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While SrTiO3 exhibits promising electronic transport properties, its high thermal conductivity (κ) is detrimental for its use as a thermoelectric material. Here, we investigate the influence of oxygen non-stoichiometry on κ in bulk SrTiO3 ceramics. A significant reduction in κ was achieved in oxygen deficient SrTiO3−δ, owing to the presence of oxygen vacancies that act as phonon scattering centers. Upon oxidation of SrTiO3−δ, the κ of pristine SrTiO3 was recovered, suggesting that oxygen vacancies were indeed responsible for the reduction in κ. Raman spectroscopy was used as an independent tool to confirm the reduction of oxygen vacancies in SrTiO3−δ upon oxidation.
To study the effects of the support morphology on the hydrodesulfurization (HDS) activity of NiMoS catalysts, ordered mesoporous SiO2 (KIT-6) and nonporous nanospheres of SiO2 were used as supports. Metal species (Ni and Mo) were incorporated through a sequential impregnation technique. The aqueous solution of nickel nitrate was introduced first on the supports, followed by the solution of ammonium molybdate. Subsequently, a sulfidation treatment was carried out in gaseous H2S/H2 atmosphere. The NiMo/Al2O3 commercial catalyst was used as reference. The materials obtained were characterized by N2 physisorption, X-ray diffraction (XRD), and high-resolution transmission electron microscopy (HRTEM) and evaluated in the HDS catalytic reaction of dibenzothiophene in a batch reactor. The results indicate that the textural properties of KIT-6 were the key factors to obtain disperse NiMoS stacks, and a better metal sulfidation, which lead to a higher catalytic activity of the NiMo/KIT-6 catalyst (twice as active) compared to the NiMo/Nanosilica catalyst. In addition, the activity of the NiMo/KIT-6 catalyst was also superior to that obtained for the commercial catalyst.
The acidity of SBA-15 was tuned with the incorporation of Al+3, Ti+4, and –PrSO3H groups through sol–gel, employing molar ratios of Si/M = 10 (M = Al, Ti) and Si/S = 10. This results in mesoporous materials with the typical hexagonal structure of SBA-15, large surface areas, and great pore diameter. The incorporation of Al+3 and Ti+4 mainly leads to catalysts with both Brönsted and Lewis acid sites. The addition of sulfonic groups to these samples enhanced their surface acidity, creating preferentially Brönsted acid sites. Among the evaluated catalysts, the SBA-15-SO3H showed the highest catalytic activity, which was related to the high concentration of Lewis acid sites, and a remarkable resistance to deactivation, probably due to its low hydrophilicity. A first order kinetic equation fits well the experimental data and an activation energy of 31.5 kJ/mol similar to other reports for this reaction was calculated for the SBA-15-SO3H catalyst.
Magnesium alloy (AZ31) reinforced with carbon nanotubes (CNTs) and grapheme nanoplatelets (GNPs) were fabricated with the method of hot-pressing sintering and hot extrusion processes. GNPs and CNTs were predispersed with Al and Zn powders by ball milling used as precursor for sintering, which effectively guaranteed the integrity and dispersion of them. The microstructure and mechanical properties of the composites (denoted as Mg–3 wt% Al–1 wt% Zn–1 wt% (xCNTs + yGNPs)(x:y = 1:1, 1:2, 1:3) were investigated. The results show that the CNTs and GNPs are uniformly distributed in the matrix and closely combined with the matrix in nanoscale. Among the tested composites, Mg–3 wt% Al–1 wt% Zn–1 wt% (xCNTs + yGNPs)(x:y = 1:2) exhibits the most favorable mechanical properties, and the yield strength, tensile and compressed strength, and elongation of composites are substantially improved by the addition of 0.33 wt% CNTs and 0.67 wt% GNPs. Novel strengthening mechanisms such as three-dimensional reinforced structure formed by CNTs and GNPs are found for the remarkable improvement in mechanical properties.
The oxidation behavior of nanograined and coarse-grained alloys may differ significantly. This empirical observation has been justified on the basis of accelerated grain boundary diffusion. However, thermal destabilization of nanograined microstructures studied in model sputter deposited NiCrAl alloys progresses concurrently with the onset of oxidation. This phenomenon makes it challenging to pinpoint the specific contribution of the original grain boundary network. In this study, dilute additions of Y are used to delay the onset of microstructural evolution at elevated temperatures through nanocluster formation and grain boundary pinning. The enhanced microstructural stability resulted in measurably different oxide morphologies during the transient stages of oxidation and slower oxidation rates overall. This coupling between the earliest stages of oxidation and microstructural evolution are directly manipulated to study fundamental oxidation processes in sputtered NiCrAl. Insights gained from this study may ultimately be used to develop novel strategies for improved oxidation resistance in structural alloys.
The grain boundary network of nanocrystalline Cu foils was modified by the application of cyclic loadings and elevated temperatures. Broadly, the changes to the boundary network were directly correlated with the applied temperature and accumulated strain, including a 300% increase in the twin length fraction. By independently varying each treatment variable, a matrix of grain boundary statistics was built to check the plausibility of hypothesized mechanisms against their expected temperature and stress/strain dependences. These comparisons allow the field of candidate mechanisms to be significantly narrowed. Most importantly, the effects of temperature and strain on twin length fraction were found to be strongly synergistic, with the combined effect being ∼150% that of the summed individual contributions. Looking beyond scalar metrics, an analysis of the grain boundary network showed that twin related domain formation favored larger sizes and repeated twin variant selection over the creation of many small domains with diverse variants.
High-purity niobium single crystals of five different orientations were compressed at 77 K to 2–4% plastic strain to investigate the mechanisms operative in the initial stage of yielding. The crystals deformed in the direction close to the [001] axis exhibit predominant slip on the high-stressed (101) and a much lower stressed $\left( {0\bar{1}1} \right)$ plane. The expected slip on the $\left( {\bar{1}01} \right)$ plane is nearly homogeneously distributed with only a few sharp slip traces corresponding to localized slip. The samples compressed along center-triangle orientations and those close to the $\left[ {011} \right] - \left[ {\bar{1}11} \right]$ edge deform predominantly by twinning on {112}〈111〉 systems with some contribution from slip on the $\left( {\bar{1}01} \right)\left[ {\bar{1}\bar{1}\bar{1}} \right]$ system with the highest Schmid factor. A majority of twins exhibit internal contrast due to alternating slip on $\left( {\bar{1}01} \right)$ and $\left( {0\bar{1}1} \right)$ planes. No slip traces are observed in the matrix adjacent to the twin, which implies that twin boundaries are impenetrable obstacles for the motion of dislocations.
Manganese sulfides (MnS) with a diversity of well-defined morphologies and phases have been successfully synthesized by the solvothermal approach. The phase structure and morphology of MnS could readily be tuned by adjusting the sulfur sources and solvents. Hollow γ-MnS spheres were obtained by treating L-cysteine and manganese source in ethylene glycol (EG) at 200 °C for 2 h, whereas a replacement of the mixture solvent by EG and deionized water yields the hierarchical flower-like γ-MnS. γ-MnS tubes were also produced under the same condition by using diethylene glycol and deionized water as solvents. When thioacetamide used as the sulfur source and oleylamine used as the solvent, monodisperse α-MnS nanoparticles with the mean diameter of 17 nm could be synthesized successfully. The phase structures, sizes, and morphologies of samples were investigated in detail by powder X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The UV-vis absorption peak and the width of band gap with different morphologies of the as-prepared MnS were measured. The samples described in this paper are promising to be utilized in solar cells, biomedicine, short wavelength electronic devices, photocatalysis, and other fields.
The layer-by-layer self-assembly technology was adopted to prepare a new generation of supercapacitor electrode material, GOQDs@NiAl-LDH, between Ni–Al layered double hydroxide (LDH) and graphene oxide quantum dots (GOQDs). First, Ni–Al LDH was prepared by coprecipitation of nickel nitrate and aluminum nitrate and then delaminated by ultrasonication. Second, NiAl-LDH was combined with GOQDs that were prepared by a ball milling reaction using hexachlorobenzene as raw material. The electrochemical data indicate that the composite (OGL9) exhibits highest specific capacitance, large current charge and discharge characteristics, and excellent cycle stability when the content of GOQDs is 10%. And the specific capacitance of composite reaches to 869 F/g at the current density of 1 A/g. Moreover, the capacitance retention at 1 A/g discharge current condition is 69.6% after 2000 cycles. And the results indicate that the OGL9 can be a promising electrode material for supercapacitor applications.
The aim of this study was to investigate the in vivo degradation mechanism and the mechanical properties of poly(lactide-co-glycolide)/beta-tricalcium phosphate (PLGA/β-TCP) composite anchors. Anchors composed of PLGA and β-TCP were implanted in the dorsal subcutaneous tissue of beagle dogs for 6, 12, 16, and 26 weeks. The degradation of the materials was evaluated by measuring the changes in thermal behavior, crystallinity, and mechanical properties. Scanning electron microscope (SEM) was used to observe the surface and longitudinal section of the material. The evaluation of mechanical strength retention and degradation properties suggest that the addition of β-TCP particles efficiently enhances their mechanical properties and thermal characteristics and delays their degradation rate. By analyzing the results of SEM, X-ray diffraction, and differential scanning calorimetry, we can infer that after 12 weeks, the connection between β-TCP and PLGA becomes less compact, which accelerates the decline of mechanical strength.
AZ31 magnesium alloy sheets were A-TIG-welded through a coating of flux, which contained different ratios of Ce powder and nano-sized SiC as reinforcement particles and equal mass of TiO2 as activating fluxes. The microscopic analysis results illustrated that relatively low content of Ce in the reinforcement particles caused the formation of Al3Ce precipitates and refined the grains of α-Mg phase together with β-Mg17Al12 and SiC particles. The increase in microhardness and ultimate tensile strength of the joints was 6.2% and 19.2%, respectively, when reinforcement particles contain 20 wt% Ce compared to the joints coated without Ce. By studying the electrochemical test results, when using 20 wt% Ce + 80 wt% SiC as reinforcement particles, the corrosion current density was the lowest and the corrosion resistance reached the largest value, reflecting the improvement of corrosion property of the joint affected by Ce element.
Carbon nanotubes (CNTs) were added to carbon nanofibers (CNFs) as additives to improve their electrochemical properties. In the present work, CNFs were prepared by using pressurized gyration with polyacrylonitrile as the precursor. The microstructure and electrochemical properties of samples were investigated by scanning electron microscopy and electrochemical workstation, respectively. The results showed that the network structure formed in the fiber, and the fiber diameter decreased with the increase of working pressure. The integral area of cyclic voltammetry curve reached the maximum and the charge/discharge time of constant current charge/discharge curve reached the longest in the case of the CNT concentration is 0.50 wt% and working pressure is 0.2 MPa. At the same time, it exhibited the best electrochemical performance with a specific capacitance of 79 F/g at a current density of 100 mA/g. Compared with the specific capacitance of pure CNFs, the specific capacitance of CNFs with the concentration of CNTs 0.50 wt% increased by about 40%.
Energy-savvy auto-combustion synthesis was used to form the porous BaLi2Ti6O14 titanate anode. It registered the lowest calcination temperature (800 °C) along with the shortest calcination duration (2 h). Rietveld analysis confirmed the purity of the orthorhombic (s.g. Cmca) product phase. The bond valence site energy analysis indicated a 1D ionic conduction along c axis with low activation energy and 2D pathways along (010) with high activation energy. AC conductivity analysis revealed a bulk conductivity of 2.41 × 10−4 S/cm (at 300 °C) with a moderate activation energy barrier (0.68 eV). From cyclic voltammetry, the Li+ diffusion coefficient was calculated to be 10−11–10−12 cm2/s. The as-synthesized BaLi2Ti6O14 reversibly intercalated ∼1.3 Li+ involving a 1.42 V Ti4+/Ti3+ redox activity delivering capacity ∼100 mA h/g with good cyclability over 100 cycles. Furthermore, BaLi2Ti6O14 was found to reversibly intercalate ∼0.89 Na+. With suitable diffusional and electrochemical performance, BaLi2Ti6O14 form a safe titanate anode for secondary batteries.
Formamidinium–tin–strontium halides (CH(NH2)2Sn1−ySryX3 (FASnX3), X = I, Br and 0.0 ≤ y ≤ 0.1) were investigated. X-ray diffraction analysis revealed orthorhombic FASnI3 (space group Amm2) and SnI2 for X = I as well as cubic FASnBr3 (space group $Pm\bar{3}m$) and SnBr2 for X = Br, respectively. For X = I, the optical spectra displayed a decrease of the absorption edges with increasing Sr content (1055 nm, y = 0.0; 950–960 nm, y > 0.0) and a direct semiconducting behavior with narrow band energy gaps (1.31–1.34 eV). For X = Br, on increasing the absorption edges (492 nm, y = 0.0; 975 nm, y = 0.075), a direct semiconducting behavior with band energy gaps between 2.65 eV (y = 0.0) and 1.38 eV (y = 0.075) were observed and the emission photoluminescence (PL) spectra (excitation wavelength λexc = 380 nm) showed an increase of the luminescence response after the thermal treatment.
AlMg alloys have widespread industrial applications. Grain refinement techniques have been frequently used to achieve high strength in these alloys. Here, we report on the fabrication of epitaxial co-sputtered AlMg thin films with high-density growth twins. The microstructure evolution with varying Mg composition has been characterized. Nanoindentation and in-situ micropillar compression tests show that the strength of AlMg alloys increases with increasing Mg composition. The flow stress of epitaxial nanotwinned Al–10 at.% Mg thin film exceeds 800 MPa. The modified Hall–Petch plots incorporating the solid solution strengthening effect suggest that, compared to high angle grain boundaries, incoherent twin boundaries are equivalent barriers to the transmission of dislocations in nanotwinned AlMg alloys.
Synthesis of ZIF with zinc, cobalt, or copper was carried out by microwaves. The effect of metal center on morphologies and pores of products was studied. Nitrogen adsorption/desorption onto ZIFs was examined by density functional theory. The micro, meso, and macropores of ZIF-8, Zn/Co-ZIF-8, and Cu/ZIF-8 ranged 99.814–99.969%, 0.055–0%, and 0.031–0.130%, respectively. Average pore sizes of ZIF-8, Zn/Co-ZIF-8, and Cu/ZIF-8 are 1.291, 1.194, and 1.164 nm, respectively. Monolayer saturation limits of nitrogen onto ZIF-8, Zn/Co-ZIF-8, and Cu/ZIF-8 were 21.152, 18.943, and 17.784 mmol/g, respectively. Further, the results included densities, total surface areas, total pore volumes, and average particle sizes of ZIF-8, Zn/Co-ZIF-8, and Cu/ZIF-8.
Transient transmission oscillations in X-cut and Z-cut congruent, iron-doped, and magnesium-doped lithium niobate samples were measured using 50 fs, 800 nm, 0.5 nJ pulses from a self-mode-locked Ti:sapphire laser in an optical pump–probe system. Several Raman-active oscillation modes excited by these pulses were observed as changes in the transmitted probe intensity versus time delay between the pump and probe pulses. The samples were rotated to determine how the incident polarization of the pump pulses affects the mode excitations. The observed Raman-active oscillations correspond to previously reported symmetry modes measured with traditional, continuous-wave, Raman spectroscopy using the same scattering geometry. In addition, a polariton mode and other, previously unreported, lower-frequency modes were observed in each of the samples. The transmission intensity data for each sample were fit successfully to a superposition of sinusoidal functions with exponentially decaying amplitudes.