Surface diffusion in reversed-phase liquid chromatography using silica gels bonded with C1 and C18 ligands of different densities

Surface diffusion in reversed-phase liquid chromatography (RPLC) using silica gels bonded with C₁ and C₁₈ alkyl ligands of different densities was studied from the viewpoints of two extrathermodynamic relationships, i.e., enthalpy-entropy compensation (EEC) and linear free energy relationship (LFER). First, according to the four methods proposed by Krug et al., the values of surface diffusion coefficient (D_s) were analyzed to confirm that an actual EEC resulting from substantial physico-chemical effects takes place for surface diffusion. Then, it was also demonstrated that a LFER is observed between surface diffusion and the retention equilibrium. The establishment of EEC and LFER suggests a mechanistic similarity of molecular migration by surface diffusion, irrespective of the alkyl chain length and the densities of C₁ and C₁₈ ligands. Finally, a thermodynamic model for the LFER based on the real EEC was used to estimate D_s values under various RPLC conditions. The D_s values can be estimated with a mean square deviation of about 25–30%. The agreement between the D_s values estimated and those experimentally measured suggests that the total mass flux by surface diffusion consists of the two contributions due to C₁ and C₁₈ ligands and that the contribution of each ligand is proportional to the ligand density.     

Study of the influence of physical aging on macroradical decay in poly(methyl methacrylate)

The macroradical decay in poly(methyl methacrylate) samples with different thermal histories was investigated in the temperature interval 20–100 °C using ESR spectroscopy and the second order kinetic model. The rate constants exhibit two different regimes with the transitions atT _tr=68±1°C which are independent of thermal treatment. ForT<T _tr andT>T _tr the rate constants as well as the corresponding activation parameters are sensitive to history because of different physical microstructures. The compensation law, i.e., the linear relation between lnk _{o, eff} andE _eff, was analyzed in terms of the so-called compensation quantitiesk _c andT _c and a proximity betweenT _c=T _tr andT _o=53±3 °C — Vogel temperature for -segmental dynamics was found. A comparison of kinetic and dynamic data suggests that the decay of terminal macroradicals in the low-temperature region is controlled by secondary relaxations and that the -mobility contributes to a more rapid decay at higher temperatures belowT _g.     

基于BAS-BP-Bagging模型的光纤陀螺温度补偿

为提高光纤陀螺的输出精度,以天牛须搜索算法(BAS)优化后的BP神经网络模型为基学习器,采用Bagging并行集成学习算法建立了BAS-BP-Bagging温度补偿模型,并对某型号光纤陀螺进行了温度补偿实验。实验结果表明,在-40～+60℃温度变化环境下,该方法补偿后的光纤陀螺温度漂移相较于补偿前减小了近80%,相较于多项式补偿算法减小了55%,相较于BP神经网络补偿算法减小了30%左右。同时该模型在对新鲜样本的补偿过程中表现出了较为优越的泛化性能。     

位置敏感探测器光斑脱靶误差补偿方法研究

为了提高位置敏感探测器(PSD)的位置检测范围,解决光斑在探测器光敏面脱靶时无法准确定位光斑的问题,提出一种光斑脱靶误差补偿方法,分析了脱靶前后PSD检测光斑能量重心变化规律,建立了PSD光强信号与位置检测误差间的函数关系。实验结果表明:当PSD光敏面尺寸为12mm×12mm时,对于半径为5mm的高斯光斑,通过所提出的光斑补偿方案补偿后PSD的X轴检测范围提高了66.7%,位置检测平均相对误差不超过5%,该方法对提高PSD位置检测性能具有重要的意义。     

Motion detection in moving camera videos using background modeling and FlowNet

Real-time moving object detection is challenging for moving cameras due to the moving background. Many studies use homography matrix to compensate for global motion by warping the background model to the current frame. Then, the pixel difference between the current frame and the background model is used for background subtraction. Moving pixels are extracted by applying adaptive threshold and some post-processing techniques. On the other hand, deep learning-based dense optical flow can be efficient enough to extract the moving pixels, but it increases computational cost. This study proposes a method to enhance a classical background modeling method with deep learning-based dense optical flow. The main contribution of this paper is to propose a fusing algorithm for dense optical flow and background modeling approach. The background modeling methods are error-prone, especially with continuous camera movement, while the optical flow method alone may not always be efficient. Our hybrid method fuses both techniques to improve the detection accuracy. We propose a software architecture to run background modeling and dense optical flow methods in parallel processes. The proposed implementation approach significantly increases the method’s working speed, while the proposed fusion and combining strategy improve detection results. The experimental results show that the proposed method can run at high speed and has satisfying performance against the methods in the literature.     

Thermodynamics of mixtures of hexane and heptane isomers with normal and branched hexadecane

Molar excess mixing enthalpies h ^E , Gibbs free energies g ^E and hence entropies s ^E have been obtained using calorimetry and the vapor sorption method at 25°C for hexane isomers+2,2,4,4,6,8,8-heptamethylnonane, a highly branched C ₁₆ . The h ^E and g ^E are negative while Ts ^E are positive, but small. The values are explained by the Prigogine-Flory theory through negative free volume contributions to h ^E and Ts ^E , counterbalanced in the case of Ts ^E by the positive combinatiorial Ts ^E for mixing molecules of different size. No contribution is seen from the interaction between methyl and methylene groups. The excess quantities are also obtained for hexane and heptane isomers mixed with n-hexadecane. Values of h ^E and Ts ^E are now strongly positive, while those of g ^E are only slightly less negative. The interpretation requires two recently advanced contributions in addition to those of the Prigogine-Flory theory: 1) a decrease of order when correlations of orientations between n-C ₁₆ molecules in the pure liquid are replaced in the solution by weaker correlations whose strengths depend on the shapes of the lower alkane isomers. For lower alkane isomers of the same shape, but highly sterically hindered, h ^E and Ts ^E are small, manifesting, 2) a negative contribution, ascribed to a rotational ordering of n-C ₁₆ segments on the sterically-hindered molecule. Enthalpy-entropy compensation is observed for these new contributions, arising from their rapid fall-off with increase of temperature.     

Kinetics of thermal decomposition of alkaline phosphates

Summary The thermal behavior of KH₂PO₄, NaH₂PO₄ and Na₂HPO₄ under non-isothermal conditions using TG method with different heating rates was studied. The values of the reaction rate were processed by means of Friedmans differential-isoconversional method. A dependence of the activation energy vs. conversion was observed. Therefore a procedure based on the compensation effect (suggested by Budrugeac and Segal) was applied. A less speculative data processing protocol was offered by the non-parametric kinetics method suggested by Serra, Nomen and Sempere. Three steps were observed by non-isothermal heating: a dehydration, a dimerization and a polycondensation. The differences in the intimate reaction mechanism are determined by the initial number of water molecules.     

Dielectric behaviour of a side-chain-bearing liquid-crystalline polysiloxane

The relaxation of electric field-induced polar orientation in a side-chain-bearing liquid-crystalline polysiloxane was measured by means of thermally stimulated depolarization currents. Different relaxation mechanisms were identified and characterized: the glass transition cooperative relaxation exhibits compensation behaviour. On the other hand, lowerT _g and upperT _g discharges were observed and their molecular nature is discussed.     

光度分析中协同系数补偿方法的研究──三次标准加入法同时测定钼、钨和钛

本文在两次标准加入法[1]的基础上，提出了三组份同时测定的三次标准加入法，并应用于钼、钨和钛的流动注射同时测定。测定条件：［水杨基荧光酮（SAF）］＝1．25　×10-4mol／L，［溴化＋六烷基三甲基铵（CTMAB）」＝2．5×10－3mol／L，pH1．35，25℃，采样、进样时间分别为10s和18s，进样频率128次／h。为消除组份间协同作用引起的吸光度加合性的偏离，定义了三组份协同系数。将其引入三组份同时测定方法，补偿了吸光度对线性的偏离。补偿后钼、钨和钛的测定范围分别为0．05～0．35，0．25～1．00，0．025～0．30mg／L。测定了钢样及模拟样品中钼、钨和钛含量，结果较好。     

Compensation effect in the electrical conduction process in a series of pyrenyl polyenes

The semiconductive properties of a series of pyrenyl polyenes of the type R-(CH=CH)_n-R, are studied as a function of the adsorption of different amount of a vapour. With regard to the compensation temperature (T ₀) the compounds are divided into two groups. For compounds which have odd number of double bonds,T ₀ is infinite and in compounds having even number double bonds,T ₀ is finite.T ₀ for II₂ is higher while that of II₄ is lower than the experimental temperature. DifferentT ₀ for the compounds having odd or even number of double bonds suggests a physical basis for the compensation rule, which we believe, is related to the molecular and crystalline structure of the compounds