Effects of Yb～(3 ) codoping on visible and near infrared emissions of Er～(3 )-Yb～(3 ) codoped Al_2O_3 powders by the sol-gel method

The 0.1 mol% Er3 and 0―2 mol% Yb3 codoped Al2O3 powders were prepared by the sol-gel method,and the phase structure,including only two crystalline types of doped Al2O3 phase,γ-(Al,Er,Yb)2O3 and θ-(Al,Er,Yb)2O3,was detected at the sintering temperature of 1000℃. The visible and near infrared emissions properties depended strongly on the Yb3 codoping,and the corresponding maximal peak intensities centered at about 523,545,660 and 1533 nm were obtained respectively for the 0.1 mol% Er3 and 0.5 mol% Yb3 codoped Al2O3 powders,which were composed of θ-(Al,Er,Yb)2O3 and a small amount of γ-(Al,Er,Yb)2O3 phases. The two-photon absorption process was responsible for the visible up-conversion emissions,and the one-photon absorption process was involved in the near infrared emissions of the Er3 -Yb3 codoped Al2O3 powders.     

Nucleation and growth kinetics of La_(0.7)Sr_(0.3)Cr_(0.4)Mn_(0.6)O_(3-δ) SOFC perovskite:Symmetry alteration evolution induced by Cu~(2+) and Ni~(2+) impregnation

La_(0.7)Sr_(0.3)Cr_(0.4)Mn_(0.6)O_(3-δ) perovskite nanoparticles have been synthetized using an ethylene glycol modified solgel method and impregnated by Cu_(0.75)Ni_(0.25) nanoparticles. The phase transitions and nucleation kinetics were studied by time resolved x-ray diffraction, Rietveld, Raman spectroscopy and high resolution transmission electron microscopy. Findings have shown that, an atomic disorder dominates from room temperature to 400 °C. Nanoparticles with crystal size 26 nm start through nuclei formation of La_(0.7)Sr_(0.3)Cr_(0.4)Mn_(0.6)O_(3-δ) and SrCrO_4 solid solutions with Pm3m cubic and P2_1/n monoclinic symmetry respectively in the range of 600–650 °C. Symmetry reduction from the Pm3m→R3c space group had been obtained at a lower temperature(750 °C) than those reported in the literature in oxygen atmosphere and it was confirmed by an octahedral distortion, which takes place in the crystallographic direction[221]/(122). The Johnson-Mehl-Avrami model had described the whole process, where the existence of two phases was shown before it reached its complete D_(3d)~6 point group symmetry.     

First-principle study of interaction of H2 and H2O molecules with (ZnO)n(n=3?6) ring clusters

A density functional calculation was performed to investigate the impact of hydrogen and water molecules on zinc oxide clusters (ZnO)n=3–6 ··· X, where X=H2 and H2O. The calculated binding energies were corrected for the basis set superposition error (BSSE). The structural parameters and chemical hardness were calculated for the complexes of zinc oxide clusters and guest molecules. The strength values of the interaction between the clusters and the guest molecules were analyzed based on the topological properties of atoms in molecules (AIM) theory of Bade r. The stereo electronic interact ions inside the ZnO clusters were analyzed in detail using the natural bond orbital (NBO) analysis.     

Microstructure and electric characteristics of AETiO_3(AE=Mg,Ca, Sr)doped CaCu_3Ti_4O_(12) thin films prepared by the sol–gel method

This paper focuses on the effects of alkline-earth metal titante AETiO_3(AE = Mg,Ca,Sr) doping on the microstructure and electric characteristics of CaCu_3Ti_4O_(12) thin films prepared by the sol-gel method.The results showed that the grain size of CCTO thin films could be increased by MgTiO_3 doping.The movement of the grain boundaries was impeded by the second phases of CaTiO_3 and SrTiO_3 concentrating at grain boundaries in CaTiO_3 and SrTiO_3 doped CCTO thin films.Rapid ascent of dielectric constant could be observed in 0.1Mg TiO_3 doped CCTO thin films,which was almost as three times high as pure CCTO thin film and the descent of the dielectric loss at low frequency could also be observed.In addition,the nonlinear coefficient(α),threshold voltage(V_T) and leakage current(I_L) of AETiO_3 doped CCTO thin films(AE = Mg,Ca,Sr) showed different variation with the increasing content of the MgTiO_3,CaTiO_3 and SrTiO_3.     

Kinetics of C_2(a~3Π_u)radical reactions with NO,N_2O,O_2,H_2 and NH_3

Pulsed laser photolysis/laser-induced fluorescence (LP-LIF) is utilized to measure rate constants for C_2(a~3(multiply from)_u) reactions with NO, N_2O, O_2, H_2 and NH_3. Multiphoton dissociation of C_2CI_4 at 266 nm is employed for the generation of C_2(a~3(multiply from)_u) radicals. The C_2(a~3(multiply from)_u) concentration is monitored by the fluorescence of the (0, 0) band of the (d~3(multiply from)_g←→a~3(multiply from)_u) transition at 516.5 nm. C_2(a~3(multiply from)_u) removal rate constants for the reactions are determined as k_(NO)=(5.46±0.10)×10~(-11)cm~3molecule~(-1)s~(-1), k_(N_2O)=(1.63±0.20)×10~(-13)cm~3molecule~(-1)s~(-1), k_(N_2O)=(1.58±0.16)×10~(-11)cm~3molecule~(-1)s~(-1), k_(O_2)=(5.92±1.00)×10~(-14)cm~3molecule~(-1)s~(-1), k_(H_2)<1.0×10~(-14)cm~3molecule~(-1)s~(-1). Based on the data analysis and theoretical calculation, we suggest that the C_2(a~3(multiply from)_u) reactions with H_2 and NH_3 proceed via the hydrogen abstraction mechanism, barriers exist at the entr     

Synthesis and Crystal Structure of New Supramolecular Adducts of[PtCl_6]~(2-) with Cucurbit [7] uril:[(H_3O)_2 [PtCl_6]_3 [C_(42)H_(42)N_(28)O_ (14)_2·H_2O

0　IntroductionCucurbit [n]urils (Qn ,Fig .1.)arecyclicoligomersofnunitsofglycolurillinkedby 2nmethylenebridgesderivedfromformaldehyde.Theypossessacharacteristicannularshape,withtwoidenticalcarbonyl fringedportals[1 ,2 ] .Themostcom moncucurbituril,Q6 ,wasreportedtoaccommodatedifferentguestssuchaswater[3] ,THF[4 6] ,xenon[7] ,pyridium[8] andp xylyenediammonium[3] ionsandsoon .ThealkyldiaminesthreadthroughtheQ6 ,andformtherotaxanestructures[9 1 3] .Metalions[1 ,3 6 ,1 4 ,1 5] andclusters[8,…     

Mineral-phase evolution and sintering behavior of MO–SiO_2–Al_2O_3–B_2O_3 (M = Ca,Ba) glass-ceramics by low-temperature liquid-phase sintering

In this work, network former SiO_2 and network intermediate Al_2O_3 were introduced into typical low-melting binary compositions CaO·B_2O_3, CaO·2B_2O_3, and BaO·B_2O_3 via an aqueous solid-state suspension milling route. Accordingly, multiple-phase aluminosilicate glass-ceramics were directly obtained via liquid-phase sintering at temperatures below 950°C. On the basis of liquid-phase sintering theory, mineral-phase evolutions and glass-phase formations were systematically investigated in a wide MO–SiO_2–Al_2O_3–B_2O_3(M = Ca, Ba) composition range. The results indicate that major mineral phases of the aluminosilicate glass-ceramics are Al_(20)B_4O_(36), CaAl_2Si_2O_8, and BaAl_2Si_2O_8 and that the glass-ceramic materials are characterized by dense microstructures and excellent dielectric properties.     

A functionalized activated carbon adsorbent prepared from waste amidoxime resin by modifying with H3PO4 and ZnCl2 and its excellent Cr(Ⅵ) adsorption

With the application of resins in various fields, numerous waste resins that are difficult to treat have been produced. The industrial wastewater containing Cr(Ⅵ) has severely polluted soil and groundwater environments, thereby endangering human health. Therefore, in this paper, a novel functionalized mesoporous adsorbent PPR-Z was synthesized from waste amidoxime resin for adsorbing Cr(Ⅵ). The waste amidoxime resin was first modified with H3PO4 and ZnCl2, and subsequently, it was carbonized thr...     

Low-temperature densification sintering and properties of CaAl_2Si_2O_8 ceramics with MeO·2B_2O_3(Me=Ca,Sr,Ba)

Dense CaAl2Si2O8 ceramics were prepared via a two-step sintering process at temperatures below 1000°C. First, pre-sintered Ca Al2Si2O8 powders containing small amounts of other crystal phases were obtained by sintering a mixture of calcium hydroxide and kaolin powders at 950°C for 6 h. Subsequently, the combination of the pre-sintered ceramic powders with Me O·2B2O3(Me = Ca, Sr, Ba) flux agents enabled the low-temperature densification sintering of the CaAl2Si2O8 ceramics at 950°C. The sintering behavior and phase formation of the CaAl2Si2O8 ceramics were investigated in terms of the addition of the three MeO·2B2O3 flux agents. Furthermore, alumina and quartz were introduced into the three flux agents to investigate the sintering behaviors, phase evolvements, microstructures, and physical properties of the resulting CaAl2Si2O8 ceramics. The results showed that, because of their low-melting characteristics, the MeO·2B2O3(Me = Ca, Sr, Ba) flux agents facilitated the formation of the CaAl2Si2O8 ceramics with a dense microstructure via liquid-phase sintering. The addition of alumina and quartz to the flux agents also strongly affected the microstructures, phase formation, and physical properties of the CaAl2Si2O8 ceramics.     

Theoretical study on the lithium bond interaction of furan homologues C_4H_4Y (Y=O, S) with LiCH_3 via DFT and MP2

The optimizations geometries and interaction energy corrected by BSSE of the complexes between C4H4Y (Y=O, S) and CH3Li have been calculated at the B3LYP/6-311 G** and MP2/6-311 G** levels. Three complexes were obtained. Abnormally, the calculations showed that all the C10—Li14 bond lengths increased obviously but the blue-shift of C10—Li14 stretching frequency occurred after formed complexes. The calculated binding energy with basis set super-position error (BSSE) and zero-point vibrational energy corrections of complexes I―III is ?45.757, ?35.700 and ?39.107 kJ·mol?1, respectively. The analyses on the combining interaction with the atom-in-molecules theory (AIM) also showed that a relatively strong lithium bond interaction presented in furan homologues C4H4Y---LiCH3 systems. Natural bond orbital theory (NBO) analysis has been performed, and the results revealed that the com- plex I is formed with n-σ type lithium bond interaction between C4H4O and LiCH3, complex II is formed with π-s type lithium bond interaction between C4H4O and LiCH3, and complex III is formed with π-s and n-s type lithium bond interactions between C4H4S and LiCH3, respectively.     

Mineral-phase evolution and sintering behavior of MO-SiO2-Al2O3-B2O3 (M=Ca,Ba) glass-ceramics by low-temperature liquid-phase sintering

In this work, network former SiO₂ and network intermediate Al₂O₃ were introduced into typical low-melting binary compositions CaO·B₂O₃, CaO·2B₂O₃, and BaO·B₂O₃ via an aqueous solid-state suspension milling route. Accordingly, multiple-phase aluminosilicate glass-ceramics were directly obtained via liquid-phase sintering at temperatures below 950℃. On the basis of liquid-phase sintering theory, mineral-phase evolutions and glass-phase formations were systematically investigated in a wide MO-SiO₂-Al₂O₃-B₂O₃ (M=Ca, Ba) composition range. The results indicate that major mineral phases of the aluminosilicate glass-ceramics are Al₂₀B₄O₃₆, CaAl₂Si₂O₈, and BaAl₂Si₂O₈ and that the glass-ceramic materials are characterized by dense microstructures and excellent dielectric properties.     

Oxidation behaviours of Nb–22Ti–15Si–2Al–2Hf–2V–(2, 14)Cr alloys with Al and Y modified silicide coatings prepared by pack cementation

Al and Y modified silicide coatings on the Nb-15Si-22Ti-(2,14)Cr-2Al-2Hf-2V alloys(where the alloy with 2 at%Cr or 14 at%Cr is hereafter referred to as 2Cr and 14 Cr alloy,respectively) was prepared by pack cementation.The microstructural evolution and the oxidation behaviours of the coating 2Cr and 14 Cr samples at 1250 ℃ were studied.The 2Cr alloy consists of Nb solid solution(Nb_(SS)) and α-Nb_5Si_3 silicide,while the Laves C15-Cr_2Nb phase arised in the 14 Cr alloy.The coating structure of the coating 2Cr sample contained the outer(Nb,X)Si_2+(Nb,X)_5Si_3 layer,the middle(Nb,X)_5Si_3 layer and the inner undeveloped intermetallic(Nb,Ti)_3(Al,X) layer,the structure of the coating 14 Cr sample consisted of the outer single(Nb,X)Si_2 layer,the middle(Nb,X)_5Si_3 layer,the transition(Nb,Ti)(Cr,Al) layer and the inner(Cr,Al)_2(Nb,Ti) layer.The coating 14 Cr sample exhibited better oxidation resistance than the coating 2Cr sample.With an outer single(Nb,X)Si_2 layer,a compact oxide scale consisting of SiO_2 and TiO_2 formed on the coating14 Cr sample,which can efficiently prevent the substrate from oxidising.For the coating 2Cr sample with an outer(Nb,X)Si_2 +(Nb,X)_5Si_3 layer,the oxide scale of the SiO_2,TiO_2,Nb_2O_5 and CrNbO_4 mixture generated,and the scale spalled out from the surface of the sample,resulting in disastrous failure.     

Kinetics of C2(a3Πu) radical reactions with NO, N2O, O2, H2 and NH3

Pulsed laser photolysis/laser-induced fluorescence (LP-LIF) is utilized to measure rate constants for C₂(a³Π_u) reactions with NO, N₂O, O₂, H₂ and NH₃. Multiphoton dissociation of C₂Cl₄ at 266 nm is employed for the generation of C₂(a³Π_u) radicals. The C₂(a³Π_u) concentration is monitored by the fluorescence of the (0, 0) band of the (d³Π_g&#8596;a³Π_u) transition at 516.5 nm. C₂(a³Π_u) removal rate constants for the reactions are determined as k_NO = (5.46 ± 0.10) × 10^-11 cm³ molecule^-1 s^-1 , k_N2O = (1.63 ± 0.20) × 10^-13 cm³ molecule^-1 s^-1 , k_N2O = (1.58 ± 0.16) × 10^-11 cm³ molecule^-1 s^-1, k_O2 = (5.92 ± 1.00) × 10^-14 cm³ molecule^-1 s^-1, k_H2< 1.0× 10^-14 cm³ molecule^-1 s^-1. Based on the data analysis and theoretical calculation, we suggest that the C₂(a³Π_u) reactions with H₂ and NH₃ proceed via the hydrogen abstraction mechanism, barriers exist at the entrance channel of the reactions of C₂(a³Π_u) with H₂ and NH₃.