Effects of gas sparging and mechanical mixing on sonochemical oxidation activity

The effects of air sparging (0–16 L min⁻¹) and mechanical mixing (0–400 rpm) on enhancing the sonochemical degradation of rhodamine B (RhB) was investigated using a 28 kHz sonoreactor. The degradation of RhB followed pseudo first-order kinetics, where sparging or mixing induced a large sonochemical enhancement. The kinetic constant varied in three stages (gradually increased → increased exponentially → decreased slightly) as the rate of sparging or mixing increased, where the stages were similar for both processes. The highest sonochemical activity was obtained with sparging at 8 L min⁻¹ or mixing at 200 rpm, where the standing wave field was significantly deformed by sparging and mixing, respectively. The cavitational oxidation activity was concentrated at the bottom of the sonicator when higher sparging or mixing rates were employed. Therefore, the large enhancement in the sonochemical oxidation was attributed mainly to the direct disturbance of the ultrasound transmission and the resulting change in the cavitation-active zone in this study. The effect of the position of air sparging and mixing was investigated. The indirect inhibition of the ultrasound transmission resulted in less enhancement of the sonochemical activity. Moreover, the effect of various sparging gases including air, N₂, O₂, Ar, CO₂, and an Ar/O₂ (8:2) mixture was compared, where all gases except CO₂ induced an enhancement in the sonochemical activity, irrespective of the concentration of dissolved oxygen. The highest activity was obtained with the Ar/O₂ (8:2) mixture. Therefore, it was revealed that the sonochemical oxidation activity could be further enhanced by applying gas sparging using the optimal gas.     

Increased Flexibility in Multicolumn Chromatography (MC[sbnd]HPLC) via On-line Effluent Mixing Technique

Abstract

In continuation of our work dealing with multicolumn HPLC (MC[sbnd]HPLC) we describe in this paper an on-line on-column fraction trapping technique based on effluent mixing.

To a normal two-column switching set-up (in this case with two RP columns) an additional high-pressure pump gets inserted into the connection line between column A and column B via a low dead volume mixing tee. The in-line respectively off-line switching of pump B and the mobile phase B is time controlled by using a high pressure switching valve. With this set-up it is possible to mix on-line an effluent fraction from column A and transferred onto column B with a highly polar and pH-controlled (e.g. aqueous buffer) new effluent, to reduce or adjust significantly the overall elution strength of this mixed transferred solvent. Thus, several chromatographically effective possibilities can be created in a simple manner, which are for example: (a) pronounced peak compression respectively on-column concentration on column B; (b) due to low elution strength and/or pH adjustment during the trapping period on column B, increments to the overall selectivity of the column switching set-up can be added creating multidimensionality via mobile phase switching; (c) combining the heart cut with the effluent mixing technique enables analysis of trace peaks eluted on the back flank of an overloaded main peak.     

Phase formation and impurity effects in Ar+ ion irradiated Mo/Si thin film bilayer system

We report a dose‐dependent phase evolution in Mo/Si bilayer system upon Ar⁺ ion beam irradiation and subsequent flash annealing at 800 °C for 60 s. Micro‐structural characterization with Grazing Incidence X‐ray Diffraction and Raman scattering reveals a dose‐dependent nucleation of polymorphic phases occurring at the amorphized interface region. The ion beam mixing process has been investigated by Secondary Ion Mass Spectrometry and Rutherford Backscattering Spectrometry. While low ion doses favour nucleation of only metastable MoSi₂ phase, co‐existence of polymorphic phases are observed at high ion doses. The persistence of such polymorphic phases even after a high‐temperature anneal for high dose implanted specimen is indicative of phase retardation. The phase retardation of h‐MoSi₂ to t‐MoSi₂ is accounted in terms of nucleation and growth process. Copyright © 2012 John Wiley & Sons, Ltd.     

Computational Study of the Substitution Effect on the Mechanism for the Gold(I)‐Catalyzed Ring Expansions of Unactivated Alkynylcyclopropanes

The ring expansion reactions of unactivated alkynylcyclopropanes X‐C≡C‐C₃H₅ → X‐C=C₄H₅ (X = H, F, Cl, Me, OMe, NMe₂, CMe₃) were examined using the density functional theory calculations. All of the structures were completely optimized at the B3LYP/6‐311++G** level of theory. For clarify the effect of the cationic gold(I), we also added AuPH₃⁺ as the catalyst into the system and the structures for Au were calculated at the B3LYP/LANL2DZ level of theory. The main finding of this work is that the singlet‐triplet splitting of X‐C≡C‐C₃H₅ play an important role in determining the kinetic and thermodynamic stability of the unactivated ring expansion reactions. When X‐C≡C‐C₃H₅ with a smaller singlet‐triplet splitting is utilized, the reaction has a smaller activation energy and a larger exothermicity.     

Tools to Simulate Distributive Mixing in Twin‐Screw Extruders

The application of the mapping method in finite element modeling is extended to quantitatively compare mixing in different twin‐screw extruder layouts. The mapping method provides volumetric quantities, which are crucial for the analysis and optimization of mixing based on the tracking of particles in the velocity field. A new approach to the mapping method is developed to analyze mixing in complex, dynamic open geometries. Several screw configurations and different types of conveying screws are compared, changing the pitch and gap widths. The volume‐weighted intensity of segregation is used as a mixing measure.

     

分离重组错位通道微混合器混合及结构研究

本文对基于非对称分离重组原理优化得到的错位通道微混合器的混合特性进行了数值模拟,并采用混合强度值作为衡量指标。结果表明,Re在1到80的变化范围内,微混合器的混合效果受通道几何结构参数影响较大,即主次通道上错位通道结构的布置有利于提高微混合器的混合强度。综合考虑混合性能和微通道内压降变化等条件,当错位通道结构参数ω₃/ω₄=1时,非对称分离重组错位通道微混合器的混合强度可提高到86%左右。     

双波长外腔共振和频中Boyd-Kleinman因子优化的理论研究

双波长外腔共振是提高和频转换效率的有效手段,然而基于Boyd-Kleinman(BK)理论,和频效率除了受基频光功率密度影响外,主要受BK因子限制。本文通过分析BK因子随腔结构参数的变化关系,给出基于外腔频率转换过程中BK因子优化的一般方案,从而为搭建相关实验提供必要的理论基础。     

基于光子晶体光纤的高纯度量子关联光子对的制备

使用脉冲光在室温下抽运一根长1 m 的高非线性光子晶体光纤, 产生了中心波长分别位于830 nm 和1411 nm的具有量子关联性的闲频与信号光子. 实验中闲频和信号通道的带宽分别是15 nm和35 nm. 对单通道光子计数率的拟合结果显示光子几乎全部来源于光纤中的自发四波混频过程, 未受到Raman散射噪声的影响. 当闲频和信号通道的光子产生率约为每脉冲0.0085个时, 测得符合计数率与随机符合计数率的比值为102, 接近理论极限, 不仅证明了光子对的低噪声性, 而且表明所产生的光子对本身具有窄带频谱特性, 因而实验中对其收集效率很高. 此外, 这种高纯度关联光子对还联接了不同波段, 在量子信息技术中有着潜在的应用.     

简并四波混频实现全光信号幅度整形的系统设计

对光纤中简并四波混频(DFWM)耦合波方程进行数值求解,通过分析发现:泵浦光功率的增大会导致泵浦光与反斯托克斯光之间能量交换周期减小。阐述了优化光纤中DFWM实现全光信号幅度整形的机理。在此基础上设计了一个优化的全光信号幅度整形系统,并进行了系统仿真,结果表明:通过再生系统后,信号的消光比从9.46 dB提升到30.40 dB,品质因子从15.95提升到了180.40。     

基于光子晶体光纤中FWM的4×10 Gbit/s全光波长转换

 多波长转换对于增强波分复用光网络的灵活性具有重要意义。基于光子晶体光纤中的多四波混频原理,实现了4×10 Gbit/s全光波长转换,深入调查了泵浦功率、光纤长度、信号光与泵浦光偏振失配对波长转换信号质量的影响。结果表明：当泵浦光功率从6 dBm到20 dBm增长的过程中,转换信号Q因子随泵浦光功率增大而增大,最大为82.01,光纤长度从50 m到120 m变化过程中,转换信号Q因子最大为57.41,而随着信号光与泵浦光偏振失配角的增大,转换信号Q因子逐渐降低,当失配角大于60°后,转换信号质量急剧下降。