles exhibited not only an enhanced photocatalytic activity but also an improved stability. Among all of samples, the composite with 0.5% of Ag and 1% of Sn showed the best photocatalytic performance and stability. Further increasing the Ag proportion will result in the decrease of the photocatalytic activity. A relative mechanism was proposed and discussed in detail.

36 MATERIALS SCIENCE↗

Facile formation of Ag{sub 2}WO{sub 4}/AgX (X = Cl, Br, I) hybrid nanorods with enhanced visible-light-driven photoelectrochemical properties

Highlights: • Ag{sub 2}WO{sub 4}/AgX hybrid nanorods were prepared by a facile in-situ anion exchange reaction. • Ag{sub 2}WO{sub 4} nanorods and different X{sup −} ions were reacted in water at room temperature. • The hybrids possess significantly enhanced photoelectrochemical properties. • Ag{sub 2}WO{sub 4}/AgBr hybrids exhibit the highest photocatalytic activity among three samples. • The active species tests were also investigated to confirm photocatalytic mechanism. - Abstract: In this work, we demonstrated a general strategy for the preparation of a series of uniform Ag{sub 2}WO{sub 4}/AgX (X = Cl, Br, I) hybrid nanorods by a facile in-situ anion exchange reaction occurring at room temperature between pregrown Ag{sub 2}WO{sub 4} nanorods and different X{sup −} ions in water. Compared with Ag{sub 2}WO{sub 4} nanorods, further investigation has revealed that the as-prepared hybrid nanorods possess significantly enhanced photocurrent response and photocatalytic activity in degrading methyl orange (MO) under visible-light irradiation. In particular, the Ag{sub 2}WO{sub 4}/AgBr hybrid nanorods exhibit the highest photocatalytic activity among the three kinds of samples. The active species tests indicate that superoxide anion radicals and photogenerated holes are responsible for the enhanced photocatalytic performance.

36 MATERIALS SCIENCE↗

Halide eutectic growth experiment MA-131

Fiberlike sodium chloride/lithium fluoride eutectic mixtures have been produced on earth and in space by the directional solidification technique. Macroscopic and microscopic examinations were made on longitudinal and transverse sections of Apollo Soyuz Test Project space grown and earth grown ingots. It was found that samples grown in space have a higher percentage of fibers alined with the growth axis. The enhanced alinement of fibers is attributed to the absence of convection currents in the liquid during solidification. Optical transmittance measurements of transverse sections of the space grown and earth grown ingots were performed with an infrared spectrometer. For a given sample thickness, the highest transmittance was obtained from ingots grown in space. For samples of different thicknesses, grown either in space or on earth, it was found that the thinner the sample, the higher the transmittance. This is in agreement with the general optical property of transparent materials.

Yue, A. S.↗

Effect of reactor loading on atomic oxygen concentration as measured by NO chemiluminescence

It has previously been observed that the etch rate of polyethylene samples in the afterglow of an RF discharge in oxygen increases with reactor loading. This enhancement of the etch rate is attributed to reactive gas phase products of the polymer etching. In the present work, emission spectroscopy is employed to examine the species present in the gas phase during etching of polyethylene. In particular, the concentration of atomic oxygen downstream from the polyethylene samples is studied as a function of the reactor loading. It is found that the concentration of atomic oxygen increases as the reactor loading is increased. The increase of etch rate with increased reactor loading is attributed to the increase of atomic oxygen concentration in the vicinity of the sample.

Lerner, N. R.↗

Synthesis of crystalline carbon nanofern-like structure by dc-PECVD and study of its electrical and field emission properties

Graphical abstract: Display Omitted Highlights: ► Branched, carbon nanofern like structure have been synthesized on glass substrate via PECVD. ► Ni catalyst played important role in growing such structure. ► The as prepared sample shows good field emission property with turn on field as low as 4.8 V/mm. ► Temperature dependent conductivity of the sample showed non-linearity. -- Abstract: Carbon nanofern-like structure was synthesized by direct current plasma enhanced chemical vapor deposition at 400 °C using acetylene as carbon precursor and nickel particle as seed. High resolution transmission electron microscopy (HRTEM) study confirmed the fern-like structure of the as-synthesized sample. It was seen that when nickel was not used a cluster deposition took place without forming any structure. Atomic force microscopy study showed the surface topology of the as-prepared samples. X-ray photoelectron spectroscopy as well as HRTEM studies confirmed the presence of nickel in the carbon matrix. Current (I)–voltage (V) characteristics have been taken for three different temperatures. A non-linear I–V characteristic was obtained for the fern like sample. Field emission study showed that carbon nanofern showed efficient field emission with a turn-on field as low as 4.8 V/μm. Also, the field emission has been studied for different inter-electrode distances.

36 MATERIALS SCIENCE↗

Enhanced photosensitized degradation of rhodamine B on CdS/TiO{sub 2} nanocomposites under visible light irradiation

Graphical abstract: The photosensitized degradation of RhB was largely enhanced by the synergistic effect of the RhB and CdS/TiO{sub 2} nanocomposite. The composite of the two inorganic semiconductors with appropriate oxidation reduction energy levels enhanced the charge separation and extended the absorption response to visible region. - Highlights: • CdS/TiO{sub 2} nanocomposites were synthesized by a simple hydrothermal method. • Samples prepared at 200 °C, 12 h, CdS/TiO{sub 2} = 12% possessed the best activity. • The photosensitized degradation of RhB was largely enhanced by the composite. • The better activity was due to the synergistic effect of the RhB and CdS/TiO{sub 2}. - Abstract: Visible-light-driven photocatalysts, CdS/TiO{sub 2} nanocomposites were synthesized by a simple hydrothermal method. Their formation and structures were characterized by X-ray diffractometer, transmission electron microscopy, diffuse reflectance spectroscopy, and X-ray photoelectron spectroscopy. Taking rhodamine B (RhB) as a model, their photocatalytic activities in aqueous phase under visible light irradiation (420 < λ < 800 nm) were tested. The results showed that the composite of CdS and TiO{sub 2} with appropriate oxidation reduction energy levels enhanced the charge separation and extended the absorption response into visible light region. Thus, the photosensitized degradation of RhB was largely enhanced. The degradation mechanism was explored concretely.

36 MATERIALS SCIENCE↗

Cascaded spin motive force driven by the dynamics of the skyrmion lattice

We numerically investigate the spin motive force (SMF) driven by the dynamics of a Skyrmion lattice. The rotating mode of the Skyrmion core excited by the AC magnetic field induces the large spin-dependent electric field near the core. Due to the collective dynamics of Skyrmion lattice, the measurable voltage is enhanced by the cascade effect of the SMF. The amplitude of the AC voltage is estimated to 30 μV in a macroscopic sample, where 100 Skyrmions exist between two probes. We also investigate the SMF due to the dynamics of the helical magnetic state, where the enhancement of the SMF does not occur.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Enhanced magnetostrictive effect in epoxy-bonded Tb{sub x}Dy{sub 0.9−x}Nd{sub 0.1}(Fe{sub 0.8}Co{sub 0.2}){sub 1.93} pseudo 1–3 particulate composites

The spin configuration and spontaneous magnetostriction λ{sub 111} of Tb{sub x}Dy{sub 0.9−x}Nd{sub 0.1}(Fe{sub 0.8}Co{sub 0.2}){sub 1.93} (0.20 ≤ x ≤ 0.60) alloys have been investigated. The easy magnetization direction (EMD) at room temperature was observed towards the 〈111〉 axis when 0.40 ≤ x ≤ 0.60, accompanied by a rhombohedral distortion with large spontaneous magnetostriction coefficients λ{sub 111}, which increases from 1640 ppm for x = 0.40 to 1900 ppm for x = 0.60. The strong 〈111〉-oriented pseudo 1–3 particulate composite was fabricated by embedding and aligning particles in a passive epoxy matrix under an applied magnetic field. An enhanced magnetostrictive effect, the large low-field magnetostriction, λ{sub a}, as high as 480 ppm at 3 kOe, was obtained for the sample of x = 0.40, in an excess of 75% of its polycrystalline alloy although it only contains 27 vol. % alloy particles. This enhanced effect can be attributed to its low magnetic anisotropy, anisotropic magnetostrictive nature (e.g., λ{sub 111} ≠ λ{sub 100,} 〈111〉EMD), chain structure, and the 〈111〉-textured orientation. In addition, we give a direct experimental support that the 〈111〉EMD of particle and the strong 〈111〉-textured orientation are the crucial factors to realize the enhanced magnetostrictive effect in 1–3 particulate composites.

36 MATERIALS SCIENCE↗

Magnetic properties versus interface density in rigid-exchange-coupled amorphous multilayers with induced uniaxial anisotropy

We demonstrate the possibility to tune the saturation magnetization, coercivity, and uniaxial in-plane anisotropy constant in amorphous bilayers and multilayers of Co 85 (Al 70 Zr 30 ) 15 and Sm 11 Co 82 Ti 7 through the interface density. From magnetometry and x-ray circular dichroism (XMCD) measurements, we conclude that the easy-axis coercivity μ 0 H c increases four times when the number of bilayer repetitions, N, increases from 1 to 10 within a constant total sample thickness of 20 nm. At the same time, the anisotropy constant K u also increases by a factor four, whereas the saturation magnetization M s decreases slightly. The Co spin and orbital moments, m s and m l , are found to be approximately constant within the sample series. The average total Co moment is only 0.8-0.9 μ B /atom, but the m l /m s ratio is strongly enhanced compared to pure Co. Magnetization curves extracted from XMCD measurements show that the Co and Sm moments are ferromagnetically coupled for all samples.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Fidelity-preserving enhancement of ptychography with foundational text-to-image models

Ptychographic phase retrieval enables high-resolution imaging of complex samples but often suffers from artifacts such as grid pathology and multislice crosstalk, which degrade reconstructed images. We propose a plug-and-play (PnP) framework that integrates physics model-based phase retrieval with text-guided image editing using foundational diffusion models. By employing the alternating direction method of multipliers, our approach ensures consensus between data fidelity and artifact removal subproblems, maintaining physical consistency while enhancing image quality. Artifact removal is achieved using a text-guided diffusion image editing method (LEDITS++) with a pre-trained foundational diffusion model, allowing users to specify artifacts for removal in natural language. Demonstrations on simulated and experimental datasets show significant improvements in artifact suppression and structural fidelity, validated by metrics such as peak signal-to-noise ratio and diffraction pattern consistency. This work highlights the combination of text-guided generative models and model-based phase retrieval algorithms as a transferable and fidelity-preserving method for high-quality diffraction imaging.

image editing↗

Inorganic–organic hybrids presenting high basic center content: SBA-15 incorporation, toxic metals sorption and energetic behavior

Highlights: ► Mesoporous SBA-15 silicas were organofunctionalized with new silylant agents. ► Thiocarbamate was used to enhance the silylating agent chains and basic centers. ► The synthesized pendant chains contain nitrogen and sulfur basic centers. ► The new hybrids sorb toxic cations from aqueous solutions with high efficiency. ► The thermodynamic data demonstrated favorable cation/basic center interactions. - Abstract: Mesoporous SBA-15 samples were organofunctionalized with mono, di- and tri-aminosilanes that previously reacted with thiocarbamide to enhance the organic chains and attach nitrogen and sulfur basic centers to the surface of the solids. These new organosilanes were synthesized through a non-solvent approach to reduce both cost and hazardous wastes. The high affinities for both hard and soft Lewis acids due to the combination of nitrogen and sulfur atoms attached to the same pendant chain enabled favorable sorption capacities for Cu{sup 2+}, Cd{sup 2+} and Pb{sup 2+} cations, with maximum capacities of 1.90, 3.48 and 5.30 mmol g{sup −1}, respectively, for the most efficient mesoporous silica. Microcalorimetric investigations allowed the calculation of the thermodynamic data at the solid/liquid interface. All Gibbs energy are negative as expected for spontaneous cation/basic center interactions and the positive entropic values from 49 ± 3 to 108 ± 5 J K{sup −1} mol{sup −1}, also reinforced this favorable interactive process in heterogeneous system. The designed organosilanes covalently bonded to the inorganic siliceous skeleton can be suggested as new materials for toxic metal removal from a wastewater with high efficiency.

36 MATERIALS SCIENCE↗

BOOSTING LY α AND He ii λ 1640 LINE FLUXES FROM POPULATION III GALAXIES: STOCHASTIC IMF SAMPLING AND DEPARTURES FROM CASE-B

We revisit calculations of nebular hydrogen Ly α and He ii λ 1640 line strengths for Population III (Pop III) galaxies, undergoing continuous, and bursts of, star formation. We focus on initial mass functions (IMFs) motivated by recent theoretical studies, which generally span a lower range of stellar masses than earlier works. We also account for case-B departures and the stochastic sampling of the IMF. In agreement with previous work, we find that departures from case-B can enhance the Ly α flux by a factor of a few, but we argue that this enhancement is driven mainly by collisional excitation and ionization, and not due to photoionization from the n = 2 state of atomic hydrogen. The increased sensitivity of the Ly α flux to the high-energy end of the galaxy spectrum makes it more subject to stochastic sampling of the IMF. The latter introduces a dispersion in the predicted nebular line fluxes around the deterministic value by as much as a factor of ∼4. In contrast, the stochastic sampling of the IMF has less impact on the emerging Lyman Werner photon flux. When case-B departures and stochasticity effects are combined, nebular line emission from Pop III galaxies can be up to one order of magnitude brighter than predicted by “standard” calculations that do not include these effects. This enhances the prospects for detection with future facilities such as the James Webb Space Telescope and large, ground-based telescopes.

79 ASTRONOMY AND ASTROPHYSICS↗