混合溶剂前体法制备纳米CuO粉体及其性能表征

Nano-CuO was prepared by heating nano-Cu₂(OH)₂CO₃ precursors in different calcination temperatures. The precursor was synthesized from water-alcohol mixed solution of Cu(Ac)₂ using mixed solution of NaOH and Na₂CO₃as precipitants. XRD, FT-IR, TEM, TG-DTA and surface area measurement techniques were used to investigate the properties of the CuO powder. The results show that the spherical, well dispersed nano-CuO powder with the average size of 15 nm and higher catalytic activity for H₂O₂ decomposition was obtained at 300 ℃. With the increasing of calcination temperature, crystal of CuO grows up, agglomeration of the powder becomes heavier and catalytic activity decreases. FT-IR patterns revealed that the vibration fine structure of Cu-O bond in nano-CuO powder disappears and main absorption is red-shifted with the average size of nano-CuO reducing.     

β-二酮镧系元素络合物热行为的研究

本文用差热分析(DTA)、热重法(TG)、微商热重法(DTG)研究了十二种三价镧系金属离子与1,1,1,2,2,3,3七氟-7,7,二甲基-4,6辛二酮的络合物Ln(fod)_3·mH_2O的脱水过程和热分解过程的动力学。其脱水反应发生在100℃附近。络合物最大热分解速率的温度和热分解反应活化能均随中心金属原子——镧系元素原子序变化,呈现“双峰”现象。     

Thermal reduction and reoxidation of spinel-type Cu1−xZnxAl2O4

The thermochemical reactivity of the spinel-type quaternary metal oxide Cu_1–xZn_xAl₂O₄ has been investigated for different Cu:Zn ratios. In oxygen or inert gas atmospheres no considerable reduction is observed. In molecular hydrogen metal selective reduction of the Cu is found at relatively high temperature. The solid reduction product is made up of sintered, poorly dispersed metallic copper on a Zn-Al-O metal oxide support, a potential catalyst for the methanol synthesis. Owing to the measured high reduction temperature leading to the mentioned sintering of the metallic copper, the activity of this system cannot be high.Financial support by the Swiss National Science Foundation under project Nr. 2027933.89 is gratefully acknowledged.     

Thermal behaviour of the copper-substituted cobalt hydroxide fluoride series CuxCo1−x(OH)F

The basic salt cobalt(II) hydroxide fluoride was obtained by partial hydrolysis of a 0.2M solution CoF₂. Mixed Co(II)·Cu(II) hydroxide fluorides with an isomorphic substitution of Co(II) by Cu(II) ions up to 20% were also prepared. XRD data obtained on these compounds indicate that they are single-phase compounds, their X-ray powder patterns being almost identical to the Co(OH)_0.7F_1.3 diagram, with Zn(OH)F-type structure. However, their stoichiometries are very close to Co_1?xCu_x(OH)F (0≤x≤0.2). Thermal analysis studies carried out up to 1273 K in still air or under dynamic vacuum conditions show that in air CoO or a mixture of CoO and CuO is formed as final product. In vacuum, at high temperature, with a Ta heating surface, pure α-Co or a mixture of α-Co and Cu is formed at about 973 K.     

The Influence of the Thermal Behaviour of AgGaS2 on the Crystal Growth Process

Differential thermal analysis has been carried out on AgGaS₂ samples in order to investigate the relationship between the superheating of the melt and the supercooling behaviour of the material leading to an improvement of crystal growth conditions. The knowledge gained will be correlated to the crystal growth experiments which had been carried out by using the gradient freezing method.This revised version was published online in November 2005 with corrections to the Cover Date.     

Zr(WMo)1-x/2VxO8-x/2：多元素同/低价取代立方ZrW2O8结构类型热收缩固溶体的合成、结构与性质

利用酸蒸气水热法合成了Zr(WMo)1-x/2VxO7-x/2(OH)2·2H2O(x=0.04,0.08,0.10,0.14,0.20,0.22,0.26,0.32)四方晶相固溶体。以此为前驱体,通过高温脱水和相转变法合成了立方相Zr(WMo)1-x/2VxO8-x/2(x=0.04,0.08,0.10,0.14,0.20,0.22)固溶体。立方Zr(WMo)1-x/2VxO8-x/2固溶体具有Pa3空间群。Zr(WMo)1-x/2VxO8-x/2的平均晶体结构描述为按照化学计量的ZrV2O7结构与β-ZrWMoO8结构的叠加。ZrV2O7在立方ZrWMoO8中的固溶度为11mol%;立方Zr(WMo)1-x/2VxO8-x/2固溶体的相变温度低于200 K;在200 K～573 K温度范围内具有负热膨胀系数;线热膨胀系数近似为常数。     

Synthesis of HCN Polymer from Thermal Decomposition of Formamide

Prolonged heating of formamide (HCONH₂) at 185°C or 220°C produces a black insoluble product. The FT-IR spectroscopy and the X-ray photoelectron spectroscopy (XPS) suggest that the product has the chemical structure of a polymer of hydrocyanic acid: (HCN)_x. The pyrolysis of (HCN)_x prepared from formamide produces a large amount of gaseous HCN in a wide range of temperatures together with ammonia (NH₃) and isocyanic acid (H─N─C═O).

During the thermal decomposition of formamide to produce (HCN)_x, the volatile products evolved were monitored with gas phase infrared spectroscopy. At 185°C, the gaseous product released were CO₂, CO and NH₃ while at 220°C, also HCN was detected. In both cases, a white sublimate was collected in the upper part of the reaction vessel. It consists of ammonium carbamate and its hydrolysis products ammonium carbonate and hydrogen carbonate. It is therefore possible to synthesize the polymer of hydrocyanic acid (HCN)_x starting from formamide avoiding to handle the dangerous hydrocyanic acid.     

Synthesis and properties of the Co7Se8−xSx and Ni7Se8−xSx solid solutions

We report the synthesis and elementary properties of the Co₇Se_8−xS_x (x=0-8) and Ni₇Se_8−xS_x (x=0-7) solid solutions. Both systems form a NiAs-type structure with metal vacancies. In general, the lattice parameters decrease with increasing x, but in the Ni₇Se_8−xS_x system c increases on going from x=5 to 7. Magnetic susceptibility measurements show that all samples exhibit temperature-independent paramagnetism from 25-250 K. Samples within the Co₇Se_8−xS_x system, as well as Ni₇Se₈ and Ni₇SeS₇, were found to be poor metals with resistivities of ∼0.20 and ∼0.06 mΩ cm at 300 K, respectively. The Sommerfeld constant (γ) was determined from specific heat measurements to be ∼13 mJ/mol_CoK² and ∼7 mJ/mol_NiK² for Co₇Se_8−xS_x and Ni₇Se_8−xS_x, respectively.     

Thermal behavior of ternary Sm2Fe17Nx magnets

The Mössbauer spectra of Sm₂Fe₁₇N_x, prepared by the nitrogenation of Sm₂Fe₁₇ powders in an ammonia and hydrogen atmosphere, were observed at elevated temperatures to shed light on the thermal behavior of nitrogen in the compounds Sm₂Fe₁₇N_x. It was found that there were large differences in thermal behavior between the starting Sm₂Fe₁₇, crystalline Sm₂Fe₁₇N_x (x≈1.7) and amorphous Sm₂Fe₁₇N_x(x～7). The thermal decomposition behavior of Sm₂Fe₁₇N_3.2, developed as one of the most promising hard magnetic materials, was found to be different under different atmospheres.     

Thermal Behaviour of Some Polyhydrocarboxylic Coordination Compounds with Neodium

New Nd-Co based polynuclear coordination compounds containing as ligand polyhydrocarboxylic acid as tartaric, malic and gluconic acids were prepared, namely: [NdCo(tart)₃]·4H₂O, (NH₄)[NdCo_0.5Cu_0.5(tart)₃]·4H₂O, (NH₄)[NdCo(malic)₃]·4H₂O, (NH₄)[NdCo_0.5Cu_0.5(malic)₃]·4H₂O, [NdCo(gluc)₄]·4H₂O and [Nd₂CoCu(gluc)₇]·5H₂O. A comparison between the thermal behaviour of the studied polynuclear coordination compounds concerning thermal stability and thermal decomposition stoichiometry was inferred. Oxalic and malonic intermediates were identified at about 300°C in the thermal decomposition of tartaric and malic compounds. In all the decomposition processes at about 400°C the presence of oxocarbonate is shown. The residual products are mixed oxides of perovskite type. This revised version was published online in August 2006 with corrections to the Cover Date.     

超细CeM(M=Mg,Sr)Ox复合氧化物的性能研究

采用聚合物前驱体法首次合成了超细粒子CeM(M=Mg，Sr)O_x复合氧化物粉体。通过XRD、TEM、BET等技术对合成的粉体进行了表征，结果表明CeO₂与碱土金属形成的CeM(M=Mg，Sr)O_x新粉体材料比表面积为66～69 m²·g^-1，经800 ℃、1 000 ℃焙烧2 h后，粉体平均晶粒仍保持在10～20 nm，基本不发生团聚现象，具有较好的抗烧结能力。用甲烷催化燃烧为模型反应，发现该粉体催化剂具有很高的催化活性，优于单组分CeO₂。     

Thermal Behaviour of Silver-Filled Epoxy Adhesives. Technological implications in microelectronics

One-component silver-filled epoxy adhesives electrically conductive with low extractable ionic content have been used in microelectronics for attach applications. For the specific application described here there was evidence showing that adhesive polymerisation was not complete with negative consequences for the electronic devices. The present study aimed at understanding the causes of such disadvantages and setting up the best conditions to make the epoxy adhesive perfectly suitable for the required applications. The work was carried out mainly by means of differential scanning calorimetry (DSC) and with the help the dynamic mechanical thermal analysis (DMTA) technique. The study succeeded in determining that the technological problems were due to incomplete polymerisation that caused solvent and monomer retention. These residues produced a leakage of the insulating properties of some capacitors present in the devices jeopardising the sensor working. Moreover, the study also showed that it was possible to avoid these difficulties adjusting the polymerisation temperature to 130°C and respecting curing time of 3 h: with these new curing conditions excellent results were achieved. This revised version was published online in July 2006 with corrections to the Cover Date.     

Ce1-xTbxO2-δ复合氧化物氧缺位的拉曼光谱研究

采用溶胶-凝胶法制备了Ce1-xTbxO2-δ复合氧化物, 利用不同Raman激发波长(514和785 nm), 结合X射线衍射(XRD)、氢气-程序升温还原(H2-TPR)和氧气-程序升温脱附(O2-TPD)表征, 考察了Ce1-xTbxO2-δ复合氧化物在O2, He和H2气氛下氧缺位的原位变化情况和CeO2的F2g特征Raman峰位的偏移. 实验结果表明, 随着Tb掺杂量的提高, 由于晶胞收缩使得CeO2的F2g特征Raman振动峰发生蓝移. 514 nm Raman激发波长反映了催化剂的表面信息, 而785 nm激发波长反映了整体信息. 正是由于表面和整体变化的不一致, 造成原位Raman实验过程中氧缺位浓度变化趋势的不同. 在He和H2气氛下, 由于温度升高时伴随着Ce1-xTbxO2-δ中O2气的脱出, 使复合氧化物的微观结构发生改变, 以致Ce0.9Tb0.1O2-δ中的氧缺位浓度(A587/A465)在785 nm激发波长下出现先升高后下降的现象.     

Ozone Production in the Positive DC Corona Discharge: Model and Comparison to Experiments

A numerical model of ozone generation in clean, dry air by positive DC corona discharges from a thin wire is presented. The model combines the physical processes in the corona discharge with the chemistry of ozone formation and destruction in the air stream. The distributions of ozone and nitrogen oxides are obtained in the neighborhood of the corona discharge wire. The model is validated with previously published experimental data. About 80% of the ozone produced is attributed to the presence of excited nitrogen and oxygen molecules. A parametric study reveals the effects of linear current density (0.1–100 A/cm of wire), wire radius (10–1000 m), temperature (300–800 K) and air velocity (0.05–2 m/s) on the production of ozone. The rate of ozone production increases with increasing current and wire size and decreases with increasing temperature. The air velocity affects the distribution of ozone, but does not affect the rate of production.     

A novel route to synthesize cubic ZrW2−xMoxO8 (x=0-1.3) solid solutions and their negative thermal expansion properties

Cubic ZrW_2−xMo_xO₈ (c-ZrW_2−xMo_xO₈) (x=0-1.3) solid solutions were prepared by a novel polymorphous precursor transition route. X-ray diffraction (XRD) analysis reveals that the solid solutions are single phase with α- and β-ZrW₂O₈ structure for 0?x?0.8 and 0.9?x?1.3, respectively. The optimum synthesis conditions of ZrWMoO₈ are obtained from differential scanning calorimetry-thermal gravimetric analysis (DSC-TGA), XRD and mass loss-temperature/time curves. Following the above experience, the stoichiometric solid solutions of c-ZrW_2−xMo_xO₈ (x=0-1) are obtained within 1 wt% of mass loss. The relationships of lattice parameters (a), phase transition temperatures (T_c) and instantaneous coefficients of thermal expansion (α_i) against the content x of Mo are discussed based on the variation of order degree parameters of ZrW_2−xMo_xO₈.     

CuxC60薄膜紫外-可见吸收光谱研究

近来,有关C60的研究主要集中在有关晶格动力学、电子结构和MxC60（M代表碱金属或碱土金属）的超导电性研究。但由于MxC60在大气中不能稳定存在,制约了MxC60的深入研究和实际应用。最近,Masterov等人报导了他们对Cu/C60的超导特性研究,认为其转变温度Tc在80－120K之间,这个转变温度比现有的MxC60的转变温度Tc-40K）要高得多,但有关更进一步的研究未见报导,因此,我们拟对CuxC60体系作较为详尽的研究,这对于进一步研究其超导机理是有必要的,本工作是在成功地制备了CuxC60薄膜的基础上,对其紫外－可见吸收光谱进行了初步的研究。定性地分析了CuxC60薄膜的电子结构,利用XPS谱分析了CuxC60薄膜中Cu的化学价态。     

共沉淀法制备负热膨胀性ZrW2O8粉体及其粒径控制初探

Negative thermal expansion (NTE) material ZrW₂O₈ powders were synthesized using co-precipitation route. The precursor of ZrW₂O₈ was studied by Thermogravimetric and differential scanning calorimetry (TG-DSC). The structure and morphology of the resulting powders were characterized by Powder X-ray diffraction (XRD) and Scanning electron microscopy (SEM), respectively. The results showed that the samples were single phase of α-ZrW₂O₈ with regular shape. High temperature X-ray diffraction measurement indicated that the thermal expansion coefficient of ZrW₂O₈ was -10.35 × 10^-6 K^-1 in the temperature range from room temperature to 150 ℃, -3.08 ×10^-6 K^-1 from 200 ℃ to 600 ℃ and the average value was -5.38 × 10^-6 K^-1. At the same time, polyethylene glycol (PEG) was used as dispersant to primary control the size of ZrW₂O₈.     

CeO2/ZnO复合纳米管的制备及其光催化性能的研究

用纳米CeO2掺入ZnO纳米管制备了CeO2/ZnO复合纳米管,考察了复合纳米管的光学及其光催化性能,并运用X射线衍射、透射电镜、比表面积测定和紫外-可见漫反射光谱等技术对样品进行了表征.结果表明,与ZnO纳米管相比,CeO2/ZnO复合纳米管的比表面积虽有所降低,但光催化活性有所提高,随着复合纳米CeO2量的增加,催化剂的光催化活性相应降低,太阳光下CeO2/ZnO复合纳米管对甲基橙溶液也有较高的催化活性.     

掺入Ni2+的LiCoO2结构与电化学性能的研究

对LixCo1-yNiyO2-δ系列化合物（x=1）,0＜y＜0．5）的合成条件和它们的非完整结构及其电化学性能间的关系进行了较系统的研究,结果表明Ni2＋掺入ABO2型的化合物中,在取代了Co离子的同时,也以一定的几率分布在A位．并使结构中的A,B和O位都出现一定程度的空位在这种非完整结构中,Co离子具有超高常的平均价态,同时也使Li（Ni）－O和O－O的间距加大,提高了该系列化合物的电导及电池的比容量．     

Thermal Analysis of Pigments Based on CeO2

The synthesis of new compounds based on CeO₂ is investigated in our laboratory. The main attention is directed to the preparation of these compounds which can be used as pigments for colouring of ceramic glazes. The synthesis of these compounds is based on high-temperature calcination of starting oxides. The optimum conditions for the syntheses of compounds have been estimated and the pigments prepared have been evaluated from the standpoint of their structure. This revised version was published online in July 2006 with corrections to the Cover Date.