Luminescence properties of a thermal-responsive organogel to various metal cations

A new gelator (L) containing Schiff base, benzoimidazol and naphthayl moieties was synthesized and its self-assembly was investigated in various solvents. Gelation test revealed that it could form a thermal-responsive gel in ethylene glycol (GL) or the mixture solution of ethylene glycol and DMF. Different fluorescence behaviors were observed upon adding different metal ions. The addition of Mg^2 + maintained the gelating ability of L, meanwhile the Mg^2 +-ion-mediated organogel in ethylene glycol can enhance the fluorescence of GL. The addition of Al^3 + can destroy GL and lead to a state transition from gel to clear solution; the solution can give a brilliant blue emission excited at 365 nm UV. Interestingly, the luminescence of GL increased sharply at first but decreased finally. The fluorescence of GL was quenched when other metal cations were added.     

Effect of microstructural evolution on wettability and tribological behavior of TiO2 nanotubular arrays coated on Ti–6Al–4V

Self-organized TiO₂ nanotubular arrays were fabricated by electrochemical anodization of Ti–6Al–4V plates in an NH₄F/H₃PO₄ electrolyte. The effect of microstructural evolutions on the wettability and tribological behavior of the TiO₂ nanotubes was investigated. Based on the XRD profiles of the fabricated material, the characteristic TiO₂ peaks were not recognized after anodization; however, highly crystalline TiO₂ (anatase and rutile) was formed due to crystallization during annealing at 500 °C for 1.5 h. The nanotube arrays were converted entirely to rutile at 700 °C. From a microstructure point of view, a highly ordered nanotube structure was achieved when the specimen was annealed at 500 °C, with a length of 0.72 μm and a pore diameter of 72 nm. Further increasing the annealing temperature to 700 °C resulted in the complete collapse of the tubular structure. The results indicate that the improved wettability of the anodized specimens was due to the combination of the effects of both the surface oxide layer and the increased surface roughness achieved after anodization. Moreover, the wear resistance and wettability of the sample annealed 500 °C were improved due to the high hardness (435 HV) and low coefficient of friction (0.133–168) of the highly crystalline structure of the TiO₂ nanotubes.     

Near-infrared luminescent mesoporous MCM-41 materials covalently bonded with ternary thulium complexes

Two β-diketones 4,4,4-trifluoro-1-2-thenoyl-1,3-butanedione (Htta) and 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione (Htfnb), which contain trifluoroalkyl chain, were selected as the main sensitizer for synthesizing Tm(L)₃phen (L = tta, tfnb) complexes. The two near-infrared (NIR) luminescent thulium complexes have been covalently bonded to the ordered mesoporous material MCM-41 via a functionalized 1,10-phenanthroline (phen) group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline (phen-Si) [The resultant mesoporous materials are denoted as Tm(L)₃phen–MCM-41 (L = tta, tfnb)]. The Tm(L)₃phen–MCM-41 (L = tta, tfnb) mesoporous materials were characterized by small-angle X-ray diffraction (XRD) and N₂ adsorption/desorption, and they show characteristic mesoporous structure of MCM-41. Luminescence spectra of the Tm(L)₃phen–MCM-41 (L = tta, tfnb) mesoporous materials were recorded and the corresponding luminescence decay curves were obtained. After ligand-mediated excitation, the emission spectra of the Tm(L)₃phen–MCM-41 (L = tta, tfnb) mesoporous materials show the characteristic NIR-luminescence of the Tm³⁺ ion. The full width at half maximum (fwhm) of the 1474-nm emission band are 96 and 100 nm for Tm(tta)₃phen–MCM-41 and Tm(tfnb)₃phen–MCM-41, respectively. The good luminescent performances enable these NIR-luminescent mesoporous materials to have potential applications in optical amplification [broadening amplification band from C band (1530–1560 nm) to S⁺ band (1450–1500 nm)]. Furthermore, the comparison of the luminescence behavior for Tm(tta)₃phen–MCM-41 and Tm(tfnb)₃phen–MCM-41 mesoporous materials was investigated. It shows that Tm(tfnb)₃phen–MCM-41 is somewhat superior to Tm(tta)₃phen–MCM-41 as optical amplifier.     

Scintillation,TSL and RPL properties of MgF2 transparent ceramic and single crystal

We have prepared MgF₂ transparent ceramics by spark plasma sintering (SPS) and investigated the scintillation and dosimeter properties compared with those of a single crystal. Under X-ray irradiation, a transparent ceramic showed scintillation with a broad feature over 300–600 nm with decay times of 310 and 1940 μs while the single crystal did not show such emission. It was found that MgF₂ show radio-photoluminescence (RPL), which is a generation of new luminescence center by ionizing radiation. The RPL was only observed in the transparent ceramic samples, which appeared as two emission bands peaking around 415 and 700 nm under 340±40 nm excitation. During the PL reading, the emission band at 415 nm effectively increased over 50 s. This result suggested that the RPL in MgF₂ shows a build-up phenomenon. From PL emission/excitation characteristics and decay time, it was suggested that the RPL peak around 415 nm was due to M(C_2h) center.     

Photoluminescence,photochromism, and reversible luminescence modulation behavior of Sm-doped Na0.5Bi2.5Nb2O9 ferroelectrics

Sm-modified Na_0.5Bi_2.5Nb₂O₉ ceramics can simultaneously exhibit both visible light-driven photochromism and photoluminescence. Upon visible light irradiation, these materials change their color from green to dark gray, while exhibiting a strong red emission at 603 nm due to the ⁴G_5/2 → ⁶H_7/2 transition, whose emission intensity strongly depends on the irradiation wavelength, intensity, and time, and significantly decreases with increasing irradiation time and intensity. By alternating visible light or sunlight (λ > 400 nm) irradiation and thermal stimulus, both luminescence and absorption intensity can be reversibly switched without any significant degradation between the two colored and bleached states, with excellent reproducibility. On the basis of the trapped charge carrier and exponential relaxation decay models, we herein provide a detailed understanding of the photochromism and luminescence modulation mechanisms.     

Study on luminescence properties of co-doped nanoparticles Gd2O3:Tb3+, Eu3+ synthesized by polyol route

Spherical-like Tb³⁺ and Eu³⁺ co-doped Gd₂O₃ nanoparticles with a particle size around 5.5 nm were synthesized by a polyol route. The optimized luminescence property was obtained when 5 mol% Tb³⁺ and 2 mol% Eu³⁺ were co-doped. The influence of different polyalcohol solvents (DEG/PEG) on particle size and luminescence properties was investigated. The results show that the nanoparticles Gd₂O₃:5%Tb³⁺ prepared in PEG presented greater particle size (around 79 nm) and higher luminescence intensity.     

Preparation of WC/Co composite powders by electroless plating

Ultra-fine WC/Co composite powders were prepared by electroless plating in this study. The Co layers with an average thickness of 50–100 nm were uniformly and completely covered on raw WC particles with a diameter of 0.3–0.5 µm. The influences of electroless plating conditions on the composites were investigated. The Co layer covering on WC particles was controlled by the content of CoSO₄·7H₂O, pH value and bath temperature. With increasing the content of CoSO₄·7H₂O up to 25 g/L, both the weight gain and the plating rate markedly increased. However, when the content of CoSO₄·7H₂O further increased to 30 g/L, while the weight gain displayed a slight decrease, the plating rate continued to increase moderately. Moreover, with the increase of pH value from 9.5 to 11, both the weight gain and the reaction time decreased. Furthermore, the plating rate exhibited an exponential relationship with the bath temperature. When the pH value, bath temperature and the concentration of CoSO₄·7H₂O are 10, 80 °C and 25 g/L respectively, the weight gain of Co-coated WC composite powders is 185.1 mg/g.     

Luminescence properties of oxide films formed by anodization of aluminum in 12-tungstophosphoric acid

In this paper, we have investigated luminescence properties of oxide films formed by anodization of aluminum in 12-tungstophosphoric acid. For the first time we have measured weak luminescence during anodization of aluminum in this electrolyte (so-called galvanoluminescence GL) and showed that there are wide GL bands in the visible region of the spectrum and observed two dominant spectral peaks. The first one is at about 425 nm, and the second one shifts with anodization voltage. As the anodization voltage approaches the breakdown voltage, a large number of sparks appear superimposed on the anodic GL. Several intensive band peaks were observed under breakdown caused by electron transitions in W, P, Al, O, H atoms. Furthermore, photoluminescence (PL) of anodic oxide films and anodic-spark formed oxide coatings were performed. In both cases wide PL bands in the range from 320 nm to 600 nm were observed.     

From 1D chain to 2D layer and 3D network: Solvent-free syntheses of new metal oxalates

Four metal oxalates, Hdpa⋅Cr(ox)₂ (1), (Hdpa)₂⋅ Zn₂(ox)₃ ⋅ 2H₂O (2), Zn(H₂O)(ox) (3), and (Hgua)(H₃O) ⋅ Cd(C₂O₄)₂ (4), have been synthesized under solvent-free conditions, where dpa = diisopropylamine, ox = oxalate, and gua = guanidine. These compounds have extended structures varying from 1D chain (for 1), to 2D layer (for 2 and 3), and 3D framework network (for 4). The temperature dependence of the magnetic susceptibility of compound 1 indicates the existence of antiferromagnetic interactions between the chromium ions. Upon excitation at 230 nm, compound 3 exhibits an extensive luminescence with a peak centered at 501 nm.     

Microstructure and dielectric properties of SrTiO3 ceramics by controlled growth of silica shells on SrTiO3 nanoparticles

SrTiO₃@SiO₂ nanopowder was synthesized via a core-shell nano-scale technique that is known as the Stöber process. The effect of the SiO₂ concentration on microstructure, dielectric response and energy storage properties of SrTiO₃@SiO₂ ceramics was investigated. Transmission electron microscopy (TEM) results confirmed the formation of core–shell nanostructures with controlled shell thicknesses between 2 nm and 13 nm. After increasing SiO₂, a secondary phase with Sr₂TiSi₂O₈ appeared due to inter-diffusion reactions between the SrTiO₃ core and SiO₂ shells during the sintering process. The results show that both breakdown strength and energy density improved apparently. The homogeneous coating of silica on ST cores is considered to dominate the contribution to improved breakdown strength. The composition for SrTiO₃ coated with 2.5 wt% SiO₂ shows the maximum energy storage density (1.2 J/cm³) and a breakdown strength of 310 kV/cm. The former is higher than for pure SrTiO₃ (0.19 J/cm³). Measurements of the dielectric performance indicate that the SrTiO₃@SiO₂ ceramics possess good bias stabilities compared to pure ST ceramics.     

UV/S2O82− process for degrading polyvinyl alcohol in aqueous solutions

This investigation evaluates the effectiveness of the UV/S₂O₈²⁻ process in the degradation of polyvinyl alcohol (PVA) in aqueous solutions without adjusting their pH. The effects of UV wavelength and Na₂S₂O₈ dosage on the efficiency of degradation of PVA were examined. The efficiency of degradation of PVA under UV-254 nm exceeded that under UV-365 nm. A larger Na₂S₂O₈ dosage was associated with a higher efficiency of degradation of PVA under UV-254 nm irradiation. However, an excessive Na₂S₂O₈ dosage inhibited the degradation of PVA by the UV-365 nm/S₂O₈²⁻ process. Both UV-254 nm/S₂O₈²⁻ and UV-365 nm/S₂O₈²⁻ processes exhibited pseudo-first-order kinetics. SO₄⁻ was detected by performing quenching studies using specific alcohols, revealing that SO₄⁻ was found to be the predominant radical in the UV-254 nm/S₂O₈²⁻ process. Additionally, the presence of inorganic anions with various effects inhibited the degradation of PVA by the UV-254 nm/S₂O₈²⁻ process. Complete degradation of PVA (20 mg/L) was achieved within 5 min under UV-254 nm using an Na₂S₂O₈ dosage of 0.12 g/L in the absence of inorganic anions, indicating that UV irradiation to activate S₂O₈²⁻ promotes the degradation of PVA in aqueous solutions without adjusting their pH.     

Gd-based oxyfluoride glass ceramics: Phase transformation,optical spectroscopy and upconverting temperature sensing

A series of precursor glasses with compositions of SiO₂-Al₂O₃-AlF₃-Na₂O- NaF-Gd₂O₃/GdF₃-YbF₃-ErF₃ were prepared and their crystallization behaviors were investigated. For the samples with high F content, meta-stable hexagonal GdF₃ nanocrystals were preferentially precipitated from glass matrix and decreasing F/O ratio induced phase transformation to cubic NaGdF₄ and finally to hexagonal NaGdF₄. Benefited from its multiple active sites, significant enhanced upconversion luminescence was achieved for Yb/Er co-doped glass ceramic containing hexagonal NaGdF₄ nanocrystals. Importantly, significant temperature-sensitive upconversion fluorescence intensity ratio between Er³⁺: ²H_11/2 → ⁴I_15/2 transition (520 nm) and ⁴S_3/2 → ⁴I_15/2 one (540 nm) was detected owing to the competitive radiation transitions from these two thermally coupled emitting-states. Furthermore, linear temperature-dependent fluorescence intensity ratio between Er³⁺: ⁴F_9/2 → ⁴I_15/2 transition (650 nm) to ⁴S_3/2 → ⁴I_15/2 one (540 nm) was achieved, showing the advantages of high sensitivity, superior signal discriminability as well as excellent thermal stability for temperature determination.     

Significant enhancement in breakdown strength and energy density of the BaTiO3/BaTiO3@SiO2 layered ceramics with strong interface blocking effect

The BaTiO₃/BaTiO₃@SiO₂ (BT/BTS) ceramics with layered structure, where grain size was about 1–2 μm in the BT layer while it was about 300–400 nm in the BTS layer, were fabricated by the tape-casting and lamination method. With the increasing of SiO₂ content in the BTS layer, the dielectric constant decreased gradually, and the breakdown strength was remarkably improved. Compared to the SiO₂-added BaTiO₃ bulk ceramics, the layered ceramics displayed significant enhancements in dielectric properties, breakdown properties and energy storage properties. The enhancement in dielectric properties was mostly attributed to the diluting effects created by this structure to SiO₂. Based on the finite element analysis with the dielectric breakdown mode, it was regarded that the electric field redistribution and the interface blocking effect led to the enhancement of breakdown strength. Finally, the maximum energy density of 1.8 J/cm³ was obtained at a breakdown strength of 301.4 kV/cm for the BT/BTS3 ceramic.     

A novel two-dimensional square grid cobalt complex: Synthesis,structure, luminescent and magnetic properties

A novel cobalt(II) coordination polymer, [Co(L)₂]_n (1) (HL = 4-(imidazol-1-yl)-benzoic acid), has been hydrothermally synthesized and structurally characterized by X-ray diffraction, IR spectrum and elemental analyses. Structure determination of complex 1 reveals that the two-dimensional (2D) network framework consists of regular square grid with dimensions of ca. 11.42 × 11.42 Å. Complex 1 exhibits a strong blue luminescence centering at 409 nm in the solid. Variable temperature magnetic susceptibility study shows there is a weak antiferromagnetic interaction in complex 1. Thermal property is also investigated.     

Microphase separated structures in the solid and molten states of double-crystal graft copolymers of polyethylene and poly(ethylene oxide)

Transitions from one microphase separated structure in the solid state to a different one in the molten state in polyethylene-graft-poly(ethylene oxide) copolymers, PE-g-PEO, were investigated by variable temperature X-ray scattering measurements and thermal analyses. Small-angle X-ray scattering patterns from polymers with PEO grafts with 25, 50 and 100 ethylene oxide (EO) units show that the polymer passes through three distinct structures at ～10 nm length scales with increase in temperature (T): lamellar structures of PE and PEO at T < T_m^PEO, PE lamellae surrounded by molten PEO at T_m^PEO < T < T_m^PE, and microphase separated structures at T > T_m^PE when both PE and PEO are molten (T_m refers to the melting temperature). These phase transformations also occur during cooling but with hysteresis. Crystalline phases of PEO side chains and PE main chains could be identified in the wide-angle X-ray diffraction profiles indicating that the PE backbone and PEO grafts crystallize into separate domains, especially with longer grafted chains (50 and 100 units). At EO segment lengths > 50, PEO shows the expected increase in melting and crystallization temperatures with the increase in the grafted chain length. PE does not affect T_m^PEO but does decrease the onset of crystallization upon cooling. PEO grafts result in fractionation of PE, decrease the melting point of PE and increase the undercooling for the onset of crystallization of PE.     

Efficient near-infrared to visible and ultraviolet upconversion in polycrystalline BiOCl:Er3+/Yb3+ synthesized at low temperature

Er³⁺/Yb³⁺ co-doped BiOCl poly-crystals were synthesized by the conventional solid state method at 500 °C, which exhibited good crystalline and low phonon energy. Under 980 nm excitation, the samples showed intense red upconversion (UC) luminescence (Er³⁺: ⁴F_9/2→⁴I_15/2) as well as other four UC emission bands, including ultraviolet (UV) emission at 380 nm, violet emission at 411 nm, green UC emissions at 525 and 545 nm and near-infrared (NIR) emission between 800 and 850 nm, corresponding to the transitions of ⁴G_11/2, ²H_9/2, ²H_11/2, ⁴S_3/2 and ⁴I_9/2→⁴I_15/2 of Er³⁺, respectively. Interestingly, including the violet and green UC emissions, the red one originated a nearly three-photon process in this system, and a possible UC mechanism was proposed for the enhanced red emission.     

Synthesis,morphology, and upconversion luminescence of Tm3 +/Yb3 + codoped bulk and submicro-rod CaSc2O4 phosphors

CaSc₂O₄: Tm^3 +/Yb^3 + submicro-rods were synthesized using the mild solvothermal and annealing technique. The temperature of formed pure phase is as low as 600 °C. The synthesized submicro-rods are uniform in size and shape. The size of rod is only small with 35 nm in width and 200 nm in length, which favors the application in biological assays and medical image. Furthermore, samples prepared exhibit the stronger upconversion luminescence than that of obtained by conventional solid state reaction method under 980 nm excitation. The near infrared emission around 800 nm is enhanced twofold closely. CaSc₂O₄ phosphor synthesized through the solvothermal and annealing method is a promising submicron upconversion material. The solvothermal and annealing technique is a suitable method for preparing CaSc₂O₄ sample with rod-like morphology.     

Synthesis and characterization of the crystalline powders on the basis of Lu2O3:Eu3+spherical submicron-sized particles

This study is devoted to the preparation of the crystalline powders on the basis of non-agglomerated monodisperse Lu₂O₃:Eu³⁺ spherical particles with the diameters in the range of 50–250 nm by the soft chemistry co-precipitation route. The influence of the synthesis parameters on control morphology, particles size and agglomeration in the final Lu₂O₃:Eu³⁺ powder was considered. Lu₂O₃:Eu³⁺ crystalline powders were characterized by means of electron microscopy methods (TEM, SEM), FT-IR spectroscopy, thermal analysis (TG-DTA) and X-ray diffractometry. The mechanisms of the precursor decomposition and crystallization at the temperatures ranging from 60 to 900 °C were discussed. It was shown that the powders obtained were characterized by the effective luminescence under X-ray excitation in λ = 575–725 nm spectral region corresponding to ⁵D₀ → ⁷F_J transitions (J = 0–4) of Eu³⁺ ions with a maximum at 612 nm and the luminescence intensity strongly depends on annealing temperature. The relative densities of the green-bodies on the basis of Lu₂O₃:Eu³⁺ powders were estimated and the sintering of compacts at the temperatures up to 1500 °C was studied.     

Near-infrared luminescent properties and natural lifetime calculation of a novel Er3+ complex

In this communication, a novel Er³⁺ complex Er(PT)₃TPPO [PT = 1-phenyl-3-methyl-4-tert-butylbenzoyl-5-pyrazolone, TPPO = triphenyl phosphine oxide] is successfully synthesized and characterized by elemental analysis and single-crystal X-ray diffraction. Its optical properties and the energy transfer process from the ligand PT to the Er³⁺ ion are investigated, the typical near-infrared (NIR) luminescence (centered at around 1530 nm) is attributed to the ⁴I_13/2 → ⁴I_15/2 transition of Er³⁺ ion which results from the efficient energy transfer from PT to Er³⁺ ion (an antenna effect). The wider full width at half maximum (78 nm) peaked at 1530 nm in the emission spectrum and the Judd–Ofelt theory calculation on the radiative properties suggest that Er(PT)₃TPPO should be a promising candidate for tunable lasers and planar optical amplifiers.     

Improving electrochemical properties of LiCoO2 by enhancing thermal decomposition of Cobalt and Lithium carbonates to synthesize ultrafine powders

Ultrafine LiCoO₂ powders were directly synthesized by enhancing thermal decomposition of Cobalt and Lithium carbonates through a mechanochemical activation treatment to intensify the solid state diffusion reaction. Effects of activation treatment time on particle size and structure of the LiCoO₂ compound were investigated. In the present study, the optimum mechano-chemical activation time was found to be 10 h. In this study, the ultrafine LiCoO₂ powders (particle size in the range from 200 nm to 400 nm) show good structural stability and higher structural integrity. X-ray photoelectron spectroscopy (XPS) results indicate that most of Co cations exist as Co³⁺, which contributes to the improvement of the electrochemical performance. Cyclic voltammetry (CV) curves of different cycles display almost a complete overlap, which can be regarded as another evidence of the excellent cycle performance. The LiCoO₂ powders exhibit a high initial discharge specific capacity of 175.2 mAh/g at 0.1 C (274 mA/g at 1 C) and a remarkable cycle stability from 167.5 mAh/g to 146.2 mAh/g at 0.5 C and from 147.5 mAh/g to 115.2 mAh/g at 3 C after 100 cycles in the range of 3.3–4.3 V. The apparent activation energy and the frequency factor of the decomposition of CoCO₃ are 69.83 kJ/mol and 1.369×10⁶, respectively, indicating that the ultrafine in-process product of Co₃O₄ can be quickly prepared at a low temperature.