A tool for rapid quenching of elongated polymer melts

In this article, we present a device for rapid quenching of elongated polymer melts. The tool is an accessory to the uniaxial elongational rheometer RME of Meissner and Hostettler. It is intended to be used for microscopic and other investigations of stretched polymers. The device allows us to solidify a polymer melt by pouring liquid nitrogen on it and to cut it at the nearly same instant of time. Then the sample can be easily removed from the stretching apparatus. Solving the heat diffusion equation for a polymer melt, which is cooled by liquid nitrogen, we theoretically estimate the quenching time of this method. To demonstrate that this quenching procedure indeed rapidly cools a polymer melt, the stress birefringence of elongated and subsequently quenched polystyrene melts is measured and the stress-optical coefficient C is determined. The experimental value of the stress-optical coefficient is |C|= 4.65×10⁻⁹ Pa⁻¹, which agrees well with the data in literature. Using this tool for elongation experiments with the RME, polymer melts can be solidified in between approximately 0.2 and 2.0 s, depending on the thickness of the sample.     

A coumarin-based fluorescent PET sensor utilizing supramolecular pKa shifts

A new coumarin derivative containing benzothiazole and piperazine substituents was synthesized. Preferential inclusion of the benzothiazole group, over the coumarin and piperazine groups, inside the cavity of the molecular container cucurbit[7]uril (CB7) was evidenced by using optical and NMR techniques. The binding constant of the new complex with CB7 is higher in its protonated forms (e.g., K = 2.8 × 10⁶ M⁻¹) than in its neutral forms, which led to an increase in the pK_a value associated with protonation of the aza nitrogen on the benzothiazole ring of ca. 2.5 units. Such CB7-induced protonation disabled the photoinduced electron transfer (PET) in the included molecule, enhancing its coumarin fluorescence up to ca. 45-fold (pH 3.5, 410 nm). The results are discussed in the context of designing sensitive analytical tools for reversible monitoring of optically inactive analytes by competitive displacement experiments.     

Characterising lone-pair activity of lead(II) by 207Pb solid-state NMR spectroscopy: coordination polymers of [N(CN)2]- and [Au(CN)2]- with terpyridine ancillary ligands

A series of lead(II) coordination polymers containing [N(CN)₂]^? (DCA) or [Au(CN)₂]^? bridging ligands and substituted terpyridine (terpy) ancillary ligands ([Pb(DCA)₂] ( 1 ), [Pb(terpy)(DCA)₂] ( 2 ), [Pb(terpy){Au(CN)₂}₂] ( 3 ), [Pb(4′‐chloro‐terpy){Au(CN)₂}₂] ( 4 ) and [Pb(4′‐bromo‐terpy)(μ‐OH₂)_0.5{Au(CN)₂}₂] ( 5 )) was spectroscopically examined by solid‐state ²⁰⁷Pb MAS NMR spectroscopy in order to characterise the structural and electronic changes associated with lead(II) lone‐pair activity. Two new compounds, 2 and [Pb(4′‐hydroxy‐terpy){Au(CN)₂}₂] ( 6 ), were prepared and structurally characterised. The series displays contrasting coordination environments, bridging ligands with differing basicities and structural and electronic effects that occur with various substitutions on the terpyridine ligand (for the [Au(CN)₂]^? polymers). ²⁰⁷Pb NMR spectra show an increase in both isotropic chemical shift and span (Ω) with increasing ligand basicity (from δ_iso=?3090 ppm and Ω=389 ppm for 1 (the least basic) to δ_iso=?1553 ppm and Ω=2238 ppm for 3 (the most basic)). The trends observed in ²⁰⁷Pb NMR data correlate with the coordination sphere anisotropy through comparison and quantification of the Pb? N bond lengths about the lead centre. Density functional theory calculations confirm that the more basic ligands result in greater p‐orbital character and show a strong correlation to the ²⁰⁷Pb NMR chemical shift parameters. Preliminary trends suggest that ²⁰⁷Pb NMR chemical shift anisotropy relates to the measured birefringence, given the established correlations with structure and lone‐pair activity.     

Ionic azo-codendrimers: Influence of the acids contents in the liquid crystalline properties and the photoinduced optical anisotropy

A series of codendrimers has been prepared by the grafting of poly(propylene imine) PPI-(NH₂)₁₆ (G = 3) with two different carboxylic acids: the aromatic-based 5-[4′-(4-cyanophenylazo)phenyloxy]pentanoic acid (AZO) and the aliphatic 2,2-bis(undecanoyloxymethylene)propionic acid (BUPA) in different proportions. Their thermal properties, liquid crystalline behavior and photoinduced optical anisotropy have been investigated. The formation of the ionic compounds was confirmed by nuclear magnetic resonance (NMR) spectroscopy, and Fourier transform infrared (FT-IR) spectroscopy. The influence of the acid percentage in the liquid crystalline behavior was investigated by means of differential scanning calorimetry (DSC), polarizing optical microscopy (POM) and X-ray diffractometry (XRD). All the resulting co-dendrimers present liquid crystalline properties displaying an evolution from nematic mesophase for the azo-richer dendrimers to smectic A mesophase for the BUPA-richer dendrimers. Only materials with low azobenzene contents up to four AZO units per dendrimer on average were processable by casting from dichloromethane solutions and resulted in transparent thin films appropriate for optical studies. The photoinduced dichroism reached was higher in the dendrimer with higher azo content (four units per dendrimer) being this material a good compromise between processability and optical response.     

五角芯型保偏光子晶体光纤(Q-PM-PCF)的双折射

提出了一种内层空气孔环含有五个空气孔的新型高双折射光子晶体光纤结构;采用全矢量有限元法进行分析,研究了该光子晶体光纤两正交偏振模的有效折射率和双折射,分别给出了该五角芯型保偏光子晶体光纤双折射随输入光波长和大空气孔半径的变化曲线.分析结果表明:该五角芯型保偏光子晶体光纤的双折射很易达到i0-3量级甚至更高,比传统保偏光纤的双折射至少高出一个数量级,合理设计光纤结构参数,该保偏光纤的双折射在1550 nm处可以达到6.5×10-3以上,甚至更高,适合应用于偏振特性及稳定性要求都较高的实际光纤传感系统,例如光纤陀螺.     

Thermoelectric power generation

Although the polarisation of the light was discovered at the beginning of the nineteenth century, the Vikings could have used the polarised light around the tenth century in their navigation to America, using a ‘sunstone’ evoked in the Icelandic Sagas. Indeed, the birefringence of the Iceland spar (calcite), a common crystal in Scandinavia, permits a simple observation of the axis of polarisation of the skylight at the zenith. From this, it is possible to guess the azimuth of a hidden Sun below the horizon, for instance. The high sensitivity of the differential method provided by the ordinary and extraordinary beams of calcite at its so-called isotropy point is about two orders higher than that of the best dichroic polariser and permits to reach an accuracy of ±1° for the Sun azimuth (at sunrise and sunset). Unfortunately, due to the relative fragility of calcite, only the so-called Alderney crystal was discovered on board a 16th ancient ship. Curiously, beyond its use as a sunstone by the Vikings, during these last millennia calcite has led to the discovery of the polarisation of the light itself by Malus and is currently being used to detect the atmospheres of exoplanets. Moreover, the differential method for the light polarisation detection is widely used in the animal world.     

Optically stimulated piezooptical effects in Cu-doped ZnO films

Photoinduced changes of the piezooptical effects were discovered in the ZnO crystalline films doped by Cu. The photoexcitation was performed by the Er³⁺ doped 10 ns glass laser at wavelength 1540 nm. The piezooptical effect was determined for the diagonal tensor component at 1150 nm. A nonlinear dependence of the output piezooptical response versus the photoinducing power density was established. The effect was completely reversible and disappears within the several second after the switching off of the photoinduced treatment. The possible explanation of the observed effect is given within a framework of the possible changes of Cu aggregates which is manifested through the changes of photoluminescence.     

Photonic crystal fiber with high birefringence and low confinement loss

In this paper, a highly birefringent index-guiding photonic crystal fiber with low confinement loss is proposed by enlarging the central row of air holes in the structure. By employing the multipole method, properties of this structure, including the effective index, birefringence and confinement loss, are investigated. Simulation results indicate that high birefringence of 1.65 × 10⁻³ can be reached at the wavelength of 1.55 μm, and a low confinement loss on the order of 10⁻⁶ dB/km can be achieved at the same wavelength. Moreover, the impacts of air hole sizes on birefringence and confinement loss are also analyzed in detail.     

支撑应力对光刻透镜透射波前畸变的影响

为了设计光刻物镜的支撑结构,建立了支撑应力对透镜透射波前影响的模型,研究了该模型中支撑应力与折射率的关系及支撑应力对透镜透射波前畸变的影响。首先,根据晶体理论,建立了融石英透镜波前畸变与支撑应力之间关系的仿真模型。然后,分析了不同支撑结构下支撑应力与融石英透镜波前的关系。最后,分析了支撑应力造成的透射波前畸变的性质,并选择合适的物镜支撑结构。研究结果表明：光刻物镜支撑结构的支撑应力对透镜的透射波前有很大的影响：3点支撑的波前畸变PV值为3.69 nm;随着支撑点数量的增加,支撑应力造成的透射波前畸变逐渐减少;采用大于9点的支撑结构即可满足光刻投影物镜的元件支撑需求。