Coherent stokes scattering from gold nanorods: critical dimensions and multicolor near-resonant plasmon excitation

In this study, we detail the coherent Stokes scattering from gold nanorods in ensemble and single particle measurements. An increase of more than an order of magnitude was observed in the surface plasmon resonance enhancement of coherent Stokes scattering by gold nanorods for small changes in nanorod dimensions. The impact of this dimensional change is, in general, smaller when probed by single color linear and non-linear techniques. We find that the size sensitivity and associated wavelength dependence of the enhanced coherent Stokes scattering from individual gold nanorods is consistent with predictions based on local surface plasmon resonances found from exact solutions obtained using boundary element methods.     

HDPE及其共混物的挤出压力振荡现象

采用恒速型双毛细管流变仪研究高密度聚乙烯及其共混物的压力振荡现象,测量了压力振荡的振幅及频率,计算了熔体在管壁的滑移速率和临界外推滑移长度。结果表明,发生压力振荡时,熔体与毛细管壁的界面出现“时黏时滑”转变。黏界面时,挤出物表面出现“鲨鱼皮”现象;滑界面时,挤出物表面粗糙,类似于无规破裂。随剪切速率的增加,压力振荡的振幅减小,而滑移速率、临界外推滑移长度及振荡频率均有提高。升高挤出温度和采用共混改性都可抑制压力振荡现象。     

Role of a surfactant in the electrical potential oscillation across a liquid membrane

Electrical potential oscillation across a liquid membrane of a water/octanol/water system, in which a surfactant and ethanol are present in one of the waters, and electrical potential between octanol and aqueous phases of the octanol/water system were measured. On using sodium dodecyl sulfate (SDS) as the surfactant, potential oscillation was initiated with a sudden potential change toward the more negative potential. The upper potential (E_A,SDS) and lower potential (E_B,SDS) of the first oscillation were affected by the electrolyte added to the aqueous phase containing no previous surfactant. With hexadecyltrimethylammonium bromide (CTAB) as the surfactant, direction of the pulse was opposite that when using SDS. The lower potential (E_A,CTAB) and upper potential (E_B,CTAB) of The first oscillation were affected by the electrolyte. For instance, E_A,SDS and E_B,CTAB were greatly affected by halide ion size. In contrast, E_A,CTAB and E_B,SDS were only slightly affected by this parameter. The effects of the electrolytes on E_A,SDS and E_B,SDS were essentially the same as those on potentials at the interface between the octanol and aqueous phases of the octanol/water system in the absence of SDS (E_C,SDS) and presence of SDS (E_D,SDS), respectively. The effects of electrolytes on E_A,CTAB and E_B,CTAB were also basically the same as those on the potentials at the interface between the octanol and aqueous phases of the octanol/water system in the absence of CTAB (E_C,CTAB) and presence of CTAB (E_D,CTAB), respectively. Potential oscillation thus appears quite likely due to the repetitive formation and destruction of the surfactant layer adsorbed on the octanol/water interface.     

Hydrodynamics and mass transfer of oscillating gas‐liquid flow in ultrasonic microreactors

Ultrasonic microreactors were used to intensify gas‐liquid mass‐transfer process and study the intensification mechanism. Fierce surface wave oscillation with different modes was excited on the bubble. It was found that for slug bubbles confined in smaller microchannel, surface wave oscillations require more ultrasound energy to excite due to the confinement effect. Cavitation microstreaming with two toroidal vortices was observed near the oscillating bubble by a streak photography experiment. Surface wave oscillation at the gas‐liquid interface increases the specific surface area, while cavitation microstreaming accelerates the interface renewal and thus improves the individual mass‐transfer coefficient. With these two reasons, the overall mass‐transfer coefficient was enhanced by 3–20 times under ultrasonication. As for gas‐liquid flow hydrodynamics, ultrasound oscillation disturbs the bubble formation process and changes the initial bubble length and pressure drop. © 2015 American Institute of Chemical Engineers AIChE J, 62: 1294–1307, 2016     

Studies on melt spinning. V. Draw resonance as a limit cycle

The exact wave form of draw resonance in isothermal spinning of Newtonian liquids was sought by solving numerically the simultaneous partial differential equations¹ of melt spinning in their original nonlinear form without recourse to perturbation. When the draw-down ration of spinning exceeded 20, solution of the equations became a limit cycle, a sustained oscillation having amplitude and period independent of initial conditions. As the draw down ratio was further increased, the amplitude of the limit cycle grew very rapidly, and the wave form became close to a pulse train predicting an extreme thinning of the thread at regular intervals along the thread. The above solution for Newtonian liquids agreed well with experiment with respect to oscillation period. Agreement, however, was poor in amplitude, indicating that possibly the amplitude of draw resonance is affected by deviations of polymer viscosity from Newtonian.     

发泡塑料非线性气泡振动临界条件分析研究

通过对气泡振动方程的计算机分析模型，找出了发泡塑料非线性气泡振动发生的临界条件，阐明发泡塑料加工过程控制气泡振动的方法，为气泡振动的实验分析研究和发泡塑料成型加工提高实际指导。     

The oscillation of drops and spheres at fluid—liquid interfaces

A theoretical model is presented which successfully predicts the experimental variation with time of the frequency and amplitude of a rigid sphere oscillating at a fluid-liquid interface in terms of radius, height of fall and physical properties, when the sphere is separated from the interface by a draining film. The model may be modified to describe the observed behaviour of liquid drops. In particular it successfully predicts the initial attenuation in amplitude and irregular increase in frequency with time. The amplitude of oscillation increases and frequency decreases with increasing diameter and density of the sphere, and decreasing interfacial tension. Increasing the height of fall (or impact velocity) has a similar, but surprisingly weaker, effect to that of increasing sphere diameter. The model predicts that a 2 mm dia. rain drop should penetrate a water surface by a few millimeters and oscillate with a frequency of about 30 cycles/sec if it does not immediately coalesce.     

Total internal reflection second harmonic generation from the interface between two immiscible electrolyte solutions

Total internal reflection second harmonic generation (TIR SHG) is used to investigate the interface between two immiscible electrolyte solutions (ITIES) under potential control. The observed potential dependent second harmonic response is attributed to a resonance enhanced process arising from the tetraphenylborate (TPB⁻) ion. As the aqueous phase is biased positive of the organic phase, a large increase in the SH response is observed and is attributed to the adsorption of the TPB⁻ ion at the interface. The potential dependent SH data allows for the determination of the TPB⁻ anion concentration at the interface. TIR SHG compliments measurements of the electrolyte surface excess and can function as a means of measuring the relative concentration of electrolytic species responsible for the potential drop across the electrochemical double layer.     

Dynamical resonances in the fluorine atom reaction with the hydrogen molecule

[Reaction: see text]. The concept of transition state has played a crucial role in the field of chemical kinetics and reaction dynamics. Resonances in the transition state region are important in many chemical reactions at reaction energies near the thresholds. Detecting and characterizing isolated reaction resonances, however, have been a major challenge in both experiment and theory. In this Account, we review the most recent developments in the study of reaction resonances in the benchmark F + H 2 --> HF + H reaction. Crossed molecular beam scattering experiments on the F + H 2 reaction have been carried out recently using the high-resolution, highly sensitive H-atom Rydberg tagging technique with HF rovibrational states almost fully resolved. Pronounced forward scattering for the HF (nu' = 2) product has been observed at the collision energy of 0.52 kcal/mol in the F + H 2 (j = 0) reaction. Quantum dynamical calculations based on two new potential energy surfaces, the Xu-Xie-Zhang (XXZ) surface and the Fu-Xu-Zhang (FXZ) surface, show that the observed forward scattering of HF (nu' = 2) in the F + H 2 reaction is caused by two Feshbach resonances (the ground resonance and first excited resonance). More interestingly, the pronounced forward scattering of HF (nu' = 2) at 0.52 kcal/mol is enhanced considerably by the constructive interference between the two resonances. In order to probe the resonance potential more accurately, the isotope substituted F + HD --> HF + D reaction has been studied using the D-atom Rydberg tagging technique. A remarkable and fast changing dynamical picture has been mapped out in the collision energy range of 0.3-1.2 kcal/mol for this reaction. Quantum dynamical calculations based on the XXZ surface suggest that the ground resonance on this potential is too high in comparison with the experimental results of the F + HD reaction. However, quantum scattering calculations on the FXZ surface can reproduce nearly quantitatively the resonance picture of the F + HD reaction observed in the experiment. It is clear that the dynamics of the F + HD reaction below the threshold was dominated by the ground resonance state. Furthermore, the forward scattering HF (nu' = 3) channel from the F + H 2 ( j = 0) reaction was investigated and was attributed mainly to a slow-down mechanism over the centrifugal exit barrier, with small contributions from a shape resonance mechanism in a narrow collision energy range. A striking effect of the reagent rotational excitation on resonance was also observed in F + H 2 ( j = 1), in comparison with F + H 2 ( j = 0). From these concerted experimental and theoretical studies, a clear physical picture of the reaction resonances in this benchmark reaction has emerged, providing a textbook example of dynamical resonances in elementary chemical reactions.     

平面气固撞击流周期振荡的模拟分析

由于喷嘴截面的高宽比远小于1,平面狭缝喷嘴撞击流可看作二维撞击流。采用欧拉双流体模型对二维气固撞击流进行数值模拟。模拟结果表明,当固相负载率m≤8.2,颗粒粒径为60 μm≤d_p≤175 μm时,大间距的平面气固撞击流也出现了周期振荡。通过分析射流轴线上不同位置的压力和速度的瞬时值和平均值,认为周期振荡是由于撞击面上压力释放和持续射流的共同作用导致。讨论了不同条件对振荡周期的影响:振荡周期随喷嘴间距或颗粒粒径的增加而增加;而随射流Reynolds数的增加或者固相负载率的增加而减小。     

Micro-buckling of paper during blade metering

Multiphysics models were used to simulate the deformational characteristics experienced by paper under metering blades. Paper is found to slip microscopically at the backing roll interface and subsequently buckle either side of the blade during metering operations. Micro-slippage of the paper at the interface is a linear function of the separation height incurred during buckling. The effects of altering the static coefficient of friction as well as the properties of the backing roll material are studied. Increasing the coefficient of static friction reduces the extent of buckling while a non-linear relationship is found to arise on increasing the elastic modulus of the backing roll material. The mechanisms involved in micro-buckling deformation are explicated herein.     

微细通道内蒸汽直接接触间歇凝结汽液相界面运动特性

为探究T形微细通道内蒸汽直接接触间歇凝结汽液相界面的运动特性,利用高速摄像机（帧率为5000帧/s）获取过冷水温33℃、过冷水质量流量6.325g/min、蒸汽温度100℃及蒸汽质量流量0.25g/min工况下的可视化图像。在此基础上定性分析汽液相界面的瞬时演变特征,进一步应用图像批处理技术定量分析相界面的前端运动规律,包括相界面位置及速度的瞬时波动特性。研究发现,不同凝结周期内的汽液相界面在蒸汽泡生成直至最大时的形貌、蒸汽泡的溃灭特性等方面有很大差异,主要体现在气泡溃灭时是否发生“局部收缩”和“内爆”等。此外,对于一个典型相界面运动周期而言,蒸汽泡消失阶段所占时间比例最小约为12%。通过分析相界面前端瞬时位置波动曲线,发现利用该曲线获得该工况下的凝结频率为23Hz,且该曲线的峰值分布具有较强周期振荡特性。通过分析相界面前端瞬时速度波动曲线,发现在多个极短时间内出现了速度的瞬时转变以及较为剧烈的多次振荡,速度峰值最大可达11m/s。结合可视化图像,详细描述了相界面速度振荡时的界面演变情况,并揭示“局部收缩”和“内爆”导致速度振荡的机理。     

Detection and Analysis of Crack Propagation in PZT Multilayer Ceramics

The flaw propagation in Lead zirconate titanate (PZT) multilayer ceramics under mechanical load was examined using impedance spectroscopy and three‐point bending studies. Initial flaws were generated by applying a positive sinusoidal electric field to the specimens. The cracks were sequentially propagated and after the release of the external mechanical load, impedance spectroscopy was conducted. The shift in the resonance frequencies and the subresonance height of the impedance spectroscopy were used as a measure of flaw extension. A functional dependence of the resonance frequency and the phase shift on the crack length was found. The crack propagation was studied on flaws starting at the positive and negative electrode, respectively. The maximum fracture strength, as well as the crack path, depends on the electrode potential. The variation in the fracture strength was caused by different observed fracture mode: interface cracking, matrix‐cracking, or a combination of both. The morphology of the fracture surfaces was ascribed to a textured microstructure, which is created by the sample processing, for example, by the poling process. A modified poling procedure with a lower poling temperature was analyzed, which yielded a reduction of the anisotropy of the electrode strength. Impedance spectroscopy was found to be a reliable measurement tool for automated flaw detection in PZT multilayer ceramics.     

Domain-boundary structure of styrene-isoprene block copolymer films cast from solutions. III. Preliminary results on spherical microdomains

The microdomain structure of styrene-isoprene A-B type block copolymers having a nearly constant fraction of polyisoprene block segments (13 ～ 22 wt percent) was investigated by small-angle X-ray scattering (SAXS) as a function of the molecular weights of the copolymers. The styrene-rich block copolymers all have spherical microdomains of polyisoprene block segments dispersed in a matrix of polystyrene block segments. The size of the spherical domains increases with increasing molecular weight of the polyisoprene segment with a power of ca. 0.6. The thickness of the domain-boundary interphase arising from a partial mixing of the incompatible segments at the domain-boundary interface is also estimated by analyzing a systematic deviation of the SAXS intensity distribution from Porod's law at large scattering angles on the basis of the infinite slit-height approximation. The results indicate the interfacial thickness to be about 20Å and to be almost independent of the molecular weight of the block copolymers studied. The applicability of the infinite-slit height approximation in the analysis of SAXS intensity distributions at large scattering angles is also discussed in an approximate fashion.     

高密度差体系中单液滴运动的数值模拟

采用VOSET方法捕捉液液两相运动界面,对高密度差体系中单液滴的运动进行数值模拟,分析不同时刻的表面图和流线图及瞬态速度变化图,研究了单液滴运动过程的速度变化及形变。研究结果表明：液滴形变随密度差和液滴粒径以及界面张力减小而变得剧烈;液滴上升速度随密度差和界面张力的增大而增大;液滴速度振荡幅度随粒径减小而减小;液滴形变的频率随界面张力增大或粒径减小而变小。     

平面撞击流偏斜振荡影响因素的大涡模拟

采用大涡模拟对35≤Re≤145000、4≤L/h≤40范围内的平面撞击流偏斜振荡特性进行了研究。通过对平面撞击流模拟与实验结果的比较验证了数值模拟的可靠性,重点考察了不同流体介质、边界受限程度及喷嘴出口高宽比等因素对平面撞击流偏斜振荡特性的影响,并对平面撞击流发生偏斜振荡的量纲1参数范围进行划分。研究结果表明,不同流体介质对平面撞击流量纲1偏斜振荡周期几乎没有影响,量纲1偏斜振荡周期随着边界受限程度的增大而增大,随着喷嘴出口高宽比的增大而减小。     

用双毛细管流变仪对 HDPE与LLDPE挤出压力振荡的研究

用RH2000恒速型双毛细管流变仪研究了3种HDPE和3种LLDPE的挤出压力振荡现象。通过压力振荡图、流动曲线和挤出物表观3方面,对两种类型聚乙烯压力振荡的差异进行了分析。发现HDPE的压力振荡很明显,振幅在2~3MPa,而LLDPE的振幅很小,甚至在压力-时间图上看不出来。6种聚合物的流动曲线都发生了断裂。在柱塞下降速度恒定下发生压力振荡时,流速并不恒定,粘界面条件下流速较小,滑界面条件下流速较大,并通过计算获得了3种HDPE发生压力振荡时对应于粘界面与滑界面的流速。HDPE和LLDPE在粘界面条件下挤出物都是鲨鱼皮,而滑界面条件下HDPE的挤出物类似于无规破裂,LLDPE挤出物表观较光滑,且没有鲨鱼皮。     

含圆孔双压电陶瓷的动态性能研究

采用Green函数法研究界面附近含圆形孔洞的两半无限压电陶瓷对SH波的散射问题。首先利用复变函数和多极坐标的方法构造出适合于本文问题的位移Green函数和电场Green函数。然后利用契合思想,根据界面上的连续性条件建立起求解问题的第一类Fredholm型积分方程。得到了孔边周向剪应力动应力集中系数的解析表达式。最后作为算例,给出了界面两侧圆孔的两组动应力集中系数的计算结果图并进行了讨论。     

Controlled electrodeposition of ZnO nanostructures for enhanced light scattering properties

This paper outlined how to control density and shape of electrodeposited ZnO nanorods to achieve high scattering properties. Light scattering at nanostructured metal–semiconductor interfaces is a proven method to improve absorption in photovoltaic devices. Adjustment of nanostructure shape and mean distance is critical to achieve efficient light scattering. A simple model is introduced that predicts maximal suppression of the specular transmitted light, resulting in maximal light scattering. This model predicts in an ideal case, 50 % nanostructure coverage of the electrode. Furthermore, an optimal nanostructure height has been determined depending on the incident wavelength and the refractive indices. Experimentally, the crystal density on ITO substrates was adjusted by pulsing the deposition potential, thus, removing the requirement for an additional seeding layer. The solution of the diffusion equation indicated a break-to-pulse ratio of at least 2.4 for an efficient control of the crystal density during pulsed electrodeposition. In addition, the structure height was set by varying the number of pulse cycles. Such tailored ZnO nanostructures showed a suppression of the specular transmitted light beam of 83.5 % and a diffusive forward scattering efficiency of 39 % at a wavelength of 406 nm. Thus, the optical absorption of e.g. an 80-nm thick polymeric active layer of P3HT could be increased by 47 % by applying such tailored ZnO nanostructures.     

Hindered oscillation and e.s.r. spectra of alkyl free radicals trapped in irradiated polyethylene crystals

Structures of alkyl radicals trapped in solution grown crystals of polyethylene and urea-polyethylene complex were studied in detail. A twisted configuration of methylene group with angle of 4.6° from the regular trans-trans configuration was found for the rigid state configuration of the alkyl radical at 77K. Temperature dependences of hyperfine splitting widths due to the β-protons were observed, and analysed in terms of the hindered oscillation of the β-methylene group. The value of the potential barrier height of hindered oscillation was found to be 900 kcal/mol for polyethylene crystal and 600 kcal/mol for urea-polyethylene complex; indicating that the radical site in urea-polyethylene complex is more mobile than that in polyethylene crystal.