Critical Phenomena in Fluid Films: Critical-Temperature-Shift, Crossover-Temperature, and Coexistence-Curve-Amplitude Exponents, and a Fluid-Boundary Interaction

Meadows, Michael R.; Scheibner, B. A.; Mockler, R. C.; O'Sullivan, W.J.

doi:10.1103/physrevlett.43.592

Cited by 32 publications

(1 citation statement)

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“…86 We also point out that the Keddie et al 7 have proposed an alternative empirical relation for the shift in T g due to confinement. Their relation apparently draws on the phenomenology of transition shifts in second-order phase transitions rather than melting, which is a first-order transition, and correspondingly they argue for a shift involving the ratio (a/h) δ where the exponent δ is close to 2 (δ = 2 in mean field theory, but fluctuations make δ smaller in this type of transition 75,89,90 ). We can also fit our data to this form, but Eq.…”

Section: Gibbs-thomson Model For Finite-size Dependence Of T Gmentioning

confidence: 99%

A unifying framework to quantify the effects of substrate interactions, stiffness, and roughness on the dynamics of thin supported polymer films

Hanakata

Betancourt

Douglas

et al. 2015

The Journal of Chemical Physics

131

180

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Changes in the dynamics of supported polymer films in comparison to bulk materials involve a complex convolution of effects, such as substrate interactions, roughness, and compliance, in addition to film thickness. We consider molecular dynamics simulations of substrate-supported, coarse-grained polymer films where these parameters are tuned separately to determine how each of these variables influence the molecular dynamics of thin polymer films. We find that all these variables significantly influence the film dynamics, leading to a seemingly intractable degree of complexity in describing these changes. However, by considering how these constraining variables influence string-like collective motion within the film, we show that all our observations can be understood in a unified and quantitative way. More specifically, the string model for glass-forming liquids implies that the changes in the structural relaxation of these films are governed by the changes in the average length of string-like cooperative motions and this model is confirmed under all conditions considered in our simulations. Ultimately, these changes are parameterized in terms of just the activation enthalpy and entropy for molecular organization, which have predictable dependences on substrate properties and film thickness, offering a promising approach for the rational design of film properties. C 2015 AIP Publishing LLC. [http://dx

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