Coarse Grained End Bridging Monte Carlo Simulations of Poly(ethylene terephthalate) Melt

Kamio, Kazunori; Moorthi, Krzysztof; Theodorou, Doros N.

doi:10.1021/ma060803s

Cited by 68 publications

(107 citation statements)

References 49 publications

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“…For example the cumulative probability of the PP length as obtained from MC simulations of entangled athermal chains (Foteinopoulou et al, 2008) is in excellent agreement with the predictions of the thermodynamicalry-consistent slip-link model by Khaliullin and Schieber (2009). Same is true when we compare the distribution of the entanglement spacing against the exponential-type master curve proposed by Tzoumanekas and Theodorou (Kamio et al, 2007;Tzoumanekas and Theodorou, 2006).…”

Section: Scaling Of Entanglementssupporting

confidence: 79%

Monte Carlo simulations of densely-packed athermal polymers in the bulk and under confinement

Foteinopoulou

Karayiannis

Laso

2015

Chemical Engineering Science

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HIGHLIGHTS• Identification of the maximally random jammed state for polymer packings.• Molecular simulation of the phase transition in hard-sphere chains.• Molecular modelling of the effect of confinement in densely-packed athermal polymers.• Numerical calculation of the topological constraints in polymeric systems.• First-principles calculation of the scaling regimes in flexible polymers. ABSTRACTWe review the main results from extensive Monte Carlo (MC) simulations on athermal polymer packings in the bulk and under confinement. By employing the simplest possible model of excluded volume, macromolecules are represented as freely-jointed chains of hard spheres of uniform size. Simulations are carried out in a wide concentration range: from very dilute up to very high volume fractions, reaching the maximally random jammed (MRJ) state. We study how factors like chain length, volume fraction and flexibility of bond lengths affect the structure, shape and size of polymers, their packing efficiency and their phase behaviour (disorder-order transition). In addition, we observe how these properties are affected by confinement realized by fiat, impenetrable walls in one dimension. Finally, by mapping the parent polymer chains to primitive paths through direct geometrical algorithms, we analyse the characteristics of the entanglement network as a function of packing density.

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Section: Scaling Of Entanglementssupporting

confidence: 79%

Monte Carlo simulations of densely-packed athermal polymers in the bulk and under confinement

Foteinopoulou

Karayiannis

Laso

2015

Chemical Engineering Science

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“…This formula provided accurate predictions for a wide range of atomistic or coarse-grained polymers [19]. As shown in the main part of Fig.…”

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confidence: 69%

Universal Scaling, Entanglements, and Knots of Model Chain Molecules

et al. 2008

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By identifying the maximally random jammed state of freely jointed chains of tangent hard spheres we are able to determine the distinct scaling regimes characterizing the dependence of chain dimensions and topology on volume fraction. Calculated distributions of (i) the contour length of the primitive paths and (ii) the number of entanglements per chain agree remarkably well with recent theoretical predictions in all scaling regimes. Furthermore, our simulations reveal a hitherto unsuspected connection between purely intramolecular (knots) and intermolecular (entanglements) topological constraints. DOI: 10.1103/PhysRevLett.101.265702 PACS numbers: 61.20.Ja, 02.10.Kn, 64.70.QÀ, 64.75.Gh Since Bernal's pioneering work almost half a century ago [1], a great deal of experimental, theoretical, and simulation effort has been devoted to the investigation of random packings of single spheres and other nonsymmetric hard-body objects, especially in the vicinity of the configuration referred to nowadays as the maximally random jammed (MRJ) state [2][3][4]. MRJ is defined as the state in which the most sensitive measure of order parameter is minimized among all statistically homogeneous and isotropic jammed structures [3]. In practice, as the MRJ state is approached the ability of hard spheres to move (''rattle'' [3] and ''flip' ' [5] for monoatomic and chain systems, respectively) without incurring overlaps declines precipitously. Regarding random assemblies of chains of hard spheres, connectivity endows them with a rich physical behavior. The problem of densely packed polymers is of vital importance in thermodynamics, biology, phase transitions, glassy state, colloids, granular media, combinatorics, and perturbation theory. Recently, the computational challenge of determining the MRJ state could be solved, albeit for short chains only [5]. Thus, universal scaling, and asymptotic behavior in the infinite chain length (N) limit, as predicted by Edwards [6] and de Gennes [6] could only be conjectured.In this Letter we determine, through extensive simulations, the MRJ state for strongly entangled freely jointed chains of tangent hard spheres (where bond length is fixed and equal to sphere diameter), deep in the asymptotic regime. This MRJ state is determined by means of large scale [Oð10 11 Þ steps], off-lattice, Monte Carlo simulations using a suite of powerful importance sampling, chainconnectivity altering algorithms [7] on a number of bulk systems ranging from 100 chains of N ¼ 12 to 54 chains of N ¼ 1000. Preliminary tests on cells of different sizes revealed the absence of system size effects on all calculated properties.We show that, within statistical uncertainty, hard-sphere chains reach their MRJ state at the same volume fraction (') as single spheres, ' MRJ % 0:638 AE 0:004, irrespective of chain length. The question is thus settled that neither chain length nor the tangency constraint of connectivity hinder random packing of chains with respect to assemblies of single spheres. This alone is an important resul...

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“…Moreover, other PIB systems with varying carbon number (C 80 , C 120 and C 240 , as shown in Figure 4) will also be studied in the future to verify which system has the lowest permeability to air. In conjunction with its low glass transition temperature (Kamio et al, 2007;Abrams and Kremer, 2003), PIB seems to be an excellent candidate for use as a hermetic stopper in medical applications. The next step is to recommend the polymer for laboratory scale synthesis, which will provide the experimental validation of the properties claimed here.…”

Section: Discussion Of Resultsmentioning

confidence: 99%

“…PIB is known to be an important elastomer with several interesting properties such as low glass transition temperature (it is classified as the least fragile polymer in Angell's terminology (Angell, 1995) and high friction coefficient. From different literature sources (Kamio et al, 2007;Abrams and Kremer, 2003), it is also reported that this polymer presents markedly low permeability properties to small gas molecules in comparison to other elastomers due to the presence of the two bulky pendant methyl groups on each basic repeat unit structure. The results from the macro-scale stage therefore confirm known data and gives confidence that the methodology is able to find potentially good candidates.…”

Section: Structural Constraintsmentioning

confidence: 98%

“…obtained from molecular simulations depends mainly on the efficiency of the method used to carry out the simulations and the reliability of the force-field employed for the description of the intra-and interatomic interactions. Examples of polymers typically addressed with such a method include polystyrene (Spyriouni et al, 2007;Harmandaris et al, 2006;Milano and Müller-Plathe, 2005), polyethylene terephthalate (Kamio et al, 2007), polycarbonates (Abrams and Kremer, 2003), polyphenylene dendrimers (Carbone et al, 2007), and also DNA (Knotts et al, 2007). In this paper, the method developed by Tsolou et al (2008) is used.…”

Section: Brazilian Journal Of Chemical Engineeringmentioning

confidence: 99%

See 1 more Smart Citation

Computer aided polymer design using multi-scale modelling

Satyanarayana¹,

Abildskov²,

Gani³

et al. 2010

Braz. J. Chem. Eng.

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-The ability to predict the key physical and chemical properties of polymeric materials from their repeat-unit structure and chain-length architecture prior to synthesis is of great value for the design of polymerbased chemical products, with new functionalities and improved performance. Computer aided molecular design (CAMD) methods can expedite the design process by establishing input-output relations between the type and number of functional groups in a polymer repeat unit and the desired macroscopic properties. A multi-scale model-based approach that combines a CAMD technique based on group contribution plus models for predicting polymer repeat unit properties with atomistic simulations for providing first-principles arrangements of the repeat units and for predictions of physical properties of the chosen candidate polymer structures, has been developed and tested for design of polymers with desired properties. A case study is used to highlight the main features of this multi-scale model-based approach for the design of a polymer-based product.

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Coarse Grained End Bridging Monte Carlo Simulations of Poly(ethylene terephthalate) Melt

Cited by 68 publications

References 49 publications

Monte Carlo simulations of densely-packed athermal polymers in the bulk and under confinement

Monte Carlo simulations of densely-packed athermal polymers in the bulk and under confinement

Universal Scaling, Entanglements, and Knots of Model Chain Molecules

Computer aided polymer design using multi-scale modelling

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