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沥青质的溶液性质。

Solution properties of asphaltenes.

作者信息

Barré Loïc, Simon Sébastien, Palermo Thierry

机构信息

Institut Français du Pétrole (IFP), 1&4 Avenue du Bois-Préau, 92852 Rueil-Malmaison, France.

出版信息

Langmuir. 2008 Apr 15;24(8):3709-17. doi: 10.1021/la702611s. Epub 2008 Mar 4.

Abstract

Ultracentrifugation has been used to produce asphaltene fractions of reduced polydispersity. The structure of these asphaltene fraction solutions has been investigated using viscosity and X-ray scattering (SAXS) measurements as a function of concentration. The relative viscosities of the solutions were found to be fraction-dependent: intrinsic viscosities, radii of gyration, and second viriel coefficients followed a power law with molar mass Mw. A flat disc model succeeded in describing scattering data but failed to take viscosity data into account. By contrast, a fractal model has been found to be consistent with dependence of all measured parameters. Asphaltene-in-toluene solutions were found to form nanometric mass fractal aggregates of fractal dimension 2.1, which in consequence trapped solvent. When, instead of concentration, effective volume fractions are used, the relative viscosities of fractions merge on a master curve which can be fitted by a hard sphere model. In addition, the reduced osmotic moduli deduced from scattering measurements of the different solutions, when expressed as a function of a concentration adimensional parameter, merge again on a master curve which is in accordance with the hard sphere behavior. The viscosities of solutions can be fully predicted from structure considerations if the ratio of hydrodynamic to gyration radius is taken as 0.6. This ratio is found consistent with the fractal description of the aggregates.

摘要

超速离心已被用于制备多分散性降低的沥青质馏分。已使用粘度和小角X射线散射(SAXS)测量作为浓度的函数来研究这些沥青质馏分溶液的结构。发现溶液的相对粘度与馏分有关:特性粘度、回转半径和第二维里系数遵循与摩尔质量Mw的幂律关系。扁平圆盘模型成功地描述了散射数据,但未能考虑粘度数据。相比之下,已发现分形模型与所有测量参数的依赖性一致。发现沥青质在甲苯中的溶液形成分形维数为2.1的纳米级质量分形聚集体,因此捕获了溶剂。当使用有效体积分数而非浓度时,馏分的相对粘度在一条主曲线上合并,该主曲线可用硬球模型拟合。此外,从不同溶液的散射测量推导的约化渗透模量,当表示为浓度无量纲参数的函数时,再次在一条与硬球行为相符的主曲线上合并。如果将流体动力学半径与回转半径之比取为0.6,则可以从结构考虑完全预测溶液的粘度。发现该比率与聚集体的分形描述一致。

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