Structure, magnetic and thermal properties of Gd2MnTiO6

A new perovskite compound Gd₂MnTiO₆ was synthesized and its crystal structure, magnetic and thermal properties have been investigated. The XRD patterns were refined by the Rietveld method and the refined lattice parameters with the monoclinic space group P2₁/n (No. 14) were a=0.5398 (2), b=0.5704 (2), c=0.7767 (2) nm and β=89.68 (2)°. The antiferromagnetic behavior was observed below 16.0 K and λ-type heat capacity was measured near this temperature.     

Chemical vapour deposition of praseodymium oxide films on silicon: influence of temperature and oxygen pressure

Metal-organic chemical vapour deposition (MOCVD) of various phases in PrO_x system has been studied in relation with deposition temperature (450–750 °C) and oxygen partial pressure (0.027–100 Pa or 0.2–750 mTorr). Depositions were carried out by pulsed liquid injection MOCVD using Pr(thd)₃ (thd = 2,2,6,6-tetramethyl-3,5-heptanedionate) precursor dissolved in toluene or monoglyme. By varying deposition temperature and oxygen partial pressure amorphous films or various crystalline PrO_x phases (Pr₂O₃, Pr₇O₁₂, Pr₆O₁₁) and their mixtures can be grown. The pure crystalline Pr₂O₃ phase grows only in a narrow range of partial oxygen pressure and temperature, while high oxygen pressure (40–100 Pa) always leads to the most stable Pr₆O₁₁ phase. The influence of annealing under vacuum at 750 °C on film phase composition was also studied. Near 90% step coverage conformity was achieved for PrO_x films on structured silicon substrates with aspect ratio 1:10. In air degradation of Pr₂O₃ films with transformation to Pr(OH)₃ was observed in contrast to Pr₆O₁₁ films.     

掺锶量对羟基磷灰石形貌及其荧光特性的影响

采用水热合成法制备了一系列具有不同微观形貌和荧光性能的掺锶羟基磷灰石粉末。通过X射线衍射、红外光谱、电子能谱、扫描电镜和荧光光谱表征样品的物相、形貌及荧光性能。结果表明: 所制备的样品形貌为1~ 3 μm的由微小晶粒聚集而成的球形颗粒, 但随着掺锶量的变化, 组成球形颗粒的微小晶粒形貌会出现较大的差异。 未掺锶羟基磷灰石晶粒形貌为短棒状, 随着掺锶量的增加, 微小晶粒逐渐变为片状而后转变为长棒状。样品能在紫外光(波长351 nm)激发下发出明亮的蓝色荧光(波长375~500 nm, 最强峰位432 nm), 且荧光强度随掺锶量增加先增强, 而后减弱, 在掺锶量为30mol%时达到最大。     

Spectroscopic Investigations of M(CO)5-C60 (M = W, MO) Complexes: Precursors for Metal Fullerides

Photochemical reactions of M(CO)₆ (M = W, Mo) with C₆₀ in solution yield η:²-complexes of M(CO)₅ with C₆₀. The complexes have been characterised by IR, UV/VIS, NMR and DSC. They do not show any orientational ordering down to 12 K and all the infrared bandwidths remain the same down to this temperature. The complexes can be decomposed thermally or photochemically yielding metal fullerides, which show characteristic reduction in peak width in the variable temperature IR spectra due to orientational ordering. Transitions are manifested in calorimetric studies also. Metal → C₆₀ charge-transfer is observed in IR and XPS. A high temperature IR study of the C₆₀-W(CO)₅ complex reveals sequential elimination of the carbonyls yielding MC₆₀. The study shows that carbonyl complexes can be used as precursors to make transition metal fullerides.     

Up-conversion dynamics in GdAlO3:Er single crystal fibre

Green fluorescence has been obtained under continuous laser excitation in the 780–860 nm range in GdAlO₃:Er³⁺. With the help of the Judd-Ofelt treatment we built a model based on population rate equations to describe its time evolution. We found the intensity parameters to be Ω₂ = 2.045 × 10⁻²⁰ cm², Ω₄ = 1.356 × 10⁻²⁰ cm² Ω₆ = 1. 125 × 10⁻²⁰ cm². Even if a two-photon absorption and a looping mechanism are necessary to well describe the dynamics, the main process responsible for up-conversion is energy transfer between erbium ions.     

具有超亲水光催化性能的λ/4-λ/2型两层宽频增透膜的制备和性能研究

以多孔SiO₂/TiO₂复合膜为膜层材料, 采用溶胶-凝胶法制备得到λ/4-λ/2型无峰两层宽频增透膜, 此工艺制备过程简, 单且对膜层折射率要求较低, 镀制两层膜的K9基片在500~700 nm波段维持较高的透过率, 在此区间透过率平均值为99.4%, 在可见光区400~800 nm的平均透过率为99.0%。两层膜表现出优异的超亲水性能, 在无需紫外光照的条件下, 其在0.5 s的水接触角仅为2.2°, 且超亲水性能能够维持超过20 d。同时, 两层膜表现出一定的光催化降解有机污染物的能力。     

Physics and diagnostics of laser ablation plume propagation for high-Tc superconductor film growth

The formation, composition and propagation of laser-produced plasmas used for pulsed laser deposition (PLD) of Y₁Ba₂Cu₃O_7−x have been studied under film growth conditions. Four complementary spatially and temporally resolved in situ diagnostic techniques are applied to characterize the expansion of the laser plume into both vacuum and ambient gases: optical emission and absorption spectroscopy, fast ion probe measurements, and fast photography with a gated, image-intensified charge-coupled detector-array (ICCD) camera system. Transient optical absorption spectroscopy reveals large densities of ground state atoms, ions, and molecules in the plume as well as a slower component to the plume transport than is indicated by the plasma fluorescence and ion current.

Ablation into background gases results in scattering and attenuation of the laser plume. The exponential attenuation of the positive ion flux transmitted through 50–300 mTorr background oxygen is measured and used to define an overall ion-oxygen reaction cross-section σ_i−O2 = 2.3 × 10⁻¹⁶ cm² under the described film growth conditions.

The slowing of the laser plasma and formation of shock structures due to collisions with the ambient gas are described using ion probe measurements and ICCD photographic comparisons of expansion into vacuum and background oxygen. At the pressures used for PLD, distance-time R−t plots derived from the photographs and ion probe waveforms indicate that the higher pressure plume initially expands through the ambient gas in accordance with a drag model (where R = x_f[1 − exp( − βt)]), experiencing little slowing until a visible shock structure forms. Following a transition period, in which the plume appears to have two components, a single-component shock structure propagates in better agreement with a shock, or blast wave (R = ξ₀(E/₀)^1/5t^2/5) model.     

Fracture-resistant ultralloys for space-power applications: Normal-spectral-emissivity and electron-emission studies of tungsten, rhenium, hafnium-carbide alloys at elevated temperatures

A series in this journal on high-temperature properties of “fracture-resistant ultralloys for space-power systems” preceded the present paper: the antecedent publications covered tungsten(W), rhenium(Re) alloys with and without thoria(ThO₂) (W, 23Re; W, 27Re; W, 30Re and W, 30Re, 1ThO₂). This paper reports radiative and thermionic effects of hafnium carbide(HfC) and Re variation in W alloys: normal spectral emissivity(ε_λ) is used in pyrometry to determine the true temperature of a surface. Effective work function (φ_e) is an important consideration in the selection of the electrode materials for high-temperature thermionic energy converters in space-power applications. The _0.535μ, ε_0.65μ and φ_e trends of W, Re, 0.35HfC with 5–20% Re were measured in the range of 1700–2500K. The results indicate that ε_λ decreases with increasing temperatures and Re contents. The presence of HfC produced higher ε_λ values than those of sintered materials with comparable W,Re alloy contents. The results also indicate that φ_e increases with rhenium contents. This can be explained as growth of the potential barrier at the metal, vacuum boundary associated with a volume effect—the decrease in the lattice constant of W.     

氧缺陷Bi2WO6-x可见光催化剂的制备和性能

采用乙二醇溶剂热法原位制备氧缺陷Bi₂WO_6-x催化剂, 利用XRD、SEM、N₂吸附-脱附、XPS、ESR、UV-Vis DRS、PL及电化学方法对样品的理化性能进行了表征, 考察了样品在可见光下(λ > 400 nm)对气相苯的光催化降解性能。结果表明: 乙二醇溶剂热法制备的催化剂具有较大比表面积, 形成了Bi-O_v和W-O_v氧缺陷中心; 缺陷的生成改变了催化剂的能带结构, 缩小其光响应带隙宽度, 并有效抑制了光生电子-空穴对的复合, 催化剂的活性增强。Bi₂WO_6-x降解苯的转化率和矿化率分别为52.5%和80.6%, 是Bi₂WO₆的1.72倍和1.84倍。     

Eu掺杂KNN陶瓷的制备及可调性发光研究

稀土离子掺杂铁电陶瓷是一类新型光致变色材料, 在光开关、光信息存储等领域具有潜在应用价值。本研究采用水热法制备了(K_0.5 Na_0.5)_1-xEu_xNbO₃(KNN:xEu)前驱体粉体, 随后利用高温烧结得到对应陶瓷样品。在465 nm激发下, 观察到615 nm处有强的红色发光, 对应于Eu ³⁺的 ⁵D₀→ ⁷F₂跃迁。通过紫外光照射, KNN:Eu陶瓷从乳白色变为深灰色。随后经过200 ℃加热10 min, 着色陶瓷又变回到初始颜色, 显示出良好的光致变色行为。紫外照射和反复加热循环可以有效调控该陶瓷的发光强度。且经过多次循环之后, 发光强度没有明显衰减。在紫外光照射下, KNN:0.06Eu陶瓷发光强度的可调比(ΔR_t)高达83.9%, 说明发光具有良好的可调性。进而结合发光中心和色心之间的能量转移, 对KNN:Eu陶瓷的光致变色和发光机理进行了解释。     

研磨-焙烧法制备La2O3/BiOCl复合光催化剂及其对高浓度染料降解性能

首先利用沉淀法合成了BiOCl纳米片, 然后利用研磨-焙烧法将La₂O₃纳米颗粒复合到BiOCl纳米片中, 制备了一系列La₂O₃/BiOCl复合光催化剂(La₂O₃: 1wt%、2wt%、4wt%、8wt%)。运用X射线粉末衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、光电子能谱(XPS)、紫外-可见漫反射光谱(UV-Vis DRS)、傅里叶红外光谱(FT-IR)和光致发光(PL)谱等对样品的晶相、光吸收和表面性能等进行了表征。以紫外灯(λ = 254 nm)为光源, 评价了所制备样品光催化降解高浓度染料酸性橙II(40×10^-6)的活性。结果表明, 经过研磨-焙烧后该系列催化剂均具有较好的结晶性能, 同时2~5 nm的La₂O₃纳米粒子粘附在BiOCl纳米片表面。200℃焙烧制备的1wt%La₂O₃/BiOCl催化剂具有丰富的表面羟基, 对染料表现出较强的吸附性能。该催化剂表现了最高的光催化活性, 活性为纯BiOCl的2.4倍。另外, La₂O₃/BiOCl中的La³⁺提供的氧化-还原势阱可能捕获光生电子, 从而阻止了光生电子(e^-)和空穴(h⁺)的复合, 有利于光催化活性的提高。     

Microstructural response to controlled accelerations during the directional solidification of Al-6 wt.% Si Alloys

After establishing steady-state directional growth, aluminum-6 wt.% silicon alloys were subjected to a series of programmed accelerations and decelerations. The response of the primary dendrite arm spacing (λ₁), the eutectic spacing (λ_E), and the primary dendrite trunk diameter (d) to the imposed rate changes were evaluated and compared with results from constant growth velocity experiments. It was found that both λ_E and d responded to a continually changing growth rate, whereas λ₁ did not. The implication of using these microstructural features to characterize solidification histories is discussed.     

Energy Transfer from Photoexcited State of Water Soluble Hexa(Sulfobutyl)fullerene (C60((CH2)4SO3Na)6)

Photophysical properties and reactivities of water-soluble micelle-like C₆₀ derivative, C₆₀((CH₂)₄SO₃Na)₆ (abbreviated as FC₄S), at the excited triplet state were investigated using laser flash photolysis. A new transient absorption band appearing at ca. 700 nm was attributed to the triplet-triplet (T-T) absorption band of FC₄S. This absorption was quenched by O₂ via energy transfer forming singlet oxygen, which was confirmed by its luminescence emission band; the quantum yield was evaluated to be 0.36.     

Study of the pumping regimes in Ti-sapphire and Nd0.5La0.5Al3(BO3)4 powders

Stimulated emission without a cavity was obtained (at λ=800 nm) in powders of Ti-sapphire laser crystal and compared to that in Nd_0.5La_0.5Al₃(BO₃)₄. The formation of a narrow channel in a powder sample by a pumping laser beam was found to be advantageous for stimulated emission in Ti-sapphire and disadvantageous in Nd_0.5La_0.5Al₃(BO₃)₄. The effect of the material volume density on stimulated emission in scattering Nd_0.5La_0.5Al₃(BO₃)₄ was experimentally studied. The experimental results are explained in terms of absorption of pumping light in scattering materials, penetration depth for pumping, and residence time for emission photon in the pumped volume.     

Ultra intense glass laser system and laser–plasma interactions

The 30 TW GEKKO MII short pulse laser (25 J in 0.71 ps at 1 μm) is completed and is used for fast ignitor and particle accelerator research. The photon pressure of the laser at 10¹⁷-10¹⁸ W/cm² pushed the critical and quarter critical density plasmas forward, resulting in the strong red shifts of the second (2ω₀) and three-halves (3ω₀/2) harmonic emissions backscattered from CH or CD planes. A few hundred keV proton and deuteron emissions are also observed from CD planes.     

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.     

Eu3+掺杂Y2O3单分散红色荧光球形颗粒的尺寸可控合成与荧光性能

结合籽晶法和添加矿化剂硝酸铵, 通过均相沉淀合成和后续煅烧实现了(Y, Eu)₂O₃单分散球形颗粒(直径范围110~550 nm)的可控合成。通过XRD、FE-SEM、TEM和PLE/PL分析等手段对产物进行了系统表征。发现采用籽晶法和添加矿化剂硝酸铵可以促进球形颗粒长大。碱式碳酸盐前驱体经600℃煅烧分解为立方晶(Y, Eu)₂O₃, 且经1000℃煅烧后(Y, Eu)₂O₃依然继承球形形貌特征。所得多晶(Y, Eu)₂O₃球形荧光颗粒在242 nm激发下于615 nm处呈现最强红色荧光发射(Eu³⁺的⁵D₀→⁷F₂跃迁)。荧光粉的荧光性能呈现明显的尺寸依存性。增大球形颗粒尺寸减小了荧光寿命(1.15~1.57 ms)和荧光不对称因子[I(⁵D₀→⁷F₂)/I(⁵D₀→⁷F₁)], 但增强了荧光发射强度。     

RADIATION CHEMICAL AND PHOTOPHYSICAL PROPERTIES OF C60(C4H8SO3Na)n IN AQUEOUS SOLUTION: A LASER FLASH PHOTOLYSIS AND PULSE RADIOLYSIS STUDY

Optical absorption studies on aqueous solutions of C₆₀(C₄H₈SO₃Na)_n (n = 4-6) revealed deviation from the Beer-Lambert law in the 250-350 nm region, which is assigned to the formation of solute aggregates at concentrations higher than 1 × 10^-3 mol dm^-3. Dynamic light scattering experiments showed aggregates with an average size of ∼100 nm. The solute has a broad weak fluorescence emission (ϕ_f = 1.8 × 10^-3) in the 450-650 nm region, which remained independent of solute concentration. The broad transient absorption band in the 450-900 nm region (ε₆₆₀ = 2170 dm³ mol^-1 cm^-1), which formed immediately on laser flash photolysis (λ_ex = 355 nm, 35 ps), is assigned to singlet-singlet transition. It decays to a triplet excited state whose absorption is observed to depend strongly on solute concentration. In dilute solutions, an absorption band with λ_max = 590 nm is seen, and at high solute concentration a broad absorption in the 500-900 nm region is observed. The e_aq^- reacts with the solute with a bimolecular rate constant of 1.7 × 10⁸ dm³ mol^-1 s^-1 and forms weak broad absorption bands at 440, 540, 620, 870, 940, and 1020 nm. Isopropanol radicals also react with the solute with a bimolecular rate constant of 2.3 × 10⁸ dm³ mol^-1 s^-1 with the formation of a transient optical absorption spectrum similar to that observed on reaction with e_aq^- and assigned to a solute radical anion. The ^•H and ^-OH radicals react with bimolecular rate constants of 3.2 × 10⁹ and 4.4 × 10⁹ dm³ mol^-1 s^-1, respectively, and form transient absorption bands at 440, 510, and 660 nm. Based on electron transfer studies with suitable electron donor/acceptor substrates, the ranges of the reduction and oxidation potentials of the solute an estimated.     

杂化钙钛矿(HOC2H4NH3)2CuCl4的制备与表征

采用低温溶液法合成了新型层状有序的含有羟基的有机/无机杂化钙钛矿材料(HOC₂H₄NH₃)₂CuCl₄, 采用元素分析、红外光谱、紫外-可见光吸收光谱、X射线衍射和X射线吸收精细结构等手段对其结构与性能进行了表征。结果表明:该材料通过无机框架诱导有机组分有序排列, 形成了规则的层状结构, 有序性高。该杂化钙钛矿材料的分解温度为212℃, 电阻率为2.86×10⁶ Ω·cm, 比不含羟基杂化钙钛矿的电阻率低两个数量级。紫外-可见光吸收光谱显示285 nm左右有一归因于电子从Cl(3p)价带顶跃迁到Cu(4s)导带底而产生的吸收峰。X射线吸收精细结构谱图表明: 二维层状杂化钙钛矿晶体中的Cu²⁺与6个Cl^-形成八面体配位, Cu-Cl键长为0.191 nm, 层间距为1.099 nm。