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小角散射显示添加聚合物的纳米颗粒分散体中粒子间势与吸附结构之间的相互作用

Interplay between Interparticle Potential and Adsorption Structure in Nanoparticle Dispersions with Polymer Addition as Displayed by Small-Angle Scattering.

作者信息

Kusano Takumi, Kumano Naomi, Yoshimune Wataru, Munekata Toshihisa, Matsunaga Takuro, Harada Masashi

机构信息

Toyota Central R&D Labs., Inc., 41-1 Yokomichi, Nagakute, Aichi 480-1192, Japan.

出版信息

Langmuir. 2021 Jun 22;37(24):7503-7512. doi: 10.1021/acs.langmuir.1c00968. Epub 2021 Jun 10.

Abstract

The effect of polymer adsorption on the dispersion stability of particles is an important subject applicable to various manufacturing processes. In this study, small-angle scattering was used to examine the relationship between interparticle potential and polymer adsorption in dispersions of nanoparticles with an 81 Å radius containing two types of polymers. Small-angle X-ray scattering (SAXS) measurements in a silica/polyacrylamide (PAAm) system showed an increase in interparticle attractive interactions as PAAm concentration was increased. In a silica/poly(ethylene oxide) (PEO) system, the correlation between PEO concentration and interparticle potential strength became negligible at higher concentrations. Hence, the contrast variation small-angle neutron scattering (CV-SANS) method was employed to evaluate the interparticle potential and polymer adsorption simultaneously. CV-SANS revealed that PAAm was adsorbed to silica particles with a polymer shell layer thickness of 186 Å. The attractive potential observed in the absorbed layer region can be attributed to bridging PAAm molecules between the silica particles. By contrast, CV-SANS of the silica/PEO system indicated a low-polymer-concentration layer with a thickness of 34 Å around silica particles, indicating weak adsorption of PEO molecules. Negligible interaction between PEO and silica particles was assumed to be the origin of the depletion stabilization from excess polymer addition. Thus, quantitative analyses conducted using SAXS and CV-SANS measurements for the first time clearly demonstrated a difference in the adsorption structure of the polymer, which induces changes in the interaction potential between nanoparticles.

摘要

聚合物吸附对颗粒分散稳定性的影响是一个适用于各种制造工艺的重要课题。在本研究中,小角散射被用于研究含有两种聚合物的半径为81 Å的纳米颗粒分散体中颗粒间势能与聚合物吸附之间的关系。在二氧化硅/聚丙烯酰胺(PAAm)体系中的小角X射线散射(SAXS)测量表明,随着PAAm浓度的增加,颗粒间的吸引相互作用增强。在二氧化硅/聚环氧乙烷(PEO)体系中,在较高浓度下,PEO浓度与颗粒间势能强度之间的相关性变得可以忽略不计。因此,采用对比变化小角中子散射(CV-SANS)方法同时评估颗粒间势能和聚合物吸附。CV-SANS显示PAAm吸附在二氧化硅颗粒上,聚合物壳层厚度为186 Å。在吸附层区域观察到的吸引势能可归因于二氧化硅颗粒之间的桥连PAAm分子。相比之下,二氧化硅/PEO体系的CV-SANS表明在二氧化硅颗粒周围存在厚度为34 Å的低聚合物浓度层,表明PEO分子的吸附较弱。PEO与二氧化硅颗粒之间可忽略不计的相互作用被认为是过量添加聚合物导致耗尽稳定化的原因。因此,首次使用SAXS和CV-SANS测量进行的定量分析清楚地证明了聚合物吸附结构的差异,这会引起纳米颗粒之间相互作用势能的变化。

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