Analysis of Ethylene/1‐Olefin Copolymers Made with Ziegler–Natta Catalysts by Deconvolution of Molecular Weight and Average Short Chain Branching Distributions

In this article a systematic method is proposed to deconvolute the time‐dependent molecular weight distributions (MWD) and average comonomer fraction profiles of ethylene/1‐olefin copolymers made with heterogeneous Ziegler–Natta catalysts. These distributions with a high‐temperature gel permeation chromatography equipped with an infrared detector at four different polymerization times have been measured and used this information to infer how the fractions of polymer made on each site type varied with polymerization time. The model estimates here the minimum number of active site types needed to describe these copolymers, the MWD of polymer populations made on each site type, and their average comonomer fractions. This method is useful to quantify the microstructure of olefin copolymers made with multiple site type catalysts using the least number of adjustable parameters.

     

迭代正则化方法求解电介质中空间电荷分布

首先介绍了迭代正则化方法的理论基础,建立了含有空间电荷密度分布的Fredholm第一类积分方程的反卷积算法,利用数值实验研究了加性高斯白噪声对迭代反卷积算法的影响,以及迭代停止标准对非适定问题的数值解的影响,最后使用该方法求解电介质样品中的空间电荷分布.结果表明,在无噪或者低噪环境下,反卷积算法能够非常好地计算出非适定问题的解.当噪声影响增大,信噪比降低时,反卷积的计算结果受到明显的影响.迭代停止标准对数值解的计算精度起着明显的作用.对实际测量数据进行处理表明,迭代正则化反卷积算法能够计算出固体电介质中的空间电荷分布.     

红藻条斑紫菜R-藻红蛋白中的能量传递过程

本文通过对条斑紫菜R-PE(藻红蛋白)及其α-β-γ亚基的吸收光谱和荧光光谱进行计算机解叠,研究了R-PE内发色团之间的能量传递过程,并对R-PE及亚基内的各发色团进行了“s”和“f”型的指认。发现在亚基中为“f”型的发色团在R-pE(αβ)₆γ中起着“s”型发色团的作用,且将能量传递给最后的“f”型发色团。荧光激发偏振光谱进一步证明了R-PE内的能量转移过程与计算机解叠的结果一致。     

Deconvolution of Molecular Weight Distributions Using Dynamic Flory‐Schulz Distributions

Summary: The deconvolution of molecular weight distributions (MWDs) may be useful for obtaining information about the polymerization kinetics and properties of catalytic systems. However, deconvolution techniques are normally based on steady‐state assumptions and very little has been reported about the use of non‐stationary approaches for the deconvolution of MWDs. In spite of this, polymerization reactions are often performed in batch or semi‐batch modes. For this reason, dynamic solutions are proposed here for simple kinetic models and are then used for deconvolution of actual MWD data. Deconvolution results obtained with dynamic models are compared to deconvolution results obtained with the standard stationary Flory‐Schulz distributions. For coordination polymerizations, results show that dynamic MWD models are able to describe experimental data with fewer catalytic sites, which indicates that the proper interpretation of the reaction dynamics may be of fundamental importance for kinetic characterization. On the other hand, reaction dynamics induced by modification of chain transfer agent concentration seem to play a minor role in the shape of the MWD in free‐radical polymerizations.

This Figure illustrates that MWDs obtained at unsteady conditions should not be deconvoluted with standard steady‐state Flory‐Schulz distributions.     

增量维纳滤波法在波前探测解卷积中的应用

一个常规的自适应光学系统通常包含三个重要环节：波前探测、波前校正和波前重构。因此对系统的技术要求非常高,造成系统复杂,成本昂贵。基于哈特曼-夏克波前探测的图像解卷积处理就是“事后”处理的一种,它省去了波前校正环节,使常规的自适应光学系统得到简化,降低了系统成本。其基本原理为对瞬时波面进行短时间曝光探测,同时记录相应的短时间曝光图像,来进行解卷积处理。将增量维纳滤波法应用于基于哈特曼-夏克波前探测的解卷积中,并对室内模拟点源情况下的三组畸变光斑图像数据进行了解卷积恢复处理。结果表明,将增量维纳滤波法应用于基于波前探测的解卷积是完全可行的,在室内模拟点源情况下,恢复的图像可以达到衍射极限分辨力。与维纳滤波相比,它扩展了噪声抑制因子的选取范围,在噪声抑制因子选取不正确的情况下,仍能得到比维纳滤波更好的结果。     

Richardson–Lucy deconvolution of reflection electron energy loss spectra

A procedure for deconvolving the energy spread introduced by the primary beam and the analyzer in a reflection electron energy loss spectrum (REELS) has been developed. The procedure is based on the Richardson–Lucy (RL) algorithm. The approach has been successfully tested on experimental spectra by comparison with spectra with an inherent high‐energy resolution. As a typical result, it was found that the effective energy resolution of spectra with a full width half maximum (FWHM) of the elastic peak of ～1.5 eV in the raw experimental data can be reduced to ～0.7 eV in the deconvoluted spectra. Copyright © 2009 John Wiley & Sons, Ltd.     

Combined on-line transmission FTIR measurements and BTEM analysis for the kinetic study of a consecutive reaction in aqueous-organic phase medium

Combined on-line transmission FTIR spectroscopy and band-target entropy minimization (BTEM) analysis were employed in order to monitor and analyze the kinetics of the alkaline hydrolysis reaction of diethyl phthalate (DEP) in aqueous-ethanol solvent mixture. This reaction is irreversible and involves two consecutive steps with the formation of the observable mono-ion intermediate species. The pure component mid-FTIR spectra of the reactive species involved in this reaction, namely DEP, mono-ion intermediate and di-ion product were successfully reconstructed using BTEM. Their corresponding concentrations were also calculated and subsequently employed to derive the kinetic rate parameters. The effect of temperature and the solvent mixture compositions on these two consecutive reaction steps were also discussed. The temperature variation study showed that both reaction rate coefficients increased with temperature. Both rate coefficients were also affected by the solvent mixture compositions and reached minimum values at certain water-ethanol solvent composition (circa 60% (v/v)). This study shows the utility of combined on-line transmission FTIR spectroscopy and chemometric techniques for the present, rather complex, consecutive organic reaction. Moreover, the present type of approach could facilitate better understanding of a wide variety of organic reactions that are performed in aqueous and mixed aqueous-organic solvents.     

基于干涉原理的双图像加密系统

提出一种新的虚拟光学加密方法,该方法分3个步骤将两幅图像隐藏于3个随机相位板中。将两幅图像分别作为相位和幅度信息隐藏于一个复数场中,利用随机相位板作为参考光,并采用数字全息术将该复数场转换成平稳随机白噪声,利用干涉加密原理进一步将此白噪声储存于2个随机相位板中,从而将两幅图像信息隐藏于3个纯随机相位板中。该方法原理简单,无需进行迭代操作。计算机模拟结果显示:任何一个密钥错误,均无法得到原始图像的任何信息。同时,解密过程对系统中距离及波长等参数非常敏感,较大地提升了系统的安全性。     

采用色差先验约束的像差校正技术

本文通过分析自然图像的边缘3个通道之间的关联性,提出"同一物体的边缘在3个颜色通道应处于相同位置"的色差先验约束,该约束在数学上近似为各通道的相对导数相等,基于此色差先验约束,建立了一种新的像差校正模型即图像解卷积模型,并给出了基于交替方向乘子法的模型求解算法。实验结果表明:本文的像差校正技术可以提升图像的峰值信噪比10 dB以上,明显优于目前主流的BM3D和YUV算法,并且视觉提升效果明显,基本满足普通光学系统对像差的校正要求。     

改进的盲解卷积技术在远距离激光光斑图像复原中的应用

为了提高外场实验中远距离测量激光光斑位置的精度,提出利用盲解卷积技术对光斑图像进行事后复原来削弱大气湍流对光斑成像的影响。首先,介绍了经典盲解卷积算法,分析了其不足之处,并提出了一种改进的盲解卷积算法。为了提高目标函数的收敛性和收敛速度,在TV(Total Variation)目标函数加入惩罚项,并对交替迭代法进行改进。然后,用数学方法证明了改进的盲解卷积算法的收敛性。最后,进行了仿真实验。与传统算法相比,用改进算法恢复的图像信噪比至少提升了15%。文中给出了外场试验图像的实际复原效果。