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限制和加工对超薄聚合物薄膜玻璃化转变温度及物理老化的影响:新型荧光测量法

Confinement and processing effects on glass transition temperature and physical aging in ultrathin polymer films: novel fluorescence measurements.

作者信息

Ellison C J, Kim S D, Hall D B, Torkelson J M

机构信息

Department of Chemical Engineering, Northwestern University, Evanston, IL 60208-3120, USA.

出版信息

Eur Phys J E Soft Matter. 2002 May;8(2):155-66. doi: 10.1140/epje/i2001-10057-y.

Abstract

Fluorescence intensity measurements of chromophore-doped or -labeled polymers have been used for the first time to determine the effects of decreasing film thickness on glass transition temperature, T(g), the relative strength of the glass transition, and the relative rate of physical aging below T(g) in supported, ultrathin polymer films. The temperature dependence of fluorescence intensity measured in the glassy state of thin and ultrathin films of pyrene-doped polystyrene (PS), poly(isobutyl methacrylate) (PiBMA), and poly(2-vinylpyridine) (P2VP) differs from that in the rubbery state with a transition at T(g). Positive deviations from bulk T(g) are observed in ultrathin PiBMA and P2VP films on silica substrates while substantial negative deviations from bulk T(g) are observed in ultrathin PS films on silica substrates. The relative difference in the temperature dependences of fluorescence intensity in the rubbery and glassy states is usually reduced with decreasing film thickness, indicating that the strength of the glass transition is reduced in thinner films. The temperature dependence of fluorescence intensity also provides useful information on effects of processing history as well as on the degree of polymer-substrate interaction. In addition, when used as a polymer label, a mobility-sensitive rotor chromophore is demonstrated to be useful in measuring relative rates of physical aging in films as thin as 10 nm.

摘要

首次使用对发色团进行掺杂或标记的聚合物的荧光强度测量,来确定在支撑的超薄聚合物薄膜中,膜厚度减小对玻璃化转变温度T(g)、玻璃化转变的相对强度以及低于T(g)时物理老化的相对速率的影响。在掺杂芘的聚苯乙烯(PS)、聚(甲基丙烯酸异丁酯)(PiBMA)和聚(2-乙烯基吡啶)(P2VP)的薄膜和超薄膜的玻璃态下测量的荧光强度的温度依赖性,与在橡胶态下且在T(g)处有转变时不同。在二氧化硅衬底上的超薄PiBMA和P2VP薄膜中观察到相对于本体T(g)的正偏差,而在二氧化硅衬底上的超薄PS薄膜中观察到相对于本体T(g)的显著负偏差。橡胶态和玻璃态下荧光强度温度依赖性的相对差异通常随着膜厚度减小而减小,这表明在较薄的薄膜中玻璃化转变的强度降低。荧光强度的温度依赖性还提供了关于加工历史的影响以及聚合物-衬底相互作用程度的有用信息。此外,当用作聚合物标记时,一种对迁移率敏感的转子发色团被证明可用于测量薄至10 nm的薄膜中的物理老化相对速率。

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