期刊
LANGMUIR
卷 31, 期 37, 页码 10254-10264出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.langmuir.5b01890
关键词
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资金
- European Social Fund
- FEDER [UID/QUI/50006/2013]
- European Union (FEDER funds) [NORTE-07-0124-FEDER-000067-NANOCHEMISTRY]
- [SFRH-BPD-90265-2012]
- [SRDA-0451-11]
- [VEGA 2/0093/12]
Tuning of surface properties plays an important role in applications ranging from material engineering to biomedicine/chemistry. The interactions of chains grafted to a solid support and exposed to a matrix of chemically identical chains represent an intriguing issue. In this work, the behavior of poly(ethylene oxide) (PEO) chains grafted irreversibly onto an amorphous silica and immersed in the matrix of free PEO chains of different polymerization degree is studied using molecular dynamics simulations. The density distributions of grafted and free PEO chains, the height of the grafted layer, overlap parameters, and orientation order parameters depend not only on the grafting density but also on the length of free chains which confirm the entropic nature of the interactions between the grafted and free chains. In order to achieve a complete expulsion of the free chains from the grafted layer, a grafting density as high as 3.5 nm(-2) is necessary. Free PEO chains of 9 monomers leave the grafted layer at lower grafting densities than the longer PEO chains of 18 monomers in contrast with the theoretical predictions. The height of the grafted layer evolves with the grafting density in the presence of free chains in qualitative agreement with the theoretical phase diagram.
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