Structure and photoluminescence property of complexes of aromatic carboxylic acid-functionalized polysulfone with Eu(Ⅲ) and Tb(Ⅲ)

With chloromethylated polysulfone as starting substance, naphthoic acid (NA) and benzoic acid (BA) were bonded onto the side chains of polysulfone (PSF) via polymer reactions, obtaining two kinds of aromatic carboxyl acid-functionalized polysulfone, PSFNA and PSFBA. Subsequently, the luminescent binary and ternary polymer-rare earth complexes of Eu(Ⅲ) and Tb(Ⅲ) were prepared through coordination reactions, respectively, with PSFNA and PSFBA as macromolecule ligands and with 1,10-phenanthroline (Phen) and 4,4′-bipyridine (Bipy) as small-molecule co-ligands. This work focuses on investigating the relationship between structure and photoluminescence property of these complexes. The experimental results indicate that the macromolecule ligands PSFNA and PSFBA can strongly sensitize the fluorescence emissions of Eu³⁺ ion or Tb³⁺ ion, and the sensitization effect is strongly dependent on the structure of the ligands and the property of the central ions. The fluorescence emission of the binary complex PSF–(NA)₃–Eu(Ⅲ) is stronger than that PSF–(BA)₃–Eu(Ⅲ), suggesting the bonded ligand NA has stronger sensitization action for Eu³⁺ ion than ligand BA; The binary complex PSF–(BA)₃–Tb(Ⅲ) emit very strong characteristic fluorescence of Tb³⁺ ion, displaying that ligand BA can strongly sensitize Tb³⁺ ion, whereas PSF–(NA)₃–Tb(Ⅲ) does not emit the characteristic fluorescence of Tb³⁺ ion, showing that the bonded ligand NA does not sensitize Tb³⁺ ion. The fluorescence intensity of the ternary complexes is stronger than that of the binary complexes in the same series. The solid films of these complexes also emit the strong characteristic fluorescence of Eu³⁺ ion or Tb³⁺ ion.     

Synthesis and Characterization of Nanocapsules of α-Fe(NiCoAl) Solid-solution

α-Fe(NiCoAl) solid-solution nanocapsules were prepared with pure powders of Fe, Ni, Co and Al by the plasma arc-discharging using a copper crucible. The shapes of the nanocapsules are in polyhedrons with the core/shell structure. The body centered cubic (BCC) phase is formed in the core. The size of the nanocapsules is in the range of 10-120 nm and the thickness of the shell is 4-11 nm. Saturation magnetization JS=150 Am2/kg and coercivity iHC=24.3 kA/m are achieved for the nanocapsules.     

Synthesis and Characterization of Nanocapsules of α-Fe(NiCoAl) Solid-solution

α-Fe(NiCoAl) solid-solution nanocapsules were prepared with pure powders of Fe, Ni, Co and Al by the plasma arc-discharging using a copper crucible. The shapes of the nanocapsules are in polyhedrons with the core/shell structure. The body centered cubic (BCC) phase is formed in the core. The size of the nanocapsules is in the range of 10～120 nm and the thickness of the shell is 4～11 nm. Saturation magnetization Js=150 Am2/kg and coercivity iHC=24.3 kA/m are achieved for the nanocapsules.     

Synthesis and study of complexes of Pu(V) and Np(V) propionates with α,α′-bipyridine

New complexes of Np(V) and Pu(V) with α,α′-bipyridine of the composition AnO₂(bipy) · OOCC₂H₅·H₂O (An = Np, Pu) were synthesized. They are isostructural to each other; however, they differ essentially in the structure and characteristics from the similar complexes of An(V) formates and acetates. The new compounds were characterized by powder X-ray diffraction, thermal analysis, electronic absorption spectroscopy, and IR spectroscopy.     

Quenchability and Magnetic Properties of Nd_4Fe_(82)B_(14)

The glass forming ability (GFA), crystallization behaviour and magnetic properties of Nd4Fe82B14 produced by melt spinning were investigated. The experimental results show that the GFA is rather Strong; the crystals precipitation sequence is as follows: Am(amorphous)→Am'+bcc-Fe →Nd2Fe23B3+Fe23B6+bcc-Fe→Fe23B6+Fe3B+Nd2Fe14B+bcc-Fe→Fe3B+Nd2Fe14B+bcc-Fe. The magnetic properties after crystallization are not affected by the cooling rate and the best magnetic properties are Br=0.8436 T, Hcj=266.4 kA/m, (BH)max=48.08 kJ/m3.     

Laboratory of Fatigue and Fracture for Materials(LFFM)

This laboratory was designated as Na-tional Laboratory in 1988 and is subordi-nate to the Institute of Metal Research(IMR),Academia Sinica.It is nowwell-equipped after rebuilding under a spe-cial grant-in-aid program from the centralgovernment.According to the policy of“Opening,Flowing and Serving the WholeCountry”for the national laboratories,vis-iting research fellows at home and fromabroad are welcome to join common re-search projects in this lab.     

Work Functions of Pd_(83.5)Si_(16.5)and Cu_(70)Ti_(30)Glassy Alloys

The work functions before and aftercrystallization of two glassy alloys,Pd_(83.5)Si_(16.5) andCu_(70)Ti_(30) have been measured by means of the con-tact potential difference method in the secondaryelectron field at room temperature under 10~(-5) Pavacuum.The results show that the work functionsof both glassy alloys are higher than those of thecorresponding crystalline alloys.     

Determination of δ(18)O and δ(15)N in Nitrate

The analyses of both O and N isotopic compositions of nitrate have many potential applications in studies of nitrate sources and reactions in hydrology, oceanography, and atmospheric chemistry, but simple and precise methods for these analyses have yet to be developed. Testing of a new method involving reaction of potassium nitrate with catalyzed graphite (C + Pd + Au) at 520 °C resulted in quantitative recovery of N and O from nitrate as free CO(2), K(2)CO(3), and N(2). The δ(18)O values of nitrate reference materials were obtained by analyzing both the CO(2) and K(2)CO(3) from catalyzed graphite combustion. Provisional values of δ(18)O(VSMOW) for the internationally distributed KNO(3) reference materials IAEA-N3 and USGS-32 were both equal to +22.7 ± 0.5‰. Because the fraction of free CO(2) and the isotopic fractionation factor between CO(2) and K(2)CO(3) were constant in the combustion products, the δ(18)O value of KNO(3) could be calculated from measurements of the δ(18)O of free CO(2). Thus, δ(18)O(KNO)((3)) = aδ(18)O(free)(?)(CO)((2)) - b, where a and b were equal to 0.9967 and 3.3, respectively, for the specific conditions of the experiments. The catalyzed graphite combustion method can be used to determine δ(18)O of KNO(3) from measurements of δ(18)O of free CO(2) with reproducibility on the order of ±0.2‰ or better if local reference materials are prepared and analyzed with the samples. Reproducibility of δ(15)N was ±0.1‰ after trace amounts of CO were removed.     

An On-Line Technique for the Determination of the δ(18)O and δ(17)O of Gaseous and Dissolved Oxygen

Few studies have used the stable isotopic composition of O(2) as a tracer of gas transport or biogeochemical processes in environmental research. Here we demonstrate field sampling techniques for gaseous and dissolved O(2) and describe an analytical method for measuring δ(18)O and δ(17)O values of O(2) in air, soil gas, and water samples using continuous-flow isotope-ratio mass spectrometry (CF-IRMS). A Micromass CF-IRMS was altered to accommodate a sample gas injection port prior to a CO(2) and H(2)O trap and GC column. The GC column was a 1-m, 5-? molecular sieve column held at 35 °C. The resolved sample O(2) was introduced to the IRMS via an open split. δ(18)O and δ(17)O values were determined by measurement of O(2) isotopes at m/z 34/32 and 33/32 and comparison to a reference pulse of O(2). Repeated injections of atmospheric oxygen yielded a repeatability (±SD) of ±0.17‰ for δ(18)O and ±0.5‰ for δ(17)O. IRMS source linearity was excellent for O(2) over a sample size range of 60-400 μL. The smallest sample for routine δ(18)O and δ(17)O determinations was ～80 μL of O(2), with a sample analysis time of 180 s. Preliminary results from a riverine and soil gas study illustrate natural oxygen isotope fractionation processes.     

Preparation and properties of polyrotaxane from α-cyclodextrin and poly(ethylene glycol) with poly(vinyl alcohol)

α–Cyclodextrin (α-CD) was found to form inclusion complexes with poly(ethylene glycol) (PEG) having a crystalline state in high yields, which have been investigated extensively in the past. Formation of an inclusion complex depends strongly on structure, molecular weight and geometry of the polymer. Development of a dicomponent inclusion complex (DIC) of PEG and α-CD in the presence of poly(vinyl alcohol) (PVA) and initiation of hexagonal crystals upon sonication have exhibited various microstructures. Formation of the new inclusion complex in PVA heavily depends on the concentration of PVA, temperature and sonication time. The complexes produced are characterized by FTIR, HNMR spectra and powder X-ray. ¹HNMR of the complexes demonstrate that their stoichiometric ratio is 2:1 (two ethylene glycol units and one α-CD). X-ray patterns of PEG–α-CD complex indicate that the α-CD forms channels whereas PEG/α-CD/PVA creates cage-type structures.     

Visible photoluminescense of the (112¯0), (101¯1) and (0001) surfaces of ZnO nanofilms

Thin ZnO nanofilms 25 nm thick with (0001), $\left(11\overline{2}0\right)$ and $\left(10\overline{1}1\right)$ as surfaces were grown epitaxially on the NaCl (111) and (001) surfaces. The room temperature photoluminescence (PL) spectrum from the $\left(11\overline{2}0\right)$ nanofilm has a sharp UV emission but negligible green emission, indicating that it has good quality and low defect density. However, the PL spectra from the $\left(10\overline{1}1\right)$ and (0001) surface nanofilms have a broad green emission, and that of the $\left(10\overline{1}1\right)$ surface is stronger than the (0001) surface. The result supports that the surface oxygen vacancies are the probable origins of the green emission.     

Synthesis and Characterization of Sm_xGd_yCe_(1-x-y)O_(2-δ) Nanopowders

SmxGdyCe1-x-yO2-δ (x+y=0.2 and x=0, 0.04, 0.08, 0.12, 0.16, 0.2) nanopowders were prepared by a copre-cipitation method. The zeta potential and sedimentation volume of Ce(OH)4 aqueous dispersions at different pH values were measured. The isoelectric point (IEP) of Ce(OH)4 suspensions is 7.0. The maximum potential value of -18.5 mV and maximum sedimentation volume of 19 ml are reached at pH=10. The evolution behaviors of the xSm(OH)3·yGd(OH)3·(1-x-y)Ce(OH)4 dried powders in the heating process was characterized by DTA/TG and XRO. The powders decompose to ceria based solid solution at a temperature below 300℃ and forms cubic fluorite structure ceria at about 650℃. The properties of SmxGdyCe1-x-yO2-δ solid solutions were characterized by XRD, TEM and BET. The lattice parameter of doped Ce02 increases linearly with increasing Sm3+ substitution (or decreasing Gd3+ substitution). The particle size of the doped ceria powders is from 5 nm to 10 nm.     

Thermal Stability of Amorphous Hydride Mg_(50)Ni_(50)H_(54) and Mg_(30)Ni_(70)H_(45)

The thermal stability of amorphous ternary hydrides Mg_(50)Ni_(50)H_(54) and Mg_(30)Ni_(70)H_(45) and their corre-sponding amorphous binary alloys Mg_(50)Ni_(50) and Mg_(30)Ni_(70) were studied with X-ray diffraction(XRD) and differential scanning calorimetry(DSC). Samples of the amorphous alloys were preparedby mechanical alloying and the amorphous hydrides were obtained by charging the alloys with gas-eous hydrogen at 3.0 MPa and 423 K. It was found that the amorphous hydrides released most oftheir hydrogen before the crystallization of the essentially hydrogen depleted amorphous alloy. Thecrystallization temperature of amorphous Mg_(50)Ni_(50)H_(54) elevated and that of amorphousMg_(30)Ni_(70)H_(45) did not change in relation to the original binary amorphous alloy. This is very excep-tional for amorphous hydrides. The reason for the effects of hydrogen absorption/desorption on thecrystallization of amorphous alloys was discussed.     

Dielectric and pyroelectric properties of P(VDF-TrFE) and PCLT–P(VDF-TrFE) 0–3 nanocomposite films

Nanocrystalline calcium and lanthanum modified lead titanate (PCLT) powder prepared by a sol–gel process was incorporated into a polyvinylidene fluoride-trifluoroethylene [P(VDF-TrFE)] copolymer matrix to form PCLT–P(VDF-TrFE) nanocomposite thin films with 0.11 volume fraction of ceramic. The relative permittivity and pyroelectric coefficient of the P(VDF-TrFE) copolymer and nanocomposite films were measured as functions of the poling electric field. After poling under the same conditions, the nanocomposite film was found to have a higher pyroelectric coefficient (by ∼35%) and figures of merit than those of the P(VDF-TrFE) film of a similar thickness.     

Electrical and humidity sensing properties of lead(II) tungstate–tungsten(VI) oxide and zinc(II) tungstate–tungsten(VI) oxide composites

Lead(II) tungstate and zinc(II) tungstate were prepared by a solution route and sintered at 973 K in the form of cylindrical discs. Experimental results on PbWO₄ (PW) and WO₃ (WO) composites for humidity sensing are described. Sintered polycrystalline discs of PbWO₄ (PWWO-10), WO₃ (PWWO-01), ZnWO₄ (ZWWO-10) and composites of PW or ZW and WO in the mole ratios 8:2, 6:4, 4:6, 2:8 designated as PWWO and ZWWO-82, 64, 46 and 28, respectively and doped with 2 mol% of Li⁺ were studied. The composites were subjected to dc conductance measurements over the temperature range 373–673 K in air atmosphere from which activation energies were determined. The activation energy values for dc conductance were found to be in the range of 1.09–1.30 eV. The composites were identified by powder XRD data. The scanning electron microscopy (SEM) studies were carried out to study the surface and pores structure of the sensor materials. The composites were subjected to dc resistance measurements as a function of relative humidity in the range of 5–98% RH, achieved by different water vapor buffers thermostated at room temperature. The sensitivity factor (S_f=R_5%/R_98%) measured at 298 K revealed that PWWO-28 and ZWWO-46 composites have the highest humidity sensitivity factor of 17 615±3000 and 2666±550, respectively. The response and recovery time for these humidity sensing composites were good.     

Synthesis and properties of LiZr2(AsO4)3 and LiZr2(AsO4) x (PO4)3 − x

The LiZr₂(AsO₄)₃ arsenate and LiZr₂(AsO₄) _x (PO₄)_{3 ? x} solid solutions have been prepared through precipitation followed by heat treatment, and characterized by X-ray diffraction, X-ray structure analysis, IR spectroscopy, and impedance spectroscopy. We have established conditions for the crystallization of the arsenate and a continuous series of arsenate phosphate solid solutions (0 ≤ x ≤ 3), which have been obtained as two polymorphs: monoclinic and hexagonal. Using the Rietveld method, we have refined the crystal structures of the polymorphs of LiZr₂(AsO₄)₃ (sp. gr. P2₁/n, a = 9.1064(2), b = 9.1906(2), c = 12.7269(3) Å, β = 90.844(2)°, V =1065.03(5) ų, Z = 4; sp. gr. R $\bar 3$ c, a = 9.1600(4), c = 22.9059(13) Å, V = 1664.44(14) Å, Z = 6) and LiZr₂(AsO₄)_1.5(PO₄)_1.5. Their structural frameworks are built up of AsO₄ tetrahedra—or (As,P)O₄ tetrahedra occupied by arsenic and phosphorus atoms at random—and ZrO₆ octahedra, with the lithium atoms in between. The ionic conductivity of the materials has been measured. The cation conductivity of monoclinic LiZr₂(AsO₄) _x (PO₄)_{3 ? x} with 0 ≤ x ≤ 1 has been shown to exceed the conductivity of lithium zirconium phosphate.     

γ-Cu2(OH)3Cl as precursor in the preparation of copper (I) and (II) oxides and copper powder

When-Cu₂(OH)₃Cl is decomposed in air or nitrogen flow, different amounts of cuprous oxide are obtained as final product depending on both the heating rate and the ambient atmospheres. However, the temperature of formation of cuprous oxide only appears to depend on the partial pressure of oxygen. When thermal decomposition is carried out under dynamic vacuum in the X-ray high-temperature diffraction chamber, using a tantalum strip as the heating element, copper is obtained as final product at a comparatively low temperature.     

Temperature dependence of surface impedance Z(T, ω) and mean free paths I(T) of YBCO-superconductors

The surface impedance Z(T,) at 10 and 145 GHz and between 4 and 300 K is obtained experimentally. Z(T_aTT_c) is quantitatively fitted by the BCS theory with a mean free path I(T) increasing rapidely below T_c. This I-increase in the frame of the BCS-theory is limited at T_a by inelastic surface scattering at weak or strong links, e.g., by twin boundaries in distances a_TW which dominates scattering for a_Tw2I(T_a). Below T_a the enforced energy transfer from YBCO-crystallites to weak links may enhance Z(Ta) until at T T* the weak link surface impedance dominates Z_res(T相似文献   

Vibrational measurements of Na/Ni(111) and (Na + CO)/Ni(111)

The vibrational properties of Na atoms and of Na coadsorbed with CO on Ni(111) have been studied by high-resolution electron energy loss spectroscopy. Loss measurements showed a significant weakening of the alkali–substrate bond as a function of the alkali coverage. Moreover, we found that coadsorbed CO molecules dramatically influence the vibrational properties of Na adatoms. The Na–Ni stretching frequency (22 meV) measured on the Na/Ni(111) system shifted down to 13 meV for the (Na + CO)/Ni(111) surface. This unexpected result was ascribed to a charge transfer from Na to CO. Present findings give new insights on the nature of the alkali–substrate and alkali–CO bond.     

Magnetic Properties and Thermal Stability of Pr_(1-x)La_xCo_(5-y)Alloys

Pr1-xLaxCo5-y (x=0, 0.15. 0.25, 0.35,1.0, y=0.5, 0.7, 0.9, 1.0) alloys were investigated. The effect of the variation of x and y on magnetic properties and thermal stability of the alloys were studied. The magnetic properties for the Pr0.85La0.15Co4.3 and Pr0.75La0.25Co4.1 magnets are iHc=368 kA/m, Br=0.91 T, (BH)max=145.6 kJ/m3, αBr=-0.03%/℃ and iHc=568 kA/m,Br=0.8 T, (BH)max=127.2 kJ/m3,αBr,=-0.06%/℃, respectively The phase structures of as-cast alloys and magnets were investigated