聚苯硫醚熔体的压致凝固行为

采用施加压力的方法将聚苯硫醚熔体凝固,凝固后获得的聚苯硫醚样品经过降温和卸压后在常温常压下回收. X射线衍射和差示扫描量热分析表明:约20 ms时间的快速压缩过程可以抑制熔体结晶,制备出非晶态聚苯硫醚块材,样品的表面及中心都是非晶态.非晶态聚苯硫醚的玻璃化转变温度和晶化温度分别为318和362 K.常压下的退火实验表明,非晶态聚苯硫醚在425 K等温结晶的产物为正交相晶型.压致凝固法中熔体的凝固不是靠温度变化,而是靠压力变化,样品表面和内部处在一致的温度下同时受压凝固,避免了热传导对非晶尺寸的影响,因此非常有利于获得结构均匀的大尺寸非晶态材料.     

Exploring the surface permeability of nanoporous particles by pulsed field gradient NMR

A new method to determine the surface permeability of nanoporous particles is proposed. It is based on the comparison of experimental data on tracer exchange and intracrystalline molecular mean square displacements as obtained by the PFG NMR tracer desorption technique with the corresponding solutions of the diffusion equation via dynamical Monte Carlo simulations. The method is found to be particularly sensitive in the "intermediate" regime, when the influence of intracrystalline diffusion and surface resistances of the nanoporous crystal on molecular transport are comparable and the conventional method fails. As an example, the surface permeabilities of two samples of zeolite NaCaA with different crystal sizes are determined with methane, as a probe molecule, at room temperature.     

Nb掺杂对还原性烧结的TiO2-δ陶瓷的晶体结构及热电性能的影响

利用传统的固相反应法在还原性气氛1200 ℃下分别制备出不同Nb掺杂量的Ti_1-xNb_xO_2-δ陶瓷样品.样品的粉末X射线衍射(XRD)结果显示:Nb掺杂量x较低时样品为多相混合,当Nb掺杂量x>0.02时样品为单一的四方相金红石型结构.在室温到900 K的测试温区,测试了单相样品(x=0.02,0.03,0.04)的电导率、Seebeck系数和热导率.测试 关键词： 氧化钛陶瓷 热电性能 氧空位     

Synthesis and dielectric properties of Bi1−xNdxFeO3 perovskites

Single-phase polycrystalline samples of Bi_1−xNd_xFeO₃ were prepared by standard solid state reaction method. X-ray diffraction (XRD) patterns of the powder samples were recorded and analyzed for the confirmation of crystal structure lattice parameters. Further, these samples were characterized by IR technique to identify and understand the aspect of bonding in the present samples. The dielectric measurements were carried out on the samples as a function of frequency in the range 100 Hz to 1 MHz at room temperature and also as a function of temperature in the range 300–750 K at certain fixed frequencies. The DC and AC electrical resistivity studies were carried out in order to understand conduction mechanism in the samples.     

Spectral,Optical and Mechanical studies on pure and thiourea doped ammonium di-hydrogen phosphate NLO single crystals

Pure and thiourea substituted single crystals of ammonium di-hydrogen phosphate have been grown from aqueous solution by isothermal solvent evaporation technique. Doped crystal exhibits prominent changes in physical and chemical properties. Single crystal XRD analyses of the samples are carried out and the results are compared. FTIR and UV–vis–NIR spectral analyses have been employed to identify the presence of various functional groups and the UV cut-off range in the grown crystals. Density measurements have been made and Photoconductivity studies revealed the negative photo conducting nature. Hardness measurement shows that the mechanical strength of the doped crystal is high when compared to pure ammonium di-hydrogen phosphate. The dielectric response of the samples has been studied in the frequency range 100 Hz–5 MHz at room temperature and the results are discussed.     

A new aspect of specific radiation damage: hydrogen abstraction from organic molecules

Radiation damage is one of the major impediments in obtaining high‐resolution structural information utilizing ionizing radiation. From electron microscopy it is known that electron irradiation of biological samples results in the formation of molecular hydrogen. In the present work radiation‐induced structural changes of the polypeptide cyclosporine A were observed at a temperature of 100 K. Bond length changes are thought to be due to radiation‐induced hydrogen abstraction which chemically modifies the molecules in an irreversible way. The resulting formation of molecular hydrogen might explain the observed increase of the crystal mosaicity, which has also been reported in many previous radiation damage studies.     

Molecular dynamics of poly(L-lactide) biopolymer studied by wide-line solid-state 1H and 2H NMR spectroscopy

The molecular dynamics of poly(L-lactide) (PLLA) biopolymer was characterized through analyses of 1H and 2H NMR line-shapes and spin-lattice relaxation times at different temperatures. At low temperatures (e.g. 90 K), the methyl group rotation is dominant leading to a significant reduction in the proton second moment. Fast methyl group reorientation occurs at ca. 130 K. In additional to the fast methyl group rotation, hydroxyl groups start to reorient as the temperature increases further, eventually leading to the breakdown of the segments of the biopolymer chains above its glass transition temperature Tg of 323 K. The analyses of the 2H NMR line-shapes indicate that both the methyl and hydroxyl reorientations can be described by the so-called cone model, in which the former has three equilibrium positions with theta(C-D) = 70.5 degrees and phi = 120 degrees while the latter one exhibits two equilibrium positions with theta(O-D) = 78 degrees and phi = 180 degrees .     

高质量ZnO及BeZnO薄膜的发光性质

用分子束外延设备插入缓冲层在c面蓝宝石上生长得到高质量ZnO和BeZnO薄膜。XRD测试显示薄膜具有六方结构和c轴取向,并具有良好的晶体质量,其中ZnO薄膜的半高宽仅为108 arcsec,Be_xZn_1-xO薄膜的半高宽小于600 arcsec。对ZnO和BeZnO薄膜的拉曼光谱进行对比研究发现,随着Be元素的掺入,A₁(LO)、A₁(2LO)声子模频率往大波数方向移动,并且首次发现了与Be元素掺杂有关的局域振动模。利用变温光致发光光谱研究了薄膜的发光性质,结果显示ZnO薄膜室温光致发光只出现一个紫外发发光峰(378 nm),而低温光谱(80 K)则出现了很强的自由激子发光峰。随着温度的升高,束缚激子发光逐渐湮灭向自由激子发光转变,并且峰值位置红移。相对于ZnO薄膜,BeZnO薄膜的紫外发光主峰位置蓝移,并且由于Be元素的掺入导致薄膜晶体质量下降,在低温(80 K)光致发光光谱中没有出现强的自由激子发光峰。另外,在低温光致发光及拉曼光谱中,主峰位置在100~200 K之间有局部最大值,推测为由于合金晶格热膨胀系数失配而引起的应力效应。     

Crystal growth,optical and thermal studies of nonlinear optical γ-glycine single crystal grown from lithium nitrate

Single crystals of the nonlinear material γ-glycine have been grown in the presence of lithium nitrate by slow-evaporation method. Structural characterization of the grown crystals was carried out by powder and single crystal X-ray diffraction (XRD) methods and it is observed that the samples crystallize in hexagonal system with non-centrosymmetric space groups. The modes of vibrations of different molecular groups present in glycine have been identified by spectral analyses. UV–visible transmittance study was performed to analyze optical transparency of γ-glycine crystals and found that the crystal was transparent in the entire visible-NIR region. Second harmonic generation (SHG) conversion efficiency has been estimated as 62 mV and the output power by the crystal was 1.72 times that of potassium dihydrogen phosphate (KDP) crystal. The thermal stability and decomposition of the sample have been studied by thermal analysis and it is observed that the γ-glycine crystal have good thermal stability.     

Vibrational,NMR and UV–visible spectroscopic investigation and NLO studies on benzaldehyde thiosemicarbazone using computational calculations

In order to investigate the vibrational, electronic and NLO characteristics of the compound; benzaldehyde thiosemicarbazone (BTSC), the XRD, FT-IR, FT-Raman, NMR and UV–visible spectra were recorded and were analysed with the calculated spectra by using HF and B3LYP methods with 6-311++G(d,p) basis set. The XRD results revealed that the stabilized molecular systems were confined in orthorhombic unit cell system. The cause for the change of chemical and physical properties behind the compound has been discussed makes use of Mulliken charge levels and NBO in detail. The shift of molecular vibrational pattern by the fusing of ligand; thiosemicarbazone group with benzaldehyde has been keenly observed. The occurrence of in phase and out of phase molecular interaction over the frontier molecular orbitals was determined to evaluate the degeneracy of the electronic energy levels. The thermodynamical studies of the temperature region 100–1000 K to detect the thermal stabilization of the crystal phase of the compound were investigated. The NLO properties were evaluated by the determination of the polarizability and hyperpolarizability of the compound in crystal phase. The physical stabilization of the geometry of the compound has been explained by geometry deformation analysis.     

EPR of an exchange-coupled,hydrogen-bridged one-dimensional Cu(II) complex containing both octahedral and square pyramidal geometries in the same unit cell

Single-crystal X and Q band EPR of a hydrogen-bridged l-dimensional Cu(II) complex, [Cu(stpy)₂(CH₃COO)₂(H₂O)₂] [CU(stpy)₂(CH₃COO) ₂(H₂O)], containing both octahedral and square pyramidal geometries in the same unit cell, has been studied at 300 K. EPR of powder samples at X band frequencies at 300 K and 77 K show exchange-narrowed resonance. The peak-to-peak linewidths of the signals are 80 G and 85 G, respectively. However, at Q band frequencies it exhibits an axially symmetric spectrum with spin Hamiltonian parameters g_|| = 2.303 and g_⊥ = 2.077, corresponding to an |x² ? y²〉 ground state. Single-crystal X band EPR spectra show a single resonance line for all the orientations, indicating the complex to be in the strong exchange regime. On the other hand, Q band spectra exhibit two lines corresponding to the weak exchange regime. An estimate of the interchain-site exchange coupling constant J′ = 0.0125(3) cm^?1 also reveals weak coupling between the magnetically distinct Cu(II) centres. The ratio of J′/J = 8.25 × 10^?2 is low enough to make the interactions almost l-dimensional, in agreement with X-ray data. EPR linewidth and lineshape analyses also support l-dimensional behaviour of the system.     

Molecular dynamics simulation of defect formation in an aluminum crystal under low-energy ion bombardment

Atomic collision cascades initiated by Ar and Xe ions (with energies of 25, 40, and 50 eV) normally incident on the Al(100) crystal surface at a crystal temperature of 300 K have been simulated by the molecular dynamics technique. The formation of vacancies and radiation-adsorbed and interstitial atoms in a cascade is discussed. It is demonstrated that the numbers of surface and bulk vacancies formed in cascades under bombardment of the Al(100) surface by Xe ions reach two maxima within 0.2–0.3 and 0.7–1.0 ps after the cascade initiation, whereas the number of vacancies generated under bombardment by Ar ions reaches one maximum within 0.2–0.3 ps after the cascade initiation.     

有机分子PTCDA在P型Si单晶(100)晶面的生长机理

对PTCDA的分子结构及其化学键的形成进行了分析,并讨论了晶面指数（100）Si单晶的晶格结构。在此基础上,评述了PTCDA分子在P-Si单晶（100）晶面上生长的机理,并制备了样品PTCDA/P-Si（100）。利用XRD对样品测试得出,在P-Si（100）晶面上沉积的PTCDA薄膜中仅存在α物相。利用XPS对样品测试得出,在其界面层中PTCDA酸酐中的4个羟基O原子与C原子结合,其结合能为532.4 eV;苝核基团外围的8个C、H原子以共价键结合,其结合能为289.0 eV;在界面处,悬挂键上的Si原子与PTCDA酸酐中的C、O原子结合,形成C-Si-O键及C-Si键,构成了界面层的稳定结构。     

Magnetization and magnetic excitations in HoAl2

The magnetization of HoAl₂ single crystals parallel and perpendicular to the applied field for three crystallographic directions has been measured between 4.2 and 300 K in fields up to 8 T. Further the spin wave excitations were investigated by inelastic neutron scattering at 5.2 K along <100>, <110> and <111> directions in reciprocal space. The results are interpreted consistently in terms of a cubic crystal field using a simple molecular field to calculate the magnetization and an isotropic Heisenberg exchange interaction to obtain the magnetic excitations.     

退火温度对原子层沉积法制备ZnMgO薄膜结构和光学性能的影响

针对目前关于退火温度对原子层沉积法(ALD)制备ZnMgO薄膜晶体结构和光学性质影响鲜有报道的现象,进行了相应的实验研究分析。采用ALD在石英衬底上制备ZnMgO合金薄膜,对制得的样品在空气中进行不同温度的退火处理。利用X射线多晶衍射仪(XRD)、光致发光谱(PL)和紫外可见(UV-Vis)吸收光谱测试,系统的分析了不同退火温度对ALD法制备ZnMgO薄膜晶体结构和光学性能的影响。XRD测试结果表明：退火温度为600 ℃时,薄膜的晶体质量得到改善,且(100)衍射峰的强度明显增强。结合PL和UV-Vis吸收光谱的测试分析得出：退火温度为600 ℃时,能明显促进薄膜中Mg组分的增加使薄膜的禁带宽度进一步增大。从而说明适当温度的退火处理可有效的改善ZnMgO薄膜的晶体质量及光学特性。     

Spin singlet formation in MgTi2O4: evidence of a helical dimerization pattern

The transition-metal spinel MgTi2O4 undergoes a metal-insulator (M-I) transition on cooling below T(M-I)=260 K. A sharp reduction of the magnetic susceptibility below T(M-I) suggests the onset of a magnetic singlet state. Using high-resolution synchrotron and neutron powder diffraction, we have solved the low-temperature crystal structure of MgTi2O4, which is found to contain dimers with short Ti-Ti distances (the locations of the spin singlets) alternating with long bonds to form helices. Band structure calculations based on hybrid exchange density functional theory show that, at low temperatures, MgTi2O4 is an orbitally ordered band insulator.     

无水五硼酸钾晶体高温性质振动光谱的研究

利用自行设计的反应器研究了高温条件下水蒸汽对无水五硼酸钾晶体结构的影响,借助于X射线衍射、红外光谱、Raman光谱等手段分析了无水五硼酸钾晶体高温性质的振动光谱。在水蒸汽的作用下,五硼酸钾的B₂O₃/K₂O(摩尔比)变小,X射线衍射分析表明750 ℃时晶体中有K₅B₁₉O_<sub>31存在,而红外光谱与Raman光谱分析表明由于水蒸汽的作用使得晶体中的三角形B₍₃₎—O结构单元向四面体B₍₄₎—O结构单元转变,四面体的B₍₄₎—O含量增加并且硼氧网络结构被进一步打断。     

A new manganese-based single-molecule magnet with a record-high antiferromagnetic phase transition temperature

We perform both dc and ac magnetic measurements on the single crystal of Mn30（Et-sao）3（C104）（MeOH）3 single- molecule magnet （SMM） when the sample is preserved in air for different durations. We find that, during the oxidation process, the sample develops into another SMM with a smaller anisotropy energy barrier and a stronger antiferromagnetic intermolecular exchange interaction. The antiferromagnetic transition temperature observed at 6.65 K in the new SMM is record-high for the antiferromagnetic phase transition in all the known SMMs. Compared to the original SMM, the only apparent change for the new SMM is that each molecule has lost three methyl groups as revealed by four-circle x-ray diffraction （XRD）, which is thought to be the origin of the stronger antiferromagnetic intermolecular exchange interaction.     

Optical properties of CH3NH3PbI3 crystal grown using inverse temperature crystallization

Perovskite CH₃NH₃PbI₃ (MAPbI₃) single crystal was grown using inverse temperature crystallization method. Crystallinity of the perovskite was confirmed by X-ray diffraction. Photoluminescence (PL) spectra revealed abnormal behavior due to a temperature-induced orthorhombic to the tetragonal phase transition. Four PL emission peaks, A, B, C, and D, were observed in the low temperature regime. Peaks A and B were observed at 756 and 776?nm?at 12?K, and were blue-shifted and disappeared at 130 and 70?K, respectively. Peaks C and D were observed at 789 and 807?nm?at 40?K and were also blue-shifted to 780 and 794?nm?at 100?K. On the other hand, the peak C red-shifted to 799?nm from 100 to 140?K because of an orthorhombic to the tetragonal phase change and was also blue-shifted above 140?K. From the excitation intensity- and temperature-dependent PL results, peaks A and B were assigned to the free-exciton and bound-exciton of the orthorhombic phase crystal, respectively. In addition, peaks C and D were associated with the free-exciton and bound-exciton of the tetragonal phase crystal, respectively. The activation energy of peak C was calculated to be 98?meV from temperature dependence of the PL intensity.     

Energetic and structural characterization of 2‐R‐3‐methylquinoxaline‐1,4‐dioxides (R = benzoyl or tert‐butoxycarbonyl): experimental and computational studies

The gaseous standard molar enthalpies of formation of two 2‐R‐3‐methylquinoxaline‐1,4‐dioxides (R = benzoyl or tert‐butoxycarbonyl), at T = 298.15 K, were derived using the values for the enthalpies of formation of the compounds in the condensed phase, measured by static bomb combustion calorimetry, and for the enthalpies of sublimation, measured by Knudsen effusion, using a quartz crystal oscillator. The three dimensional structure of 2‐tert‐butoxycarbonyl‐3‐methylquinoxaline‐1,4‐dioxide has been obtained by X‐ray crystallography showing that the two N? O bond lengths in this compound are identical. The experimentally determined geometry in the crystal is similar to that obtained in the gas‐phase after computations performed at the B3LYP/6‐311 + G(2d,2p) level of theory. The experimental and computational results reported allow to extend the discussion about the influence of the molecular structure on the dissociation enthalpy of the N? O bonds for quinoxaline 1,4‐dioxide derivatives. As found previously, similar N? O bond lengths in quinoxaline‐1,4‐dioxide compounds are not linked with N? O bonds having the same strength. Copyright © 2007 John Wiley & Sons, Ltd.