Ag glasses based on Zn-phosphate

The partial substitution of Zn²⁺ for Ag⁺ in Ag₄P₂O₇ leads to the formation of a wide glassy domain of composition [Ag₄P₂O₇] _(1−y) [Zn₂P₂O₇] _(y) with 0.20y0.87. The introduction of AgI in these materials results in a new series of glasses of formula [(Ag₄P₂O₇)_(1−y) (Zn₂P₂O₇)_(y)] _(1−X) [AgI] _(x), which domain for the composition y = 0.25 corresponds to 0x 0.64. The structure as well as the thermal and electrical properties of these materials are compared with those of the [AgPO₃] _(1−X) [AgI] _(x) and [Ag₄P₂O₇] _(1−x) [AgI] _(x) glasses.     

Arylation of [60]Fullerene with Br2/FeCl3/PhH: Formation of C58 Derivatives via CO Loss

Heating a mixture of [60]fullerene, bromine, ferric chloride and benzene under reflux for 24 h products a range of phenylated [60]fullerene derivatives. The main product is C₆₀Ph₅H but other components identified by mass spectrometry (and in some cases separated by HPLC) are: C_6oPh_n(n = 4, 6, 8, 10, 12), C₆₀Ph_nO₂(n = 4, 6, 8, 10, 12), C₆₀Ph_nOH (n = 7, 9, 11), C₆₀Ph_nH₂ (n = 4, 10), C₆₀Ph₄H₄, C₆₀Ph₅H₃, C₆₀Ph_n0₂H (n = 5, 9), C₆₀Ph₄C₆H₄O₂, C₆₀Ph₉OH₃, and C₆₀Ph₁₁ O₃H₂. In the corresponding reaction with toluene, the crude reaction mixture contained C₆₀(MeC₆H₄)₄ as a main product; C₆₀(ClC₆H₄)₅H was obtained from the reaction with chlorobenzene. Formation of these derivatives is believed to involve radical bromination of the fullerene, followed by electrophilic substitution of the hatogenofullerene into the aromatic, accompanied in some case by hydrolysis, elimination and epoxide formation; oxidation may also introduce ketone/dioxetane functionality. The EI mass spectra of C₆₀Ph₄O₂ and C₆₀Ph₈O₂show degradation to C₅₈Ph_n (n = 0-8), having structures believed to be related to the pseudofollerenes C₆₈Ph_n (n = 0-8) reported recently. These results suggest that some derivatisations of fullerenes confer stability, due to the relief of strain.     

On the formation of radiation-induced defects in fluoroaluminate glasses

The spectra of electron paramagnetic resonance (EPR) of fluoroaluminate glass (FAG-36) based on mineral usovite Ba₂CaMgAlF₁₄ were studied. The paramagnetic centers responsible for EPR signals were induced by ion bombardment of the substrates prepared from this glass. The N⁺, O⁺, Ar⁺ and Pb + ions with energy E = 150 keV were used. The integrated dose D was 2 × 10¹⁶ ions/cm². It is shown by means of isochronal anneal experiments and computer simulation of the EPR spectra that they contain four components: broad Gaussian line (GL) with g = 2.016 and σ oscillating in the range 30–40; two anisotropic spectra with g_z = 2.016, g_y = 2.009; g_x = 2.001 (FA₁) and g_z = 2.045; g_y = 2.010; g_x = 1.98 (FA₂) as well as narrow isotropic line of Lorentzian shape with g = 2.0025 and ΔH = 0.6 mT. The comparison of obtained results with literature data for γ-irradiated fluoride glasses and ion-implanted oxide glasses of different compositions permitted to conclude that GL is due to hole defects typical of fluoride glasses and localized on several anions (fluorines and oxygen(s)); anisotropic FA₁- and FA₂-spectra are attributed to molecular 0₂⁻-ions, and narrow isotropic signal is supposedly assigned to big molecular ions (O₂O⁻, 0₄⁻ , CO⁺, CO⁻) located in voids of damaged implantation layer.     

高质量水系钠离子电池正极Fe4[Fe(CN)6]3的合成及其电化学性能

采用水热法合成高质量的Fe₄[Fe(CN)₆]₃(HQ-FeHCF)纳米材料, 并对材料进行X射线衍射(XRD), 扫描电子显微镜(SEM), 透射电子显微镜(TEM)和热重分析测试(TGA)等表征。结果表明：Fe₄[Fe(CN)₆]₃呈规则立方体, 颗粒大小约500 nm, 属面心立方结构。Fe₄[Fe(CN)₆]₃在NaClO₄-H₂O-聚乙二醇电解液中1C、2C、5C、10C、20C、30C和40C的容量分别为124、118、105、94、83、74和64 mAh·g ^-1, 表现出优异的倍率性能; 以5C倍率循环500次, 容量保持率接近100%, 表现出极佳的循环稳定性。以Fe₄[Fe(CN)₆]₃和磷酸钛钠分别为正负极的全电池工作电压高达1.9 V, 能量密度可达126 Wh·kg ^-1; 以5C倍率恒流充放电测试140次后全电池容量保持率为92%, 且库伦效率始终接近100%。     

Spectroscopic Evidence for Anionic Coordination Complexes of the Transition Metals with C70 and the Higher Fullerenes C76, C78, C82, C84, C86, C90, and C92

The carbonylate anions [M(CO)₅]^- (M = Mn, Re), [Co(CO)₄]^-, [CpFe(CO)₂]^-, and [CpM(CO)₃]^- (M = Mo, W) react with C₇₀ via single electron transfer processes to give, respectively, the corresponding 17-electron, metal-centered radicals Co(CO)₄, M(CO)₅ (M = Mn, Re), CpFe(CO)₂, and CpM(CO)₃ (M = Mo, W) in addition to the radical anion C₇₀^-. In secondary thermal or photochemical processes, the metal-centered radicals Co(CO)₄ and M(CO)₅ (M = Mn, Re) combine with the C₇₀^- to form the new η²-C₇₀ complexes [Co(CO)₃(η²-C₇₀)]^- and [M(CO)₄(η²-C₇₀)]^-. However, the metal-centered radicals CpM(CO)₃ (M = Mo, W) require photolysis to react with C₇₀^- to form [CpM(CO)₂(η²-C₇₀)]^-, whereas neither thermolysis nor photolysis induces reaction between CpFe(CO)₂ and C₇₀^-. The photochemical reaction of [Mn(CO)₅]^- with a mixture of higher fullerenes known to contain at least C₇₆, C₇₈, C₈₄, C₈₆, and C₉₀ resulted similarly in the formation of the higher fullerene complexes [Mn(CO)₄(η²-C_n)]^- (n = 76, 78, 80, 82, 84, 86, 88, 90, 92, 96, and 98), all identified using electrospray mass spectrometry.     

Sc3+和Ru4+联合取代BZN基陶瓷结构与介电性能的研究

采用传统的固相反应法制备致密的Bi_1.4Sc_0.1ZnNb_1.5-xRu_xO₇陶瓷样品, 研究Sc³⁺, Ru⁴⁺共同替代对Bi₂O₃-ZnO-Nb₂O₅陶瓷的相结构、晶体化学特性和介电性能的影响。结果表明: 当掺杂量x≤0.055 mol时, 样品保持单一的立方焦绿石结构。当掺杂量x=0.055 mol时, X射线衍射峰强度变弱, 峰形变宽。随着掺杂量的增加(0≤x≤0.04 mol), 陶瓷样品的晶格常数a和A位离子与第7个氧O′平均键长R_(A-O')逐渐减小, 结晶化学参数键价和AV(O')[A₄]增大, AV(O)[A₂B₂]减小, 48f(O)偏移量ξ增加。室温下样品的介电常数随着掺杂量的增加而减小, 介电损耗逐渐增加, 介电松弛特征减弱。低温下样品呈现明显的弛豫现象, 峰值温度T_m随着掺杂量的增加向高温方向移动。利用修正的Curie-Weiss(C-W)公式对样品ε_r-T曲线进行最小二乘法拟合, 得出样品的弛豫度γ由R0样品的1.57减小到R40样品的1.33。     

Field-lowering carrier excitation in cadmium arsenide thin films

Cadmium arsenide is a II–V semiconductor which exhibits n-type intrinsic conductivity with high mobility up to μ_n=1.0–1.5 m²/V s. Potential applications include magnetoresistors and both thermal and photodetectors, which require electrical characterization over a wide range of deposition and measurement conditions. The films were prepared by vacuum evaporation with deposition rates in the range 0.5–6.0 nm/s and substrate temperatures maintained at constant values of 20–120°C. Sandwich-type samples were deposited with film thicknesses of 0.1–1.1 μm using evaporated electrodes of Ag and occasionally Au or Al. Above a typical electric field F_b of up to 5×10⁷ V/m all samples showed instabilities characteristic of dielectric breakdown or electroforming. Below this field they showed a high-field conduction process with logJ∝V^1/2, where J is the current density and V the applied voltage. This type of dependence is indicative of carrier excitation over a potential barrier whose effective barrier height has been lowered by the high electric field. The field-lowering coefficient β had a value of (1.2–5.3)×10⁻⁵ eV m^1/2/V^1/2 which is reasonably consistent with the theoretical value of β_PF=2.19×10⁻⁵ eV m^1/2/V^1/2 expected when the field-lowering occurs at donor-like centres in the semiconductor (Poole–Frenkel effect). For thinner films Schottky emission was more probable. The effects of the film thickness, electrode materials, deposition rate, and substrate temperature on the conductivity behaviour are discussed.     

区熔法制备金属硫化物Ag2S及其热电性能研究

金属硫化物Ag2S具有优异的物理化学性能,在催化、传感及光电子等领域具有广阔的应用空间.本工作利用一种区熔技术制备了尺寸为?18 mm×50 mm的Ag2S并对其潜在热电性能进行了研究.Ag2S在450 K以下具有标准的 α-Ag2S单斜P21/c结构,450 K以上发生相变成为立方 β-Ag2S相.Ag2S在300～...     

Pyrolytic Trifluoromethylation of [76]-, [78]-, [84]-, and Aza[60]Fullerenes with Silver Trifluoroacetate; Evidence for Coordination of Fullerenes to Silver

Pyrolytic trifluoromethylation of [76], [78], [84], and aza[60]fullerenes with silver trifluoroacetate at 300°C results in extensive polyaddition of up to 18, 18, 20 and 20 CF₃ groups, respectively. In contrast to trifluoromethylation of [60]- and [70]fullerenes that give a full range of derivatives ranging upwards from C_n(CF₃)₂, [76]-, [78]-, and [84]-fullerenes only give C_n(CF₃)_6-18 derivatives, largely in the 10-12 CF₃ range; reaction with [76]fullerene is accompanied by formation of C₆₀(CF₃)₆ attributed to cage fragmentation. For aza[60]fullerene the hexa-addition level dominates, in contrast to its other reactions which give predominantly penta-addition products. All the compounds showed peaks at 1256±2 and 1180-1190 cm^-1, due to the CF₃ group, and peaks in this region are shown also by the soluble extract obtained on trifluoromethylation of nanotubes. As in trifluoromethylation of [60]- and [70]-fullerenes, the products obtained initially are involatile, attributed to formation os silver complexes; these are decomposed on subsequent solution in toluene. Mixed isomeric trifluoromethylated C₆₀F₈ derivatives viz. C₆₀F₇CF₃, C₆₀F₆(FG₃)₂, C₆₀F₅(CF₃)₃ and C₆₀F₄(CF₃)₄, and C₆₀F₄CF₃CF₂CF₃ (a C₆₀F₆ derivative) have been isolated from fluorination of [60]fullerene with MnF₃/K₂NilF₆ at 510°C.     

Er2O3掺杂Gd2(Zr0.8Ti0.2)2O7陶瓷的物理性能

用固相反应法制备(Gd_1-xEr_x)₂(Zr_0.8Ti_0.2)₂O₇(摩尔分数x=0,0.2,0.4)陶瓷并测试其晶体结构、显微形貌和物理性能,研究了Er₂O₃掺杂的影响。结果表明,(Gd_1-xEr_x)₂(Zr_0.8Ti_0.2)₂O₇陶瓷具有立方烧绿石结构,显微结构致密,在室温至1200℃高温相的稳定性良好;Er³⁺掺杂降低了陶瓷材料的热导率和平均热膨胀系数,当x=0.2时,其1000℃的热导率最低(为1.26 W·m^-1·k^-1)。同时,Er³⁺掺杂还提高了这种材料的硬度和断裂韧性。     

Structural and electronic properties of C3N4−nPn (n=0,1,2,3,4)

First principles electronic structure method based on the density functional theory and the local density approximation is used to investigate the structural and electronic properties of C₃N_4−nP_n (n=0,1,2,3,4). It is found that the N-rich compounds energetically favor structures with sp² bonding, while the pseudocubic structure which is characterized by sp³ bonding is preferred by the P-rich compounds. Even though C₃N₄ is a wide-gap semiconductor, the band gap of C₃N_4−nP_n decreases rapidly when N is gradually substituted with P, and the P-rich compounds are predicted to be metallic or narrow-gap semiconductors.     

YVO4∶Eu3+,Bi3+红色荧光粉的水热合成及其荧光性能

以Y₂O₃、Eu₂O₃、Bi(NO₃)₃·H₂O、浓HNO₃、偏钒酸铵、氨水、无水乙醇和一缩二乙二醇为原料,采用聚乙烯吡咯烷酮(PVP)辅助水热法合成YVO₄: Eu³⁺, Bi³⁺纳米颗粒。使用X射线衍射(XRD)、扫描电镜(SEM)、红外光谱(IR)和荧光光谱(FL)等手段对产品进行了表征和分析。结果表明：合成的样品为YVO₄: Eu³⁺, Bi³⁺纳米颗粒,均具有四方晶相结构,其微结构随反应溶液的的pH值变化。YVO₄: Eu³⁺, Bi³⁺纳米颗粒在619 nm处有较强的红光发射(电偶极跃迁⁵D₀→⁷F₂),在594 nm有较弱的橙光发射(磁偶极跃迁⁵D₀→⁷F₁)。随着Eu/Bi比值的增大材料的荧光先增强后减弱,在Eu/Bi比值为5时样品的红光发射最强。溶液的pH值影响YVO₄: Eu³⁺, Bi³⁺纳米晶的发光强度,其中pH值为10时的样品其红光发射最强。并探讨了YVO₄: Eu³⁺, Bi³⁺纳米晶的发光机理。     

Impact fatigue properties of epoxy resin filled with SiO2 particles

Impact fatigue tests were carried out on epoxy resin filled with SiO₂ particles. The effects of the percentage of SiO₂ particles and the impact cyclic loading frequency on the impact fatigue strength was investigated. The micromechanism of impact fatigue failure was examined and correlated with the morphology of the fracture surface. The impact stress amplitude, σ_t, can be estimated by the formula, σ₂(N_f · Te)^mt = D_t where (N_f· Te) is the cumulative duration time, and mt and D_t, are parameters describing impact fatigue characteristics. The impact fatigue strength and the static strength are governed by the percent of SiO₂ particles. Crack initiation under monotonie cyclic impact loading was attributed to decision of the epoxy-SiO₂ interface. Unstable crack propagation occurs when the crack passes through the SiO₂ particles.     

Highly conducting Langmuir-Blodgett films of the TMTTF-CnTCNQ system

Highly conducting Langmuir-Blodgett (LB) films of the tetramethyltetrathia-fulvalene- alkyltetracyanoquinodimethane (TMTTF-C_n TCNQ, where C_n represents C_nH_2n+1) system are reported. The electron affinities of the acceptors C_nTCNQ (n=14, 18 or 22) in solution are almost the same and lie between those of TCNQ and dimethylTCNQ. These TCNQ derivatives form solid charge transfer complexes with TMTTF. The limiting areas of the complexes, normalized to the number of TCNQ derivatives at the air-water interface, are almost the same irrespective of the donor-to-acceptor ratio and of the length of the alkyl chain, indicating that the areas are governed by the TCNQ moiety. The monolayers of TMTTF-C_n TCNQ (n=14 or 18) are transferred onto solid substrates as LB films. Polarized UV-visible absorption spectra indicate that the long axis of TCNQ is parallel to the film surface. These LB films exhibit lateral conductivities as high as 0.4 S cm^-1 and 0.1 S cm^-1 when n=14 and n=18 respectively.     

高效CdS量子点敏化B/S共掺杂纳米TiO2太阳能电池的制备及光电性能研究

采用水热法制备硼硫(B/S)共掺杂纳米二氧化钛(B-S-TiO₂), 并配制成浆料, 利用丝网印刷技术在FTO导电玻璃上制备B-S-TiO₂薄膜; 用化学浴沉积(CBD)法制备了CdS量子点敏化B-S-TiO₂薄膜电极, 并用X射线衍射(XRD)、电子显微镜(TEM)、元素分析能谱(EDS)和紫外-可见光谱对其进行表征分析; 结果显示: B/S共掺杂不会改变TiO₂的晶型, 掺杂后的TiO₂吸收边带发生明显红移, 吸收强度显著增强; 同样用化学浴沉积的方法制备NiS工作电极, 用改性的聚硫化物((CH₃)₄N)₂S/((CH₃)₄N)₂S_n)电解液, 组装CdS量子点敏化硼硫(B/S)共掺杂纳米二氧化钛(B-S-TiO₂)太阳能电池, 并测试电池光电性能。测试结果表明, 在AM1.5G的照射下, 电池的能量转化效率(η)由3.21%增大到3.69%, 提高了14.9%, 电池获得高达 (V_oc)1.218 V的开路电压和3.42 mA/cm²的短路光电流(J_sc), 以及高达88.7%的填充因子(ff)。     

Optical properties of a-(Se70Te30)100−x(Se98 Bi2)x thin films

Measurements of optical constants (absorption coefficient, refractive index, extinction coefficient, real and imaginary part of the dielectric constant) have been made on a-(Se₇₀Te₃₀)_100−x (Se₉₈Bi₂)_x thin films (where x=0, 5, 10, 15 and 20) of thickness 2000 Å in the wavelength range 450–1000 nm. It is found that the optical bandgap decreases with the increase of Se₉₈Bi₂ concentration in the a-(Se₇₀Te₃₀)_100−x(Se₉₈Bi₂)_x system. The value of refractive index (n) decreases, while the extinction coefficient (k) increases with increasing photon energy. The results are interpreted in terms of concentration of localized states varying effective Fermi level.     

硬脂酸盐熔融法合成(Y,Lu)AG:Ce荧光粉及荧光性能研究

采用硬脂酸盐熔融新方法合成了[(Y_1-xLu_x)_1-yCe_y]₃Al₅O₁₂固溶体荧光粉(x=0’0.5, y=0.005’0.03), 并通过XRD、SEM、BET和PL-PLE等方法对该荧光粉进行了表征。结果表明, 纯相石榴石在800℃的低温下即可生成, 而不经过YAM和YAP中间相。煅烧所得[(Y_1-xLu_x)_1-yCe_y]₃Al₅O₁₂ 荧光粉具有良好的均一性和分散性, 并在455 nm蓝光激发下于544 nm附近呈现最强黄光发射。粉体的发光强度随煅烧温度升高而增大, 归因于结晶度提高和表面缺陷减少。发现Ce³⁺的荧光猝灭浓度为1.5%, 猝灭机制为Ce-Ce间的交换相互作用和晶格缺陷。发现发射峰位随Ce³⁺含量增加而红移, 而最强激发峰和发射峰随Lu³⁺含量增大而蓝移, 归因于Ce³⁺离子5d激发态能级重心移动和晶体场劈裂的共同作用。     

Calculation of the ferrite volume in some dual phase steels

The relation between the γ/γ + boundary temperature, T, and the equivalent values of [Cr] and [Ni], as well as the variation of the ferrite volume, V_f, with the temperature in + γ dual-phase steels have been studied. With the aid of a computer, the regressive expressions derived from the experimental results are: T (°C) = T₃ + 21.2 [Cr] − 15.8 [Ni] + 223; V_f (%) = 0.715 exp [0.015(T − T_δ)] − exp[0.015(T_c − T_δ)] + 1.85 exp [0.0083(T − T_c]).     

Development of Bi-oxide superconducting tapes and coils

We have developed Bi-2212 and 2223 tapes. For Bi-2212, two double stacked pancake type coils were fabricated using Bi-2212/Ag tapes prepared by a combination of the continuous dip-coating process and melt-solidification. A small coil (13 mm inner bore, 46.5 mm outer diameter) was inserted in a conventional superconducting magnet system. In a bias field of 20.9 T, the generated field of the coil was 0.9 T, at an I_c of 310 A (criterion 10⁻¹³ Ωm) at 1.8 K. Thus, the superconducting magnet system achieved the generation of a field of 21.8 T in the full superconducting state. A large coil (20 mm inner bore, 94 mm outer diameter) generated a field of 2.6 T (I_c = 385 A (10⁻¹³ Ωm)) at 4.2 K and 1.53 T (I_c = 225 A (10⁻¹³Ωm)) at 20 K in self-field. For Bi-2223, tapes were prepared by the powder-in-tube technique using Ag-10% Cu-x%M (x = 0–1.0, M = Ti, Zr, Hf or Au) alloy sheaths. The high J_c values of 5–7 × 10⁴ A cm⁻² at 4.2 K and 14 T were obtained for the tapes doped with x = 0.03–0.1 at.% Ti, 0.1 at.% Zr, 0.1 at.% Hf or 0.3% Au. These tapes have a modified Bi-2223 grain structure at the sheath/core interface and also a dense and more aligned microstructure, resulting in higher J_c values.     

Thermal conductivity of BaWO4 single crystal

Barium tungstate (BaWO₄) single crystal has been grown using Czochralski technique. It belongs to the scheelite structure, forming the space group I4₁/a at room temperature and the primitive cell contains two formular units. The thermal expansion, specific heat and thermal diffusivity were measured, and then the thermal conductivity was calculated. These results show that BaWO₄ possesses large anisotropic thermal expansion and its thermal expansion coefficients are _a = 1.10 × 10⁻⁵/K, _b = 1.08 × 10⁻⁵/K, and _c = 3.51 × 10⁻⁵/K in the temperature range from 303 to 1423 K. However, its thermal conductivity shows small anisotropic in the temperature range from 297 to 563 K and even displays isotropic at about 428 K. The calculated thermal conductivities are 2.59 and 2.73 W m⁻¹ K⁻¹ at room temperature, along [1 0 0] and [0 0 1] directions, respectively.