大锥角锥形床内颗粒横向混合的实验研究

在900 mm×200 mm×800 mm的冷模试验台上,试验研究了带气体入口直段的大锥角锥形床内示踪颗粒的横向扩散过程,系统考察了床料粒径dp、过余速度u—u_(mff)、静止床层高度h和气体入口直段宽度δ对床内示踪颗粒横向扩散系数D_(sr)的影响。结果表明:在大锥角锥形床中,横向混合试验持续时间间隔对示踪颗粒横向扩散系数的计算结果影响较大;示踪颗粒的横向扩散系数D_(sr),随着床料粒径dp的增大而减小,随着过余速度u—u_(mff)静止床层高度h和气体入口段宽度δ的增大而增大。     

氢及其同位素在聚苯乙烯与Cu界面的扩散

为了探索气体在固体表面高分子链中的扩散,使用分子动力学（MD）的方法,对H2,D2,T2在聚苯乙烯与金属铜（PS-Cu）界面的扩散进行了计算模拟,通过所得到气体的均方位移计算了气体在不同金属表面与聚苯乙烯界面中的扩散系数。结果显示:气体在界面的扩散系数比在聚苯乙烯本体中的扩散系数小,气体在PS-Cu(110)界面的扩散系数最大,在PS-Cu(111)界面的扩散系数最小。计算和分析了PS与金属表面的相互作用,发现其相互作用能越大,气体在此界面的扩散系数越小。同时,金属表面的晶面密度对气体在界面中的扩散也有一定的影响。     

用毛细管成像法测量液相扩散系数——等折射率薄层测量方法

本文提出了一种测量液相扩散系数的新方法. 该方法用透明毛细管构成液相扩散池, 利用毛细管成像法特有的折射率空间分辨测量能力, 通过直接观察和记录扩散介质的等折射率薄层在毛细管中的移动规律, 基于扩散过程遵循的Fick第二定律计算出液相扩散系数. 在25 ℃下研究了丙三醇和纯水间的扩散过程, 扩散系数的测量值与全息干涉法的文献报道值之间的相对误差为4.47%, 论文同时分析了折射率测量精度和毛细管管壁黏滞力对扩散系数的影响. 用毛细管成像法测量液相扩散系数具有样品需要量少、测量速度快、系统稳定性好的特点, 为快速测定微量样品的扩散系数提供了一种有效的新方法. 关键词： 扩散系数 液体折射率 毛细管成像法     

N_2O的离轴腔增强吸收光谱检测技术

基于离轴腔增强光谱检测技术,以可调谐近红外半导体激光器作激光光源,以反射率为99.97%平凹镜组成的光学谐振腔作吸收池,建立了高灵敏度离轴腔增强光谱污染气体检测系统,获得了N2O气体在6 561.39cm-1的吸收光谱.通过对不同浓度N2O样品气体吸收光谱测量,建立了气体浓度与光谱线强度的关系,讨论了气体压强与光谱线宽、检测灵敏度等问题.研究结果表明,离轴腔增强光谱检测技术的检测极限达到了86ppm,是一种设备成本低、操作方便、灵敏度较高、稳定性良好的吸收光谱技术,可以很好地实现微量气体的快速检测.     

La1.85Sr0.15CuO4纳米线阵列的微结构与超导电性

采用溶胶-凝胶结合多孔氧化铝硬模板约束的方法,成功制备出直径约30nm的La1.85Sr0.15CuO4纳米线阵列,用XRD与X-ray EDX测定了所制备纳米线的物相与成分;FE-SEM与TEM表征了其形貌特征;由HRTEM与SAED测量分析了其微结构;磁化强度的测量结果表明样品具有Tc= 30 K的超导电性,比块材La1.85Sr0.15CuO4的Tc稍低.分析表明所制备的样品中存在一种a,b轴拉伸,c轴压缩的结构畸变,减弱了铜氧面内Cu3d和O2p轨道的杂化程度,减小了a,b面内的态密度,从而压制了体系的超导电性.     

高速流动PIV示踪粒子跟随性分析

通过理论推导提出了一种评价高速流动PIV示踪粒子随流能力的松弛特性分析模型,在法向Mach数大于1.4时具有良好的适用性.将新模型应用于试验测量,发展了高速流动PIV系统和示踪粒子布撒技术,验证了高速流动PIV的定量化测量能力.针对空间发展的二维超声速气固两相混合层,数值模拟了不同Stokes数和对流Mach数（M_c）下的粒子跟随性以及弥散和迁徙运动,结果表明:相同对流Mach数,粒径越小的示踪粒子跟随性越好,Stokes数在[1, 10]范围内的粒子有最大扩散距离.示踪粒子的直径大小决定其在超声速混合层大涡拟序结构中的分布特征,且粒径越小,气体与粒子的掺混越剧烈.相同粒径的粒子,对流Mach数越大跟随性越差.      

颗粒物环境下用于气体吸收光谱测量的气固两相高温样品池系统

设计了一种气固两相高温光学样品池,模拟同时存在颗粒物的气体探测环境,并通过搭建可调谐二极管激光吸收光谱测量系统,对颗粒物环境下的温度与乙炔体积分数测量技术进行研究。使用质量流量计配置体积分数为0.1%～1%的乙炔气体,并设计颗粒物播撒装置,将直径为125μm的石英砂颗粒与不同体积分数的乙炔气体混合通入样品池,在样品池外侧设置纤维加热腔进行温度控制,产生不同温度的样品环境。使用中心波长为1540 nm的DFB激光器,通过对6489.07 cm^-1与6490.02 cm^-1位置处的一对乙炔吸收谱线进行同时探测,实现了对温度与乙炔体积分数的同时测量。分析发现,500～1000 K温度范围内的温度测量一致性R²≈0.998,相对平均标准偏差为3.05%,乙炔体积分数测量一致性R²≈0.995,相对平均标准偏差为2.65%。此系统满足颗粒物环境下气体光谱探测研究的需求,可为气固两相环境下的光谱探测技术研究提供参考。     

制备条件及添加稀土对SO_4~(2-)/ZrO_2-Al_2O_3固体超强酸酸性影响的研究

用共沉淀法制备了SO4 2 -/ZrO2 -Al2 O3 固体超强酸 ,并采用低温陈化和添加稀土La对其制备方法进行改进 .通过样品催化正丁烷异构化反应考察了该固体超强酸中nZr和nAl的最佳配比为 1∶2 .该法制备的样品的IR显示 ,在 1393cm-1处的吸收峰强度较常温陈化样品大大增加 .XRD分析表明 ,低温陈化和加入稀土添加剂的样品在6 5 0℃焙烧温度下 ,出现了亚稳态的ZrO2 四方晶相的晶体是表面酸性和催化活性增加的微观原因 .样品催化合成八乙酸蔗糖酯反应结果同样证明 ,在相同的时间内 ,低温陈化和添加稀土添加剂的样品具有较好的催化活性     

腔增强吸收光谱技术中的腔镜反射率标定方法研究

腔增强吸收光谱技术具有实验装置相对简单、灵敏度高、环境适应性强等特点,是高灵敏吸收光谱技术的重要分支之一,在其应用过程中,腔镜反射率是影响其测量准确性的重要因素。利用2.0 μm可调谐二极管激光器作为光源搭建了一套腔增强吸收光谱测量系统,使用两片反射率为99.9%的高反镜作为腔镜,以CO₂气体在5 001.49 cm-1处的吸收谱线作为研究目标,对两种简单实用的腔镜反射率标定方法进行了对比研究。第一种标定方法利用已知程长多通池作为参考池,通过测量谐振腔和多通参考池的输出吸收信号,比较二者的吸收率推导出腔增强系统中的有效吸收路径,然后通过镜片反射率和有效吸收路径的关系对腔镜反射率进行标定;第二种标定方法根据理想气体状态方程得到气体分子数密度,并结合数据库中的谱线线强值,实现了对腔镜反射率进行标定。结果表明,方法一中积分腔与参考池测得信号的积分吸收面积之比为10.5,经过多次测量并计算得到积分腔的有效吸收路径与镜片的反射率分别为302.65 m和99.85%,得到大气中CO₂气体的浓度为0.037 3%,与实际大气CO₂的含量相符合,验证了此方法的准确性;该方法的优点是不受样品浓度影响,但因引入新的参考池,需要两池中气体的压强和温度都保持一致,此方法适用于开放式的腔体结构。方法二中测得大气中CO₂分子位于5 001.49 cm-1处吸收光谱,并结合大气中CO₂气体的分子数密度N为9.099×1015 molecule·cm-3,Hitran数据库中该条谱线线强为3.902×10-22 cm·molecule-1,计算得到镜片反射率约为99.84%;此方法优点是结构相较前一种方法更简单,但需要已知被测气体的分子数密度,因此在配置气体的过程中浓度、压力的误差会影响腔镜反射率的标定。由此可见两种镜片标定方法均可精确实现对腔镜反射率的标定,根据两种方法的特点,在实际应用中可选取相应适合的方法作为参考。     

气体分子在石墨表面的吸附与扩散特性

采用分子动力学方法模拟研究气体分子在石墨表面上的吸附和扩散特性,结果表明气体分子在石墨表面上的吸附强度跟石墨中碳原子和气体分子之间的微观作用力密切相关,不同分子在石墨表面上的吸附强度不同。气体分子在石墨表面上的吸附特性符合Langmuir等温吸附模型,压力越高吸附层内分子的密度越高。通过分子的表面扩散系数随着压力的增加而降低的现象以及特定时间内分子运动距离的正常概率分布,发现石墨表面上分子的扩散主要由分子之间的碰撞控制,趋近于体相扩散。分子在石墨表面吸附层内的密度对表面扩散系数的影响非常显著,导致吸附性强的CO_2和H_2S分子扩散系数要明显低于吸附性弱的CH_4和N_2分子.     

NMR investigation of gaseous SF6 confinement into EPDM rubber

The confinement process of gaseous sulphurhexafluoride (SF6) in ethylene-propylene-diene (EPDM) rubber was investigated by spectroscopic and spatially resolved NMR techniques. A strong elongation of T1 relaxation time of SF6 and a decrease of the diffusion coefficient were found. A possible explanation may be the strong restriction of molecular mobility due to interactions between SF6 and active centers of the EPDM.     

非定常空气流场中污染气体的对流与粘性扩散

基于离散涡方法求得的非定常、不稳定空气流场，数值求解了污染气体在空气中的对流湍流扩散方程．两者在每一个时间步耦合，以求非定常对流项．考虑速度脉动，改进了扩散模式．用SF6作为示踪气体，进行了现场测量实验．测得了各测点的SF6浓度随时间的变化．实验结果与数值仿真进行了对比，两者吻合．     

Ratio of Diffusion Coefficient to Mobility for Electrons in SF6-Air and Freon-Nitrogen Mixtures

The ratio of diffusion coefficient to mobility (D/?) for electrons has been measured in SF6-air and freon-nitrogen mixtures for various concentrations of SF6 and freon in the mixtures over the range 140? E/p? 220 V.cm-1 - torr-1. In SF6-air mixtures, the values of D/? were always observed to lie intermediate between the values for the pure gases. However, in freon-nitrogen mixtures, with a small concentration (10 percent) of freon in the mixture, the values of D/? are found to lie above the boundaries determined by the pure gases. In this mixture, over the lower E/p range (140 to 190) the electrons appear to lose a large fraction of their energy by the excitation of the complex freon molecules, while at higher E/p values (200 to 240), the excitation and consequent deexcitation of nitrogen molecules and its metastables seem to cause an increased rate of ionization of freon molecules.     

基于鲁米诺修饰碳糊电极电化学发光异烟肼传感器的研制

通过化学修饰的方法将直接参与电化学发光反应的试剂鲁米诺固定于电极表面,结合醋酸纤维素修饰碳糊电极构建异烟肼电化学发光传感器。在最佳实验条件下,该传感器具有重现性好、选择性高等优点,异烟肼浓度在4.0×10-6—4.0×10-5g/mL范围内与相对电化学发光强度呈线性关系。该方法测定异烟肼的检出限为4.6×10-6g/mL,相对标准偏差为1.2%,相关系数为0.9985,用于样品测定,结果与对照方法吻合。     

Intercalation thermodynamics and chemical diffusion of oxygen in the solid solution YBa2Cu3−xCoxO6+δ

The equilibrium oxygen content as a function of the temperature and oxygen pressure was measured for the solid solution YBa₂Cu_3−xCo_xO_6+δ, where x=0, 0.2, 0.4, 0.6, 0.8, by using coulometric titration in the temperature range 600–850°C and oxygen pressures between 10⁻⁵ and 1.0 atm. The change in the partial molar enthalpy and entropy of the intercalated oxygen was determined at different oxygen and cobalt contents. The oxygen chemical diffusion was studied by thermogravimetric relaxation in the oxygen-controlled atmosphere. The thermodynamic data were employed to determine how the chemical diffusion coefficient, the thermodynamic factor and the random-diffusion coefficient depend on oxygen content in specimens with different cobalt concentration. The oxygen intercalation thermodynamics and diffusivity results provide evidence of ordering phenomena on a microscopic scale in the basal plane of the tetragonal solid solution YBa₂Cu_3−xCo_xO_6+δ. A model for the oxygen diffusion is suggested to explain the large difference between the random and tracer diffusion coefficients in YBa₂Cu₃O_6+δ     

The relationship between chemical and tracer diffusion coefficients of aliovalent ions in an ionic lattice

The theoretical model developed by Lidiard was extended to describe the relationship between the chemical and tracer diffusion coefficients of aliovalent ions in an ionic lattice.It is shown that the relationship between the chemical diffusion coefficient, D, and the tracer diffusion coefficient, D¹, is D = 2D¹ if the migration of dimers is the principal mechanism of transport and for the migration of trimers D = 3D¹ if the concentration of impurity ion is relatively small. These relationships are valid regardless of the charge of the aliovalent or lattice ions.The chemical diffusion coefficients of Cr³⁺ in Cr-doped MgO were determined for three different temperatures, 1656, 1717 and 1768K, and for the concentration region 2.5×10^?2?2.8×10^?1 mole% Cr₂O₃. Using previously determined values for the tracer diffusion coefficient of ⁵¹Cr in Cr-doped MgO it was found that for the temperature and concentration region investigated D = (2.00±0.17)D¹ which indicates that diffusion proceeds primarily by the migration of dimers.     

A new code for modelling the near field diffusion releases from the final disposal of nuclear waste

The canisters with spent nuclear fuel produced during the operation of WWER reactors at the Czech power plants are planned, like in other countries, to be disposed of in an underground repository. Canisters will be surrounded by compacted bentonite that will retard the migration of safety-relevant radionuclides into the host rock. A new code that enables the modelling of the critical radionuclides transport from the canister through the bentonite layer in the cylindrical geometry was developed. The code enables to solve the diffusion equation for various types of initial and boundary conditions by means of the finite difference method and to take into account the non-linear shape of the sorption isotherm. A comparison of the code reported here with code PAGODA, which is based on analytical solution of the transport equation, was made for the actinide chain 4N+3 that includes ²³⁹Pu. A simple parametric study of the releases of ²³⁹Pu, ¹²⁹I, and ¹⁴C into geosphere is discussed.     

Continuous wave MRI diffusion study of water in bentonite clay

Three-layered clay minerals such as montmorillonite (bentonite) exhibit very short transverse relaxation times. This is especially true for samples with relatively low water contents in the region of 20% to 30%, which is the water content typically used in environmental technology applications (e.g., as a mineral liner material for landfills). The diffusion of water in samples with such short transverse relaxation times can be measured with NMR by observing the moisture gradients or isotope tracer fronts propagating through appropriately prepared samples by means of continuous wave MRI. The first results from such studies on bentonite clays are presented in this paper.     

A voltammetric sensor based on GO–MWNTs hybrid nanomaterial-modified electrode for determination of carbendazim in soil and water samples

A voltammetric sensor for the determination of carbendazim was developed at a glassy carbon electrode modified with a hybrid nanomaterial (graphene oxide–multi-walled nanotubes/glassy carbon (GO–MWNTs/GC)). Its surface electrochemical property was studied with UV–Vis spectroscopy, TEM analysis, and electrochemical impedance spectroscopy. The electrochemical behavior of carbendazim was investigated on the modified electrode with cyclic voltammetry and differential pulse voltammetry. The influence of modifier dosage, buffer solution, pH, accumulation time, and scan rates on the determination was discussed. The results indicated that the reaction of carbendazim on the electrode was controlled by diffusion and was an irreversible process with two electrons. The effective area of GO–MWNTs/GC, anodic transfer coefficient, and apparent diffusion coefficient were calculated. The anodic peak current of carbendazim was linear with the concentration of carbendazim from 10 nM to 4 μM with a detection limit of 5 nM (S/N?=?3). The proposed sensor was successfully applied to the determination of carbendazim in soil and tap water.     

Exact Tracer Diffusion Coefficient in the Asymmetric Random Average Process

We study tracer diffusion in the continuous-time asymmetric random average process which is an interacting particle system on generalizing the Hammersley process. From the equations of motion for the particle-position correlations we obtain the exact tracer diffusion coefficient which is in agreement with a recent heuristic result by Krug and Garcia.