Improved methods for evaluating the molar mass distributions of cellulose in kraft pulp

Multi‐angle laser light scattering (MALLS) was used to characterize birch kraft pulps with respect to their absolute molecular mass distributions (MMDs). The pulps were dissolved in lithium chloride/N,N‐dimethylacetamide and separated by size exclusion chromatography (SEC). The weight‐average and number‐average molecular masses of the cellulose fractions of the pulps obtained from the absolute MALLS measurements were compared with the molar masses obtained by direct‐standard‐calibration relative pullulan standards. Discrepancies between the two detection methods were found, and two ways of correlating the relative pullulan molar masses to the absolute molar masses were examined. In the first method, the correlation was made over a large range of molecular masses. The second method correlated the molecular masses of the standards to the molecular masses of samples by the calculation of fictitious, cellulose‐equivalent molar masses of the standards. With the preferred second method, a more correct MMD of kraft pulp samples could, therefore, be obtained from an SEC system calibrated with narrow standards. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1170–1179, 2003     

Dynamic light scattering studies on random cross-linking of polystyrene in semi-dilute solution

The random cross-linking of appropriately functionalized polystyrene in semi-dilute toluene solution (c = 0.01–0.05 g/mL) was studied by time-dependent measurements of dynamic light scattering. Macroscopic gelation occurred from concentrations as low as 0.02 g/mL. The gelation time, determined from the first appearance of fluctuations of the scattering intensity and the initial amplitude of the intensity correlation function (ICF), decreases markedly from about 100 min to 10 min with an increase of polymer concentration or cross-linker content. After the gel point, the ICFs display a characteristic power-law decay. The power-law exponent, n = 0.75 ± 0.06, does not change with (i) extent of reaction, (ii) polymer concentration, and (iii) cross-linker concentration, within the inspected ranges. This universal behavior is traced back to the fact that gelation took place as a result of random cross-linking of existent macromolecules, whose state of solution does not change markedly during conversion.     

Small-angle neutron scattering from branched epoxide resins

Small-angle neutron scattering experiments in the range of q² from 0.01 to 25 nm⁻² have been carried out on branched epoxide resins based on bisphenol-A at the Institute Laue—Langevin (I.L.L) in Grenoble (q=(4π/λ) sin(θ/2)). Measurements were made with six samples in the range of M_W from 1500 to 19 000 and four concentrations between 1.3 and 10% (w/w) in deuterated diglyme. The results are as follows: (i) The mean square radius of gyration follows a relationship S²_z=4.69×10⁻⁴M^1.20_W (nm²). (ii) In all cases fairly large second virial coefficients A₂ are obtained which, however, decrease strongly with molecular weight. Above M_W=2500, the virial coefficient follows the relationship A₂=1.6M^−0.85_W (mol cm³g⁻²). (ii) The reciprocal particle scattering factor as a function of q² exhibits only a slight upturn and otherwise shows the behaviour of a randomly branched polycondensate. The slight upturn is discussed as being caused by the finite volume of the monomeric unit. Possible reasons for the high exponent in the S²_z versus M_W dependence are briefly discussed.     

基于逐次散射法的海洋-大气矢量辐射传输模式

首先推导了粗糙洋面双向偏振反射模型pBRDF(Bidirectional Polarized Reflectance Distribution Function),并将其与SOSVRT(Successive Order of Scattering Radiative Transfer)矢量辐射传输模式耦合,建立了海洋-大气耦合的矢量辐射传输模式,并对该耦合模式的模拟结果与前人模拟结果进行对比,验证了该耦合模式的可靠性与有效性。不同大气和洋面状态、不同高度的主平面内辐射强度和偏振度的模拟结果表明:pBRDF模型可以很好地模拟不同风速下洋面的偏振反射分布特征;洋面在特定角度具有很高的偏振度,并对大气顶的偏振辐射有很大影响。因此,该耦合模式可以更准确地处理辐射光谱在海洋-大气两种介质间的传输问题,对矢量辐射传输、大气遥感问题的研究有重要意义。     

Quantitative analysis of small angle neutron scattering data from montmorillonite dispersions

A new model is presented which can describe quantitatively the small angle neutron scattering from montmorillonite-type clay dispersions and polymer-clay nanocomposites. The model is shown to be able to describe well the data from a series of dilute montmorillonite in water dispersions in which the deuterium content of the water phase is varied. The fits combined with information from other techniques suggest strongly that H-D exchange occurs in the montmorillonite-water dispersions. Deviations from Q⁻² behaviour often observed experimentally for clay dispersions are convincingly explained by the presence of a small proportion of tactoids.     

Lamellar Morphology of Poly(3-hydroxybutyrate)/Poly(ethylene oxide) Blends as Studied via Small Angle X-ray Scattering

The lamellar morphology of a melt-miscible blend consisting of two crystalline constituents, poly(3-hydroxybutyrate) (PHB) and poly(ethylene oxide) (PEO) have been investigated by means of small angle X-ray scattering (SAXS). The blend was a crystalline/amorphous system when temperatures lay between the melting point of PEO (ca. T _m ^PEO=60C) and that of PHB (ca. T _m ^PHB=170C), while it became a crystalline/crystalline system below T _m ^PEO. The crystalline microstructures of the blends were induced by two types of crystallization history, i.e. one-step and two-step crystallizations. In the one-step crystallization, the blends were directly quenched from the melt to room temperature to allow simultaneous PHB and PEO crystallization. The two-step crystallization involved first cooling to 70C to allow PHB crystallization for 72 h followed by cooling to room temperature (ca. 19C) to allow PEO crystallization. In the crystalline/crystalline state, two scattering peaks have been observed in the Lorentz-corrected SAXS profiles, irrespective of the crystallization histories, meaning that crystallization created separate PHB and PEO lamellar stack domains. One-step crystallization yielded lamellar stack domains containing almost pure PHB and PEO lamellae. Two-step crystallization generated almost pure PHB lamellar domains and the PEO lamellar domains with inserted PHB lamellae. In the crystalline/amorphous state, the composition dependence of the amorphous layer thickness (l _a), the presence of zero-angle scattering, and the volume fraction of the PHB lamellar stack (_s) revealed that both one-step and two-step crystallizations, generated the interfibrillar segregation morphology, where the extent of interfibrillar segregation of amorphous PEO increased with increasing PEO content.     

On the molecular weight determination of a poly(aryl-ether-ether-ketone) (PEEK)

Attempts have been made to determine the weight average molecular weight ($\text{M}\text{?}{}_{\mathrm{<mtext>W</mtext>}}$), the radius of gyration ($\text{R}\text{?}{}_{\mathrm{<mtext>G</mtext>}}$) and the second virial coefficient (A₂) of five samples of poly(ether-ether-ketone) (PEEK) by light scattering (LS) in concentrated sulphuric acid. Account has been taken of the sulphonation of the polymer. Correlations between LS-molecular weights, melt viscosities and intrinsic viscosities in sulphuric acid or in a $\text{50}\text{50}$ phenol-trichlorobenzene mixture have been established. Gel permeation chromatography (g.p.c.) analyses at 115°C have been performed in this latter solvent and two calibration methods were compared.     

基于多散射模型的光源退化图像复原方法及应用

由于大气粒子对光的多散射作用非常显著,多散射的一般表现是在各种天气条件下光源周围的辉光现象。针对恶劣天气条件下的光源图像,采用辐射传输方程建立了点光源的多散射模型。根据所得到的点扩散函数对晴朗天气下带有光源的图像添加天气效果,并对恶劣天气条件下的光源图像进行复原,去除光源周围的辉光,从而得到清晰的光源图像。仿真结果证明了该方法的有效性.     

共振散射光谱法研究槲皮素与DNA相互作用

在BR缓冲液中,槲皮素存在微弱的共振散射现象,分别在288 nm、466 nm、562 nm处出现共振散射峰,随着DNA的加入,散射信号逐渐增强,且以上3处的峰值明显增加,并且562 nm处的增加值与DNA在3.024×10-7 mol/L～9.072×10-5 mol/L范围内呈现出良好的线性关系.在20℃时,通过Scatchard方程计算出槲皮素与DNA结合常数K=9.91×106 mol-1.L.     

有限体积法求解立体角离散误差

为解决采用有限体积法求解辐射传输方程时引起离散误差的问题,从有限体积法立体角内热流密度的求解过程出发,运用泰勒级数推导了近似误差的表达式,并分析影响离散误差的各种因素,包括离散射线数,辐射强度分布,假散射及网格比.根据分析结果,采用辐射强度的连续分布模型,模拟了各种因素对误差的影响.结果表明,辐射强度的分布函数对于有限体积法的离散误差有一定程度影响.当增加网格数及减小网格尺寸比时,可以有效地减小离散误差.假散射与离散误差间呈较强的非线性耦合关系.