具有共轭主链聚合物单晶的低温电导测定

用自行组装的低温电导测定装置对77～373K温度范围内双(对甲苯磺酸)-2,4-己二炔-1,6-二醇酯(TS)及其聚合物PTS单晶体的暗电导进行了测定。在c方向上相应于它们低温相转变的温度,TS和PTS的电导均出现异常,此时TS的相变温度是163K和208K。     

在确定的热力学状态下测量气体导热系数与黏度

气体的导热系数和黏度是重要的热物性参数,其数值大小取决于所处的热力学状态。在目前的导热系数和黏度主要测量方法中,待测工质在测量时需经历非定常的过程或处于具有物性梯度的非平衡态之下,使得待测工质的物性在时间或者空间上不处于一个确定的热力学状态。本文利用圆柱定程干涉法,通过分析气体导热系数和黏度导致的声波能量耗散,结合气体输运理论中对稀疏气体的描述,探索了在确定的热力学状态下同时测量气体导热系数和黏度的方法,并以氩(Ar)为例进行了实验验证。测量结果与已有文献一致性较好,初步证实了方法的可行性。     

纳米LaF3块体材料常温离子电导率的研究

采用水溶液直接沉淀法成功制备了LaF3纳米粉体.用透射电子显微镜(TEM)观察了粒子形貌及粒度,粒子呈球形,粒径范围在10～20 nm之间,粉体单分散性良好.用X射线衍射(XRD)分析得到的平均粒径16.7 nm.采用真空高压固结法在真空度10-4 Pa条件下常温加压至1 GPa制备了纳米LaF3块体材料.采用交流阻抗谱研究了纳米LaF3的室温离子电导率,发现纳米LaF3的室温离子电导率(10-5 S·cm-1)和单晶LaF3的室温离子电导率(10-6 S·cm-1)相比有明显提高.观察到由于纳米材料的弛豫引起电导率随测试次数增大的现象.     

Corrosion-Free EMF Measurements of Zinc-Based Intermetallic Compounds at Ambient Temperature

Material development requires in many cases information about the necessary stability of the materials against oxidation, which is encoded in the chemical activity of the constituting elements. Determination of the chemical activity is tedious, especially for metallic materials at or close to ambient temperature. To determine the chemical activity of Zn at ambient temperature, electromotive force (EMF) measurements on the intermetallic compounds ZnPd, ZnPt and Cu₅Zn₈ within their respective homogeneity range were conducted. The single-phase nature of the samples was confirmed by powder X-ray diffraction, light microscopy as well as SEM/EDX analysis. To exclude oxidation, and therefore faulty determination of the electrochemical potentials, a method was developed to conduct the electrochemical measurements under non-corrosive conditions in inert atmosphere. Corrosion by the electrolyte was avoided using anhydrous dimethylformamide as aprotic solvent. From the EMF the respective intrinsic activities of zinc in the corresponding intermetallic compounds was determined. Measurements on Cu₅Zn₈ and comparison to available data in literature verified the developed method allowing to retrieve thermodynamic data of ZnPd and ZnPt for the first time at ambient temperature. The herein developed and easy-to-use methodology is applicable to a wide range of metallic material by choosing appropriate compositions of the electrolyte and has the potential to boost material development.     

Theoretical Studies of Single Molecule Spectroscopy at Room Temperature

This talk is motivated by recent room-temperature single molecule experiments, which measure the optical spectrum along single molecular trajectories and monitor the molecular dynamics and chemical kinetics of individual reactive systems. These experiments contain new information that requires theoretical models and interpretations. Several aspects of single molecule spectroscopy are analyzed:(1) Event-averaged single molecule quantities are calculated, with the prediction of the echo signal in the joint event probability distribution function^[1]. Similar to the photon echo phenomenon, the single molecule echo signal measures solvent effects on chemical kinetics. (2) The statistics of single molecule blinking events are often correlated to underlying quantum mechanisms. The distribution functions of waiting-time sequences are examined for several quantum processes, including electron transfer, solvent relaxation, laser-induced emission, and single quantum-dot blinking^[2]. (3) Single molecule measurements of heterogeneous diffusion reveal deviations from the Gaussian distribution of Brownian motion. As a quantitative measure, the non-Gaussian indicator decays asymptotically to zero according to 1/t for finite time correlation, but saturates at a plateau value for power-law correlation.     

Ion Association of Cadmium Acetate from Conductivity Measurements

Conductivity of cadmium acetate over the concentration range of 10^?4 to 10^?3M was measured at 25°C. The approximate dissociation constant of CdAc₂ in dilute aqueous solution was estimated from the relation, α=[Λ?36.5+39√C(1+2α)]/[57.9?93√C(1+2α)]. The limiting value of log₁₀K for the association constant of CdAc⁺ ion was evaluated to be 1.75 at 25°C.     

Observation of Quantum Interference at Room Temperature in a Single Perovskite Quantum Dot

Break junction technique allows researchers to probe charge transport properties in a single Perovskite quantum dot(QD)with anÅngstrom scale resolution,and observe signatures of quantum interference effects at room temperature.     

低温条件下羰基硫催化水解反应本征动力学研究

 采用自行设计和安装的微反－色谱联用装置，在50～70℃，n（H2O）／n（COS）＝60～550的条件下，以TGH为催化剂，对羰基硫催化水解反应本征动力学进行了研究．利用不同的目标函数，采用非线性Marquart法对实验数据进行回归，所建立的本征动力学方程式为r（COS）＝－dXd（W／f（COS））＝1．82·1014p（COS）p－0．5（H2O）exp－758008．374T．并对其反应机理进行了探讨．     

单根ZnO纳米线的室温气敏特性

利用改进的CVD法制备了(002)面取向生长的ZnO纳米线, 通过光刻/剥离的自下而上的组装技术制备了基于单根ZnO纳米线的气敏元件, 其中的ZnO纳米线直径为50-300 nm, 有效长度为2-10 μm. 测试表明在室温条件下, 元件对浓度为500 μL·L-1的氧气和乙醇的灵敏度可以分别达到1.3 和1.2, 而气敏响应时间分别为10 和5 s, 由于单根纳米线的一维小尺寸结构加剧了电流的自加热效应, 因此元件在外界环境为室温的条件下的灵敏度才略有提高.     

微波场溶液电导率的现场测定(英文)

现场测定了溶液在微波场和非微波场中的电导率～温度函数,结果表明在微波场与非微波场中溶液的电导率(Lw)随温度的变化可分别用方程Lw=a′+b′T+c′T2和Ln=a+bT+cT2表述,类似于非微波场中的溶液电导率,而Lw和Ln两者的关系则可表示为lnLw=A+BLn+CL2n。以上a,b,c,…A,B,C等皆为经验系数。     

高电导率的a—SiHY合金的低温电导特性

用射央求地在硅单晶衬底上沉积出电导率高达６０Ｓ／ｃｍ的ａ－ＳｉＨＹ合金薄膜。在２０－３００Ｋ，对于钇含量高的样品，其电导仍是热激活的。ｌｇσ与１／Ｔ的关系曲线能够被拟合成斜率不同的两条直线，直线的斜率和两直线间拐点所地 温度依赖于膜中钇的含量。但对钇含量低的薄膜，电导对温度的依赖关系度为σ∝ｅｘｐ（－１／Ｔ＾１／４）。结果表明，这些钇含量不同的样品在没的温度范围内具有不同的导电机制。     

Crystallization of Polymers Studied by Temperature Modulated Calorimetric Measurements at Different Frequencies

Quasi-isothermal temperature modulated DSC (TMDSC) were performed during crystallization to determine heat capacity as function of time and frequency. Non-reversible and reversible phenomena in the crystallization region of polymers were distinguished. TMDSC yields new information about the dynamics of local processes at the surface of polymer crystals, like reversible melting. The fraction of material involved in reversible melting, which is established during main crystallization, keeps constant during secondary crystallization for polycaprolactone (PCL). This shows that also after long crystallization times the surfaces of the individual crystallites are in equilibrium with the surrounding melt. Simply speaking, polymer crystals are living crystals. A strong frequency dependence of complex heat capacity can be observed during and after crystallization of polymers.This revised version was published online in November 2005 with corrections to the Cover Date.     

单分子导电性质的研究进展

介绍了测量单个有机分子导电性质的一些进展,包括分子的尺寸效应、官能团效应、分子与电极的接触效应等,以及分子逻辑器件的初步研究.     

Temperature Measurements by a Discrete Integrator and a Thermal Converter

The possibility of designing measuring devices based on superionic conductors and thermal converters is studied. A method for measuring the average temperature difference between the supply and reflux pipelines of heat supply systems is suggested. The device based on this method has advantages over those presently used.     

Scaling in Electrical Conductivity Measurements and Rheological Measurements of Monarch 700 Dispersions Stabilized by Polymers

For making stable dispersions of graphitic carbon black (Monarch 700), the effectiveness of three dispersants/polymers (hypermer LP1, hypermer B246, and OLOA 11000) in xylene is investigated. Hypermer LP1 (polyhydroxystearic acid) is a homopolymer and hypermer B246 (PEG 30-dipolyhydroxystearate) is a polyhydroxystearic acid/polyethylene oxide/polyhydroxystearic acid ABA block copolymer, while OLOA 11000 (polyisobutylene succinimide) has a polar head group (polyamine) attached to a hydrocarbon chain (polyisobutylene). Well-dispersed graphitic carbon black dispersions were prepared using dispersants at optimum concentrations. Percolation threshold and rheological threshold were determined by analyzing the variations in electrical conductivity and elastic modulus with concentration of carbon black. Above threshold concentration, scaling law was applied to experimental data of rheology (dynamic measurements) and electrical conductivity measurements to evaluate quality of the system. Effectiveness of polymers was investigated on the basis of value of critical exponent (t and t′, respectively) in scaling power law. Hypermer LP1 was proved to be a poor dispersant for Monarch 700 dispersions while other two polymers were found to be effective stabilizers.     

Determination of Temperature Gradients with Micrometric Resolution by Local Open Circuit Potential Measurements at a Scanning Microelectrode

A method to determine localized temperature profiles using a scanning electrochemical microscopy (SECM) setup and potentiometry is presented. A Pt microelectrode was first calibrated to correlate the open circuit potential (OCP) with temperature in an electrolyte containing ferri/ferrocyanide. Using the calibration graph, the temperature at a given position and a time could be derived. For dynamic measurements, the thermal expansion of the surface was initially determined using shear force mode SECM. Following the OCP at the microelectrode static as well as dynamic temperature gradients above the heated surface were successfully probed and visualized with vertical micrometric resolution and with precision in temperature determination below 1 °C.     

低温催化精馏循环法合成2,2-二甲氧基丙烷

采用低温控制和催化精馏循环相结合的方法一次性合成了2,2-二甲氧基丙烷.实验表明该法能够缩短反应时间,大大提高反应产率.确定该合成工艺的最佳工艺参数为精馏柱柱顶温度为56.5℃,甲醇补加量流速为2 mL/min,催化剂床层温度为-10℃,丙酮转化率可以达到71%.     

Single crystal tin nano-rod arrays electrodeposited by a soft template

Single crystal tin nano-rod arrays were fabricated by the electrodeposition method when amphiphilic triblock copolymer P123 was used as a soft template at a concentration much lower than that for forming a liquid crystalline phase.