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空间稳定炭黑颗粒有效颗粒密度的测定:二嵌段共聚物稳定剂组成的影响

Determination of Effective Particle Density for Sterically Stabilized Carbon Black Particles: Effect of Diblock Copolymer Stabilizer Composition.

作者信息

Growney David J, Fowler Patrick W, Mykhaylyk Oleksandr O, Fielding Lee A, Derry Matthew J, Aragrag Najib, Lamb Gordon D, Armes Steven P

机构信息

†Department of Chemistry, University of Sheffield, Brook Hill, Sheffield, South Yorkshire S3 7HF, U.K.

‡BP Formulated Products Technology, Technology Centre, Whitchurch Hill, Pangbourne, RG8 7QR, U.K.

出版信息

Langmuir. 2015 Aug 18;31(32):8764-73. doi: 10.1021/acs.langmuir.5b01651. Epub 2015 Aug 5.

Abstract

Two poly(styrene-b-hydrogenated isoprene) (PS-PEP) copolymers and a poly(styrene-b-hydrogenated butadiene) (PS-PB) diblock copolymer of differing polystyrene content (20, 28 or 35 mol %) and molecular weight (117-183 kg mol(-1)) are examined. These copolymers form star-like micelles in n-dodecane, as judged by TEM, DLS, and SAXS studies. At ambient temperature, such micelles are known to adsorb intact onto a model colloidal substrate such as carbon black, conferring a high degree of dispersion (Growney, D. J.; Mykhaylyk, O. O.; Armes, S. P. Langmuir 2014, 30, 6047). Isotherms for micellar adsorption on carbon black at 20 °C are constructed using a supernatant depletion assay based on UV spectroscopy by utilizing the aromatic chromophore in the polystyrene block. Perhaps surprisingly, the diblock copolymer with the lowest polystyrene content has the strongest affinity for the carbon black particles. Assuming that the star-like diblock copolymer micelles adsorb onto carbon black to form hemi-micelles with a stabilizer layer thickness equal to the mean micelle radius, the effective particle density of the resulting sterically stabilized carbon black particles in n-dodecane can be estimated from the SAXS micelle dimensions based on geometric considerations. As an approximation, a spherical core-shell morphology was assumed, and the primary grain size of the carbon black particles was determined to be 74 nm diameter as judged by BET surface area analysis. Using this approach, effective particle densities of 0.90, 0.91, and 0.92 g cm(-3) were calculated for sterically stabilized carbon black particles prepared using the PS-PB20, PS-PEP28, and PS-PEP35 diblock copolymers, respectively. These densities are significantly lower than that of carbon black (1.89 g cm(-3)), which indicates that the sterically stabilized carbon black particles are substantially solvated. Since the rate of sedimentation of the sterically stabilized carbon black particles depends on the density difference between the effective particle density and that of n-dodecane (0.75 g cm(-3)), particle size analysis via analytical centrifugation incurs large sizing errors unless the above corrected effective particle densities are utilized. This is important because analytical centrifugation is a highly convenient technique for assessing the relative degree of dispersion of sterically stabilized carbon black particles, which are utilized to inkjet inks and coatings formulations.

摘要

研究了两种聚苯乙烯-氢化异戊二烯(PS-PEP)共聚物和一种聚苯乙烯含量(20%、28%或35%摩尔)和分子量(117 - 183 kg mol⁻¹)不同的聚苯乙烯-氢化丁二烯(PS-PB)二嵌段共聚物。通过透射电子显微镜(TEM)、动态光散射(DLS)和小角X射线散射(SAXS)研究判断,这些共聚物在正十二烷中形成星状胶束。在环境温度下,已知这种胶束能完整地吸附到诸如炭黑等模型胶体基质上,赋予高度分散性(Growney, D. J.; Mykhaylyk, O. O.; Armes, S. P. Langmuir 2014, 30, 6047)。利用聚苯乙烯嵌段中的芳香发色团,通过基于紫外光谱的上清液耗尽测定法构建了20℃下胶束在炭黑上的吸附等温线。也许令人惊讶的是,聚苯乙烯含量最低的二嵌段共聚物对炭黑颗粒具有最强的亲和力。假设星状二嵌段共聚物胶束吸附到炭黑上形成半胶束,其稳定剂层厚度等于平均胶束半径,基于几何考虑,可根据SAXS胶束尺寸估算在正十二烷中所得空间稳定化炭黑颗粒的有效颗粒密度。作为近似,假设为球形核壳形态,通过BET表面积分析判断炭黑颗粒的初级粒径为直径74 nm。使用这种方法,分别计算出使用PS-PB20、PS-PEP28和PS-PEP35二嵌段共聚物制备的空间稳定化炭黑颗粒的有效颗粒密度为0.90、0.91和0.92 g cm⁻³。这些密度显著低于炭黑的密度(1.89 g cm⁻³),这表明空间稳定化炭黑颗粒大量被溶剂化。由于空间稳定化炭黑颗粒的沉降速率取决于有效颗粒密度与正十二烷密度(0.75 g cm⁻³)之间的密度差,除非使用上述校正后的有效颗粒密度,否则通过分析离心进行的粒度分析会产生较大的尺寸误差。这很重要,因为分析离心是评估空间稳定化炭黑颗粒相对分散程度(用于喷墨油墨和涂料配方)一种非常方便的技术。

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