Highly porous ZnS microspheres for superior photoactivity after Au and Pt deposition and thermal treatment

This work highlights the enhanced photocatalytic activity of porous ZnS microspheres after Au and Pt deposition and heat treatment at 500 °C for 2 h. Microporous ZnS particles of size 2–5 μm with large surface area 173.14 m² g⁻¹ and pore volume 0.0212 cm³ g⁻¹ were prepared by refluxing under an alkaline medium. Photoluminescence of ZnS at 437 nm attributed to sulfur or zinc vacancies were quenched to 30% and 49%, respectively, after 1 wt% Au and Pt loading. SEM images revealed that each ZnS microparticle consist of several smaller ZnS spheres of size 2.13 nm as calculated by Scherrer's equation. The rate of photooxidation of 4-nitrophenol (10 μM) under UV (125 W Hg arc–10.4 mW/cm²) irradiation has been significantly improved by Au and Pt deposition followed by sintering due to better electron capturing capacity of deposited metals and growth of crystalline ZnS phase with less surface defects.     

Binder-free graphene/carbon nanotube/silicon hybrid grid as freestanding anode for high capacity lithium ion batteries

Light-weight graphene/Si (G/Si) hybrid binder-free electrode is deemed a high energy density anode contender for lithium ion batteries (LIBs). However, paper-like G/Si electrodes tend to show an increased migration distance for Li⁺ through the fast interlayer channel with the increment of electrode size, in addition to an intrinsically slow diffusion kinetics; thereby encumbering their commercial realisation in high energy density and long life LIBs. To address these problems, herein, sandwich-structured graphene/carbon nanotube/silicon (G/CNT/Si, Si: 56 wt.%, ∼500 nm) hybrid grid is designed, cognizant of its uniform and shorter Li⁺ migration distance. Cyclic voltammograms indicate G/CNT/Si paper and grid anode to exhibit good electrochemical activity at both low and high temperatures. Noteworthy is that the Li⁺ diffusion coefficient ratio between G/CNT/Si grid and paper anodes are 1.82, 1.64, 1.43, 1.36 and 1.53 at a temperature of −5, 10, 25, 40 and 55 °C, respectively. The initial coulombic efficiencies of both paper and grid anode are as high as ∼82%. After 60 cycles at 420 mA g⁻¹, the charge capacity of G/CNT/Si grid is retained at 808 mA h g⁻¹, which by far surpasses that of paper anode (i.e., 490 mA h g⁻¹). The attained lithium ion storage performance at both high and low temperatures, underpins the G/CNT/Si sandwiched grid as effective to realise the practical deployment of paper-like graphene electrodes for high energy density and long life LIBs.     

The cation inversion and magnetization in nanopowder zinc ferrite obtained by soft mechanochemical processing

Two zinc ferrite nanoparticle materials were prepared by the same method – soft mechanochemical synthesis, but starting from different powder mixtures: (1) Zn(OH)₂/α-Fe₂O₃ and (2) Zn(OH)₂/Fe(OH)₃. In both cases a single phase system was obtained after 18 h of milling. The progress of the synthesis was controlled by X-ray diffractometry (XRD), Raman spectroscopy, TEM and magnetic measurements. Analysis of the XRD patterns by Rietveld refinement allowed determination of the cation inversion degree for both obtained single phase ZnFe₂O₄ samples. The sample obtained from mixture (1) has the cation inversion degree 0.3482 and the sample obtained from mixture (2) 0.400. Magnetization measurements were confirmed that the degrees of the inversion were well estimated. Comparison with published data shows that used method of synthesis gives nano powder samples with extremely high values of saturation magnetizations: sample (1) 78.3 emu g⁻¹ and sample (2) 91.5 emu g⁻¹ at T = 4.5 K.     

Effect of oxygen partial pressure on microstructural and optical properties of titanium oxide thin films prepared by pulsed laser deposition

Nanocrystalline titanium oxide (TiO₂) thin films were deposited on silicon (1 0 0) and quartz substrates at various oxygen partial pressures (1 × 10⁻⁵ to 3.5 × 10⁻¹ mbar) with a substrate temperature of 973 K by pulsed laser deposition. The microstructural and optical properties were characterized using Grazing incidence X-ray diffraction, atomic force microscopy, UV–visible spectroscopy and photoluminescence. The X-ray diffraction studies indicated the formation of mixed phases (anatase and rutile) at higher oxygen partial pressures (3.5 × 10⁻² to 3.5 × 10⁻¹ mbar) and strong rutile phase at lower oxygen partial pressures (1 × 10⁻⁵ to 3.5 × 10⁻³ mbar). The atomic force microscopy studies showed the dense and uniform distribution of nanocrystallites. The root mean square surface roughness of the films increased with increasing oxygen partial pressures. The UV–visible studies showed that the bandgap of the films increased from 3.20 eV to 3.60 eV with the increase of oxygen partial pressures. The refractive index was found to decrease from 2.73 to 2.06 (at 550 nm) as the oxygen partial pressure increased from 1.5 × 10⁻⁴ mbar to 3.5 × 10⁻¹ mbar. The photoluminescence peaks were fitted to Gaussian function and the bandgap was found to be in the range ∼3.28–3.40 eV for anatase and 2.98–3.13 eV for rutile phases with increasing oxygen partial pressure from 1 × 10⁻⁵ to 3.5 × 10⁻¹ mbar.     

Room temperature multiferroic properties of (Bi0.95La0.05)(Fe0.97Mn0.03)O3/NiFe2O4 double layered thin film

(Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃/NiFe₂O₄ double layered thin film was prepared on a Pt(111)/Ti/SiO₂/Si(100) substrate by a chemical solution deposition method. X-ray diffraction and Raman scattering spectroscopy studies confirmed the formation of the distorted rhombohedral perovskite and the inverse spinel cubic structures for the (Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃/NiFe₂O₄ double layered thin film. The (Bi_0.95La_0.05)(Fe_0.97Mn_0.03)O₃/NiFe₂O₄ double layered thin film exhibited well saturated ferromagnetic (2 M_r of 18.1 emu/cm³ and 2H_c of 0.32 kOe at 20 kOe) and ferroelectric (2P_r of 60 μC/cm² and 2E_c of 813 kV/cm at 866 kV/cm) hysteresis loops with low order of leakage current density (4.5 × 10⁻⁶ A/cm² at an applied electric field of 100 kV/cm), which suggest the ferroelectric and ferromagnetic multi-layers applications in real devices.     

Low-temperature synthesis,structural and magnetic properties of self-dopant LaMnO3+δ nanoparticles from a metal-organic polymeric precursor

Self-dopant LaMnO_3+δ nanoparticles have been successfully synthesized by metal citrate complex method based on Pechini-type reaction route, at low temperature (773 K). Powder X-ray diffraction and transmission electron microscope revealed pure and nanostructured phase of LaMnO_3+δ (δ = 0.125) with an average grain size of ∼72 nm (773 K) and ∼80 nm (1173 K). DC-magnetization measurements under an applied magnetic field of H = ±60 kOe showed an increase in the magnetization with the increase of calcination temperature. Ferromagnetic nature shown by non-stoichiometric LaMnO_3+δ was verified by well-defined hysteresis loop with large remanent magnetization (M_r) and coercive field (H_c). Surface areas of LaMnO_3+δ nanoparticles were found to be 157.4 and 153 m² g⁻¹ for the samples annealed at 773 K and 1173 K, respectively.     

Transparent and flexible cellulose nanofibers/silver nanowires/acrylic resin composite electrode

In this study, we report a novel, eco-friendly and simple method to fabricate cellulose nanofibers (CNFs)/silver nanowires (AgNWs)/acrylic resin (AR) composite electrode. CNFs with average diameter of 15 nm were disintegrated only by one time-pass grinding. Aqueous dispersion of AgNWs was embedded onto the surface of CNFs film by simple vacuum filtration. The final composite electrode was obtained by impregnating CNFs/AgNWs film to AR with the assist of adhesive tape. This electrode with AgNWs density of 134 mg/m² showed low sheet resistance (4 Ω/sq), and high light transmittance (85%) which was 6% lower than that of neat AR. The coefficient of thermal expansion of the composite electrode was as low as 25.32 ppm K⁻¹. The tensile strength and Young’s modulus of CNFs/AgNWs/AR composite film were 35.71 MPa and 1.63 GPa, which were about 8 and 5.8 times larger than neat AR film, respectively.     

Growing polystyrene chains from the surface of graphene layers via RAFT polymerization and the influence on their thermal properties

The polystyrene (PS) macromolecular chains were grafted on the surface of graphene layers by reversible addition-fragmentation chain transfer (RAFT) polymerization. In this procedure, a RAFT agent, 4-Cyano-4-[(dodecylsulfanylthiocarbonyl) sulfanyl] pentanoic acid, was used to functionalize the thermal reduced graphene oxide (TRGO) to obtain the precursor (TRGO-RAFT). It can be calculated that the grafting density of PS/graphene (PRG) composites was about 0.18 chains per 100 carbons. Successful in-plain attachment of RAFT agent to TRGO and PS chain to TRGO-RAFT was shown an influence on the thermal property of the PRG composites. The thermal conductivity (λ) improved from 0.150 W m⁻¹ K⁻¹ of neat PS to 0.250 W m⁻¹ K⁻¹ of PRG composites with 10 wt% graphene sheets loading. The thermal property of PRG composites increased due to the homogeneous dispersion and ordered arrangement of graphene sheets in PS matrix and the formation of PRG composites.     

Fluorescence properties and relaxation processes of Tb3+ ions in ZnCl2-based glasses

60ZnCl₂–20KCl–20BaCl₂–xTbCl₃ glasses (x = 0.10, 0.25, 0.50, 0.75, 1.00, and 1.25) were prepared by melt-quenching method, and Tb³⁺ fluorescence properties were investigated under 355 nm excitation. Regardless of x values, the electrons that were relaxed from the ⁵D₃ to ⁵D₄ level of Tb³⁺ ions by the multiphonon relaxation, were repressed to 28% of all the excited electrons because the ZnCl₂-based glass had much lower phonon energy than oxide glasses. For 0 < x ≤ 0.34, the cross relaxation, (⁵D₃ → ⁵D₄) → (⁷F₀ ← ⁷F₆), was repressed, and consequently 72% and 28% of all the excited electrons were radiatively relaxed by the ⁵D₃ → ⁷F_J (J = 6, 5, 4, 3, and 2) and ⁵D₄ → ⁷F_J (J = 6, 5, 4, and 3) transitions, respectively. The lifetimes of the ⁵D₃ and ⁵D₄ initial levels were obtained to be 1.1 and 2.1 ms, respectively.     

Thermal conductivity of Cu/diamond composites prepared by a new pretreatment of diamond powder

Cu/diamond composites were fabricated by spark plasma sintering (SPS) after the surface pretreatment of the diamond powders, in which the diamond particles were mixed with copper powder and tungsten powder (carbide forming element W). The effects of the pretreatment temperature and the diamond particle size on the thermal conductivity of diamond/copper composites were investigated. It was found that when 300 μm diamond particles and Cu–5 wt.% W were mixed and preheated at 1313 K, the composites has a relatively higher density and its thermal conductivity approaches 672 W (m K)⁻¹.     

Bifunction in Er3+/Yb3+ co-doped BaTi2O5–Gd2O3 glasses prepared by aerodynamic levitation method

Novel Er³⁺/Yb³⁺ co-doped BaTi₂O₅–Gd₂O₃ spherical glasses have been fabricated by aerodynamic levitation method. The thermal stability, upconversion luminescence, and magnetic properties of the present glass have been studied. The glasses show high thermal stability with 763.3 °C of the onset temperature of the glass transition. Red and green emissions centered at 671 nm, 548 nm and 535 nm are obtained at 980 nm excitation. The upconversion is based on a two-photon process by energy transfer, excited-state absorption, and energy back transfer. Yb³⁺ ions are more than Er³⁺ ions in the glass, resulting in efficient energy back transfer from Er³⁺ to Yb³⁺. So the red emission is stronger than the green emissions. Magnetization curves indicate that magnetic rare earth ions are paramagnetic and the distribution is homogeneous and random in the glass matrix. Aerodynamic levitation method is an efficient way to prepare glasses with homogeneous rare earth ions.     

Preparation,microstructure, and improved dielectric and nonlinear electrical properties of Na1/2La1/2Cu3Ti4O12 ceramics by sol–gel method

Na_1/2La_1/2Cu₃Ti₄O₁₂ (NLCTO) ceramics were prepared by the sol–gel method (SG) and solid-state method (SS), and the effect of sintered temperature on microstructure and dielectric and nonlinear electrical properties has investigated. The experimental results indicated that NLCTO-SG ceramics sintered at 1090 °C for 10 h showed larger grain size, higher density and more homogeneous microstructure, especially higher dielectric constant up to ca 1.3–1.8 × 10⁴, lower dielectric loss of about 0.057 and better temperature stability than NLCTO-SS counterparts. However, the good low-voltage varistor behavior and the third kind of dielectric relaxation behavior could not be observed from the NLCTO-SS ceramics. The higher dielectric constant of the NLCTO-SG ceramics may be due to the stronger internal barrier layer capacitor (IBLC) effect. Two values of grain activation energy were obtained above room temperature for the first time. The transition temperature of two values was basically coincident with that of sudden changes of the dielectric properties.     

Utilization of residual CdCl2 in CBD-CdS to realize grain growth in CdTe: A novel route

CdTe films were deposited by thermal evaporation onto chemical bath deposited CdS (CBD-CdS) films. The composite films were subjected to rapid thermal annealing (RTA) to observe simultaneous grain growth in both the CdS and CdTe layers. The films were characterized by measuring the compositional, microstructural and photoluminescence (PL) properties. PL spectra is dominated by the characteristic peaks (∼1.42 eV and ∼1.26 eV) associated with the virgin CdTe film. Additional features located at ∼2.56 eV and ∼1.99 eV could also be detected. The Fourier Transform Infra Red (FTIR) peak at ∼482 cm⁻¹ appeared due to the simultaneous presence of absorption peaks for CdTe stretching mode as well as Cd-S modes. Appearance of the broad peak between 1000 cm⁻¹ and 1165 cm⁻¹ may be an indication of interfacial alloying. Secondary ion mass Spectroscopy (SIMS) measurements were done to observe the compositional uniformity in the film and to measure the interfacial mixing behaviour.     

Fabrication and characterization of three-dimensional PMR polyimide composites reinforced with woven basalt fabric

A PMR polyimide composite reinforced with three-dimensional (3D) woven basalt fabric is fabricated for medium high temperature applications. The PMR polyimide matrix resin is derived from 4,4′-methylenediamine (MDA), diethyl ester of 3,3′,4,4′-oxydiphthalic (ODPE) and monoethyl ester of Cis-5-norbornene-endo-2,3-dicarboxylic acid (NE). The rheological properties of the PMR polyimide matrix resin are investigated. Based on the curing reaction of the PMR type polyimide and the rheological properties, an optimum two-step fabrication method is proposed. The three dimensional fabric preforms are impregnated with the polyimide resin in a vacuum oven at 70 °C for 1 h followed by removing the solvent and pre-imidization. The composites are then consolidated by an optimized molding procedure. Scanning electron microscopy analysis shows that needle shaped voids are generated in yarns and the void volume fraction is 4.27%. The decomposition temperature and the temperature at 5% weight loss of the composite post-cured at 320 °C for 24 h are 440 °C and 577 °C, respectively. The dielectric constant and the dielectric loss of the composite are measured by circular cavity method at 7–12 GHz. The tensile strength and the modulus in the warp direction of the composite are 436 MPa and 22.7 GPa. The composite shows a layer-by-layer fracture mode in three-point bending test. The flexure strength and modulus in the warp direction of the composite are 673 MPa and 27.1 GPa, respectively.     

The AMWCNTs supported porous nanocarbon composites for high-performance supercapacitor

The porous nanocarbons supported by acid-treated multiwall carbon nanotubes (PC@ACNTs) were prepared by the combination of the hydrothermal polymerization of glucose on ACNTs, carbonization under N₂ protection and final activation with ZnCl₂. The materials were characterized by transmission electron microscopy, X-ray powder diffraction and Raman spectra. The results indicated that the ACNTs distributed uniformly into the framework of the porous carbon. The composites showed the high BET specific surface area up to 1712 m² g⁻¹ and good conductivity. The electrochemical measurements indicated that the composites processed good performances for electrochemical energy storage (210 F g⁻¹ at 0.5 A g⁻¹), and high stability (>99.9%), much higher than the corresponding ACNTs, porous carbons and the samples prepared by using raw MWCNTs as source. The good performance of PC@ACNTs composites was relative with the synergy of good conductivity of ACNTs and large specific surface areas of PC.     

Effect of CuO nanostructure morphology on the mechanical properties of CuO/woven carbon fiber/vinyl ester composites

The effect of CuO nanostructure morphology on the mechanical properties of CuO/woven carbon fiber (WCF)/vinyl ester composites was investigated. The growth of CuO nanostructures embedded in the surface of woven carbon fibers (WCFs) was carried out by a two-step seed-mediated hydrothermal method; i.e., seeding and growth treatments with controlled chemical precursors. CuO nanostructural morphologies ranging from petal-like to cuboid-like nanorods (NRs) were obtained by controlling the thermal growth temperature in the hydrothermal process over a growth time of 12 h. The Cu²⁺/O⁻ ratio and the rate of reaction greatly influenced the formation of CuO nanostructures as self-assembled shapes on the crystal planes in the order L[0 1 0] > L[1 0 0] > L[0 0 1]. Morphological variations were analyzed by scanning electron microscopy, X-ray diffraction, and Brunauer–Emmett–Teller surface area analysis. The impact behavior, in-plane shear strength, and tensile properties of the CuO/WCF/vinyl ester composites were analyzed for different CuO NR morphologies at various growth temperatures and molar concentrations. The CuO/WCF/vinyl ester composites had improved impact energy absorption and mechanical properties because the higher specific surface area of CuO NRs grown as secondary reinforced nanomaterials on WCFs enhanced load transfer and load-bearing capacity.     

Full-field shear analyses of sandwich core materials using Digital Image Correlation (DIC)

Mechanical properties and global stability of foam core sandwich structures are highly controlled by the shear response of the core material. In this work, we have studied the shear deformations of three common structural core materials with the aid of full-field optical analysis. The chosen core materials are namely extruded PET foam (ρ = 105 kg/m³, G_xz = 21 MPa,) and cross-linked PVC foam (ρ = 60 kg/m³, G_xz = 22 MPa) which have comparable shear properties, as well as Balsa wood with the lowest density commercially available (ρ = 94 kg/m³, G_xz = 106 MPa) as a reference core material. Both global and local shear strains in the core materials are calculated and graphically visualized. In the elastic region, foam cores showed more uniform deformations than Balsa. Yielding and shear failure of the two foam core materials were quite different. The PVC foam experienced a high local deformation under the load introduction bars, from which sub-interface shear failure initiated. The PET foam, in contrast, showed no sign of stress concentrations, resulting in a homogenous evolution of shear deformations in the mid-core regions. A comparison between the direct foam shear test and sandwich specimen bending suggested that the former method might not be capable of capturing a full picture of the in-service core shear response.     

Effect of stitch density on fatigue characteristics and damage mechanisms of stitched carbon/epoxy composites

The effect of stitch density (SD) on fatigue life, stiffness degradation and fatigue damage mechanisms in carbon/epoxy (T800SC/XNRH6813) stitched using Vectran thread is presented in this paper. Moderately stitched composite (SD = 0.028/mm²; ‘stitched 6 × 6’) and densely stitched composite (SD = 0.111/mm²; ‘stitched 3 × 3’) are tested and compared with composite without stitch thread (SD = 0.0; ‘unstitched’). The experiments show that the fatigue life of stitched 3 × 3 is moderately better than that of unstitched and stitched 6 × 6. Stitched 3 × 3 pattern is also able to postpone the stiffness degradation onset. The improvement of fatigue properties and postponement of stiffness degradation onset in stitched 3 × 3 is primarily due to an effective impediment of edge-delamination. Quantification of damage at various cycles and stress levels shows that stitch density primarily affects the growth rate of delamination.     

Microstructure and strength of pure Cu with large grains processed by equal channel angular pressing

The pure Cu rods with an initial grain size of 410 μm were treated by using equal channel angular pressing (ECAP). The deformed microstructure and mechanical properties of ECAPed Cu samples were investigated. Special attention was paid on the refinement of grain size and local micromechanics of ECAPed Cu samples. The original coarse grains were refined to 320 μm after 4 passes. The final grains were composed of dislocation cells with a size of 500 nm–3 μm after 5–8 passes. The yield strength reached a saturation value of 368 MPa after 5 passes. The maps of microhardness distribution illustrated the inhomogeneity of local mechanical properties. The dislocation subdivision was the main deformation mode to refine the grain size, while twin fragmentation was restrained by dislocation slips for the reason of large initial grain size. Furthermore, the strengthening of ECAPed Cu was discussed.     

A facile preparation and the luminescent properties of Eu3+-doped Y2O2SO4 nanopieces

The europium(III)-doped yttrium oxysulfate (Y₂O₂SO₄:Eu³⁺) nanopieces have been prepared via electrospinning followed by calcination at 1000 °C in mixed gas of sulfur dioxide and air. Based on the experimental results, a possible formation mechanism for the nanopieces is that the nanopieces are determined by the directing template of electrospun nanoribbons and the multilayer crystal structure of Y₂O₂SO₄. Besides, the nanopieces show excellent luminescent properties with emissions at 581, 589, 597, 653, 619, and 697 nm resulting from the ⁵D₀ → ⁷F_J (J = 0, 1, 2, 3, 4) transition of Eu³⁺. The peaks of charge transfer and ⁵D₀ → ⁷F₂ transition of Eu³⁺ obviously have red shifts comparing to those of both Y₂O₃:Eu³⁺ nanoribbons and commercial Y₂O₃:Eu³⁺. Moreover, the nanopieces exhibit stronger intensities than the Y₂O₃:Eu³⁺ in excitation and emission spectra. Concentration quenching in the nanopieces occurs when Eu³⁺ concentration is 11 mol%, indicating that the nanopieces have an optimum luminescent intensity under this doping concentration.