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Journal ArticleDOI

Prediction of Structure and Energy of Trans-1,4-Polybutadiene Glassy Surface by Atomistic Simulations of Free-Standing Ultrathin Films

02 Mar 2012-Journal of Macromolecular Science, Part B (Taylor & Francis Group)-Vol. 51, Iss: 11, pp 2201-2221
Abstract: Atomistic modeling of amorphous trans-1,4-polybutadiene (TPBD), using molecular mechanics and molecular dynamics (MD) simulations, is performed to generate three-dimensionally periodic bulk and two-dimensionally periodic thin film condensed phases. The condensed structures are constructed using multiple polymer chains. Structural and energetic relaxations and sampling of properties are performed using MD in the canonical ensemble (NVT) by a procedure that relieves local high-energy spots and brings the system to realistic thermodynamic states. The calculated surface energy for TPBD, 30.72 erg/cm2, is in excellent agreement with the reported experimental value of 31 erg/cm2. The structure of the surface layers is probed in terms of the atomic mass density variations, bond-bond orientation function profiles, and the distribution of the dihedral angles about the rotatable backbone bonds. The thickness of the surface layer over which the density varies smoothly but rapidly is found to be approximately 15 A. T... more

Topics: Surface energy (55%), Molecular dynamics (53%), Canonical ensemble (52%) more
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01 Jan 1964-
Abstract: In his opening remarks at the first symposium in this series Professor Robert Good pointed out that Galileo in the 17 century was quite likely the first investigator to observe contact angle behavior with his experiment of floating a thin gold leaf on top of a water surface. Since that time contact angle measurements have found wide application as a method for determining the energetics of surfaces. This, in turn, has a profound effect on the wettability and adhesion of liquids and coatings to surfaces. more

1,568 citations

Book ChapterDOI
01 Jan 1964-

1,520 citations

01 Jan 1972-

782 citations

"Prediction of Structure and Energy ..." refers background or result in this paper

  • ...6 cal1/2/cm3/2.[41] The statistics on the individual values of the solubility parameter of the sample of structures here are acceptable on the basis of the standard deviation and by comparison with experimental data and with those available from earlier studies on such atomistic models[7,8,21–23,28,42] for various polyolefins and slightly polar polymers....


  • ...89 gm/cm3 which is the experimental amorphous density of polybutadienes at room temperature.[41] The cell edge dimensions were therefore set to a value of 23....


Journal ArticleDOI
01 Jul 1985-Macromolecules

758 citations

"Prediction of Structure and Energy ..." refers methods in this paper

  • ...The packing of the three TPBD chains into the box with periodic boundary conditions was according to the method of Theodorou and Suter.[42] A constant volume, constant temperature, constant moles (NVT) ensemble was used to perform the relaxation of the bulk cells....


  • ...The packing of the three TPBD chains into the box with periodic boundary conditions was according to the method of Theodorou and Suter....


  • ...the periodic box is greater than the sizes previously used in polybutadiene simulations[7–9] and satisfies the persistence length criterion[42] that the cell dimensions should be greater than twice the value of the persistence length of the polymer....


13 May 1999-
Abstract: This text deals from a fundamental viewpoint with the behaviour of polymers at surfaces and interfaces. Topics covered include the nature and properties of the surface of a polymer melt, the structure of interfaces between different polymers and between polymers and non-polymers, the molecular basis of adhesion, and the properties of polymers at liquid surfaces. Emphasis is placed on the underlying physical principles. Statistical mechanics models of the behaviour of polymers near interfaces are introduced, with the emphasis on theory that is tractable and applicable to experimental situations. Advanced undergraduates, graduate students and research workers in physics, chemistry and materials science with an interest in polymers will find this book of value. more

421 citations

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