Mapping atomistic simulations to mesoscopic models: a systematic coarse-graining procedure for vinyl polymer chains

The paper introduces a systematic procedure to coarse-grain atomistic models of the largest family of synthetic polymers into a mesoscopic model that is able to keep detailed information about chain stereosequences. The mesoscopic model consists of sequences of superatoms centered on methylene carbons of two different types according to the kind of diad (m or r) they belong to. The corresponding force-field contains three different bonds, six angle and three nonbonded terms. Recently developed analytical potentials, based on sums of Gaussians for bond and angle terms of the mesoscale force field have been used. For the nonbonded part, numerical potentials optimized by pressure-corrected iterative Boltzmann inversion have been used. As test case we coarse-grained an atomistic all-atom model of atactic polystyrene. The proposed mesoscale model has been successfully tested against structural and dynamical properties for different chain lengths and opens the possibility of relaxing melts of high molecular weight vinyl polymers.     

Effects of heat and pressure on intercalation structures of isobutylene‐isoprene rubber/clay nanocomposites. I. Prepared by melt blending

In this work, the effects of heat and pressure on intercalated structures of isobutylene‐isoprene rubber/clay nanocomposites (IIRCNs) prepared by melt blending were investigated. Not only the local intercalated structures were monitored by wide‐angle X‐ray diffraction, but also the spatial distributions of intercalated structures were observed by transmission electron microscope. The experimental result reveals that the intercalated structures and their spatial distributions in the matrix are extensively altered by the thermal treatment at atmospheric or higher pressure. The possible microstructural models for untreated and treated IIRCNs were put forward. The observed phenomena were interpreted from the viewpoints of thermodynamics and kinetics theories as well as the feature of rubber. Finally, guidelines were proposed for designing curing system to achieve desired intercalated/exfoliated morphology. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2653–2664, 2005     

Non-iterative and exact method for constraining particles in a linear geometry

We present a practical numerical method for evaluating the Lagrange multipliers necessary for maintaining a constrained linear geometry of particles in dynamical simulations. The method involves no iterations and is limited in accuracy only by the numerical methods for solving small systems of linear equations. As a result of the non-iterative and exact (within numerical accuracy) nature of the procedure, there is no drift in the constrained geometry, and the method is therefore readily applied to molecular dynamics simulations of, for example, rigid linear molecules or materials of non-spherical grains. We illustrate the approach through implementation in the commonly used second-order velocity-explicit Verlet method. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 911-916, 2005     

Segmental orientations and deformation mechanism of a poly(ether‐block‐amide) film

Simultaneous measurements of microscopic infrared dichroism, mesoscale deformation, and macroscopic stress have been made for a microphase‐separated film of poly(ether‐block‐amide) 4033 during uniaxial stretching at temperatures between 30 and 91 °C, well below the melting point of the hard polyamide‐12 (PA) domains. Before the onset of dramatic microstructural alterations, the true stress–strain relationship on the mesoscale can be described with an interpenetrating network model, and poly(tetramethylene oxide) (PTMO) soft segments undergo affine deformation. Beyond a threshold strain at which stress from the soft network becomes larger than that from the hard network, plastic deformation occurs in the hard PA domains, and this is accompanied by the downward derivations of the true stress and molecular orientation of PTMO blocks from the model predictions. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1161–1167, 2005     

Effects of formulation variables on liquid‐crystal droplet size distributions in ultraviolet‐cured polymer‐dispersed liquid‐crystal cells

The size distributions of liquid‐crystal droplets in ultraviolet‐cured polymer‐dispersed liquid‐crystal cells have been studied with optical microscopy. It has been observed that (1) the relative masses of the liquid crystal and crosslinking agent determine the droplet size distribution for submicrometer droplet diameters and (2) only the liquid‐crystal mass fraction affects the droplet size distribution for diameters ranging from 1 to 4 μm. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1842–1848, 2005     

Fitting properties from density functional theory based molecular dynamics simulations to parameterize a rigid water force field

In the quest towards coarse-grained potentials and new water models, we present an extension of the force matching technique to parameterize an all-atom force field for rigid water. The methodology presented here allows to improve the matching procedure by first optimizing the weighting exponents present in the objective function. A new gauge for unambiguously evaluating the quality of the fit has been introduced; it is based on the root mean square difference of the distributions of target properties between reference data and fitted potentials. Four rigid water models have been parameterized; the matching procedure has been used to assess the role of the ghost atom in TIP4P-like models and of electrostatic damping. In the former case, burying the negative charge inside the molecule allows to fit better the torques. In the latter, since short-range interactions are damped, a better fit of the forces is obtained. Overall, the best performing model is the one with a ghost atom and with electrostatic damping. The approach shown in this paper is of general validity and could be applied to any matching algorithm and to any level of coarse graining, also for non-rigid molecules.     

A mesoscopic Archimedean tiling having a new complexity in an ABC star polymer

The Archimedean tiling (3².4.3.4) is a regular but complex polygonal assembly of equilateral triangles and squares. This tiling pattern with mesoscopic repeating distance has been found for an ABC star‐branched three‐component polymer composed of polyisoprene, polystyrene, and poly(2‐vinylpyridine). In this structure the environment of a molecule splits into multiple sites and two microdomains with different sizes and shapes are formed for one component. This complexity is the first observation in complex polymer systems and can lead to a new type of mesoscale self‐organization. The tiling pattern has been observed for the other materials on much shorter length‐scale; therefore, the experimental fact observed in the present study is demonstrating that the complexity is universal over different hierarchies. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2427–2432, 2005     

Deformation and molecular orientation in films of metallocene polypropylene,ethylene–butylene rubber,and their 80/20 (w/w) blend revealed by the simultaneous kinetic measurement of microscopic infrared dichroism,macroscopic stress,and mesoscale strain

Simultaneous kinetic measurement of microscopic infrared dichroism, macroscopic stress, and mesoscale strain was used to study the deformation mechanisms of metallocene polypropylene (MPP), ethylene–butylene rubber (EBR), and their blend (MPP/EBR = 80/20 w/w). As with pure MPP, the molecular orientation in the blend is dominated by the necking of the isotactic polypropylene matrix. During the necking passage through the mesoscale sampling area, the molecular orientation of the polypropylene matrix in the blend is smaller than that in the pure polypropylene film at the same level of mesoscale strain. However, the orientation of the EBR dispersed phase in the blend is larger than that in the pure EBR film. This may result from the partial miscibility of the two ingredients in the amorphous phases and their resultant strong interfacial interaction. The large stress supported by the MPP matrix extends to the island of the EBR domain and leads to its large deformation. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1520–1531, 2005     

Fractionation process in TREF systems: Validation of thermodynamic model and calculation procedure by Raman LAM studies

In this paper, possible sources for the unexpected distributions of crystalline sequence lengths calculated from temperature rising elution fractionation (TREF) calibration experiments, as reported in a previous work, are investigated. With this aim, chain folding and cocrystalization phenomena were explored in the conditions of crystallization as used for TREF or crystallization analysis fractionation (CRYSTAF). Slow crystallizations were performed from xylene solutions of model low molecular weight ethylene homopolymers with narrow molecular weight distributions. The same experiments were performed with homopolymers having narrow molecular weight distributions and with blends having wide molecular weight distributions. The resulting distributions of the lengths of crystalline methylene sequences were directly studied by Raman in the so‐called longitudinal acoustic mode (LAM) and by DSC. For ethylene homopolymers with molecular weights below 2000 g/mol, the results from Raman LAM indicate that slow crystallization in TREF or CRYSTAF systems occurs in the extended‐chain mode. For higher molecular weights, evidence of chain folding was found. In the case of blends, independent crystallization was observed for each molecular weight when the molecular weight ranges used for the blends are relatively narrow. Cocrystallization was observed when this range was increased. Overall, these results strongly support the inverse technique calculation procedure developed by our group for the calculation of distributions of lengths of crystallizable sequences from TREF spectra. In this context, the results confirm that the unexpected crystallizable sequence lengths found in our previous work really exist and can be associated to chain folding or cocrystallization phenomena. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3083–3092, 2005     

Role of electrostatic forces in cluster formation in a dry ionomer

This simulation study investigates the dependence of the structure of dry Nafion-like ionomers on the electrostatic interactions between the components of the molecules. In order to speed equilibration, a procedure was adopted which involved detaching the side chains from the backbone and cutting the backbone into segments, and then reassembling the macromolecule by means of a strong imposed attractive force between the cut ends of the backbone, and between the nonionic ends of the side chains and the midpoints of the backbone segments. Parameters varied in this study include the dielectric constant, the free volume, side chain length, and strength of head group interactions. A series of coarse-grained mesoscale simulations shows the morphology to depend sensitively on the ratio of the strength of the dipole-dipole interactions between the side-chain acidic end groups to the strength of the other electrostatic components of the Hamiltonian. Examples of the two differing morphologies proposed by Gierke and co-workers [J. Polym. Sci., Polym. Phys. Ed. 19, 1687 (1981); Macromolecules 15, 101 (1982); J. Membr. Sci. 13, 307 (1982)] and by Gebel [Fuel Cells 5, 261 (2005); Macromolecules 37, 7772 (2004)] emerge from our simulations.     

Nanoscale mechanical characterization of polymeric fibers

The mechanical and viscoelastic behaviors of polymeric fibers varying in molecular weight have been determined at the nanometer scale with a surface force apparatus. The existence of a skin–core structure resulting from the elaboration process is pointed out. The role of fiber anisotropy is also discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 264–275, 2005     

Crystallization analysis fractionation

Crystallization analysis fractionation (CRYSTAF) is an analytical technique for determining the distribution of chain crystallizabilities of semicrystalline polymers. After only approximately a decade since it was developed, CRYSTAF has become one of the most important characterization techniques in polyolefin characterization laboratories because it provides fast and crucial information required for the proper understanding of polymerization mechanisms and structure–property relationships. In the polyolefin industry, it has been established as an indispensable tool for product development and product quality monitoring. This highlight article covers basic operation procedures, applications, and theoretical aspects of polymer fractionation with CRYSTAF. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1557–1570, 2005     

Modification of photoinitiated cationic epoxide polymerizations by sulfides

The addition of sulfides has a marked effect on the rates of onium salt induced photoinitiated cationic ring‐opening polymerizations of epoxide monomers. Various behaviors have been observed that depend on the structure of the sulfide. Dialkyl sulfides strongly inhibit the photopolymerizations of these monomers, whereas diaryl sulfides have a retarding effect on the photopolymerizations. Real‐time infrared spectroscopy and optical pyrometry have been employed as analytical methods to probe the kinetic effects of the addition of a variety of sulfides on cationic epoxide ring‐opening photopolymerizations. A mechanism is proposed that involves the formation of sulfonium salts as intermediates. The observations made in this study have important implications for cationic photopolymerizations in general and for photoinitiated cationic ring‐opening polymerizations of epoxides in particular. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2504–2519, 2005     

Nitrogen plasma modification on polyimide films for copper metallization on microelectronic flex substrates

Surface modification of polyimide films Kapton E(N) and Upilex S by nitrogen plasmas were investigated for their enhanced adhesion strength with sputtered coppers. Peel tests demonstrate this improvement, with peel strengths of 7 and 12 N/m for unmodified Kapton E(N) and Upilex S, and 1522 and 1401 N/m for nitrogen plasma‐modified Kapton E(N) and Upilex S at certain plasma conditions. Atomic force microscopy (AFM) and the sessile drop method indicated the surface roughness, and the surface energy of polyimide films were highly increased by nitrogen plasmas. This study shows the enhanced adhesion strengths of polyimide films with sputtered coppers by nitrogen plasmas, and these nitrogen plasmas were strongly affected by the surface characteristics of polyimide films. Electron spectroscopy for chemical analysis (ESCA) observed the increased surface energy on polyimide films by nitrogen plasmas was due to the increased surface composition of O and the increased chemical bond of C? O. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2023–2038, 2005     

Newly synthesized polybenzoxazole derivative with an adjacent hydroxyphenyl ring for optical sensing

A photoluminescent polymer with a 2‐(2′‐hydroxyphenyl)benzoxazole unit in the molecular main chain was synthesized through the deprotection reaction of a precursor polymer. The amorphous, conjugated polymer emitted green light, both in solution and as a solid, with a fluorescence emission maximum at 518 nm from an excited keto tautomer because of excited‐state intramolecular proton transfer. The polymer showed different fluorescence emission spectra in solvents with different polarities because of intramolecular hydrogen‐bond interruption. The intramolecular hydrogen‐bond‐induced emission change was successfully used as a sensitive sensing signal for metal cations as expected, the polymer acting as a fluorescence‐based chemosensor. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1397–1403, 2005     

Physics of thick polymers

We present the results of analytical calculations and numerical simulations of the behavior of a new class of chain molecules that we call thick polymers. The concept of the thickness of such a polymer, viewed as a tube, is encapsulated by a special three‐body interaction and impacts on the behavior both locally and nonlocally. When thick polymers undergo compaction because of an attractive self‐interaction, we find a new type of phase transition between a compact phase and a swollen phase at zero temperature with increasing thickness. In the vicinity of this transition, short tubes form space‐filling helices and sheets as observed in protein native‐state structures. With increasing chain length, or with an increasing number of chains, we numerically find a crossover from secondary‐structure motifs to a quite distinct class of structures akin to the semicrystalline phases of polymers or amyloid fibers in polypeptides. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 650–679, 2005     

In Situ fibril formation of thermotropic liquid crystal polymer in polyesters blends

Polymer blends based on poly(ethylene 2,6‐naphthalate) (PEN) and poly‐(ethylene terephthalate) (PET) reinforced with a thermotropic liquid crystal polymer (TLCP) were prepared using a melt blending process. Polymer blends consisting of conventional cheap polyester with a small quantity of expensive TLCP are of interest from an economic point of view. The shear viscosity of the TLCP and polyester blends decreased with increasing shear rate and depended on TLCP content. The lower values of the structural viscosity index for the TLCP and polyester blends were attributed to the formation of fibrillar TLCP structures having elongated fibrils in the polyester matrix. The TLCP/PEN blends exhibited long TLCP fibrils that had smaller average diameters and narrower distributions of the diameter compared with those of the TLCP/PET blends. The higher shear force and lower viscosity ratio observed may favor the in situ TLCP fibril formation in the polyester matrix. The viscosity ratio was the most crucial factor in controlling the morphology of the TLCP phase in the TLCP and polyester blends. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3600–3610, 2005     

Vinyl addition polymerization of norbornene with cationic (allyl)Ni catalysts: Mechanistic insights and characterization of first insertion products

Several cationic (allyl)Ni(II) complexes were synthesized and shown to be highly active for (2,3)‐vinyl addition polymerization of norbornene to yield polymers with low molecular weight distributions (MWDs) ranging from 1.4–1.9. In all cases slow initiation was followed by rapid propagation which prevents molecular weight control of the poly(norbornene). One of the intermediates in the polymerization process has been identified and characterized by NMR spectroscopy as the first insertion product resulting from the insertion of norbornene into the Ni? C allyl bond in cis‐exo fashion. This insertion product was synthesized independently and NMR studies showed that the first insertion of norbornene into the Ni? C allyl bond is a reversible process. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2560–2573, 2009     

Analytical solutions to mathematical models of the surface and bulk erosion of solid polymers

The process by which polymeric materials hydrolyze and disappear into their environments is often called erosion. Two types of erosion have been defined according to how the hydrolysis takes place. If hydrolysis occurs throughout the entire specimen at the same time, it is called bulk erosion. If the hydrolysis is mainly confined to a region near the surface of the specimen and the surface continuously degrades by moving inward, it is termed surface erosion. In this article, a kinetic relationship for bulk erosion is developed. This relationship provides a method for estimating the hydrolysis kinetic constants for bulk‐eroding polymers. This same relationship is also applicable to surface erosion at a microscopic level. Through its combination with a diffusion–reaction equation and the provision of moving boundary conditions, an analytical solution to the steady‐state surface‐erosion problem is obtained. The erosion rate, erosion front width, and induction time can all be expressed as simple functions of the rate of polymer bond hydrolysis, water diffusivity, and solubility, plus other parameters that can be experimentally determined. The erosion front width is the product of the induction time and the erosion rate. The ratio of the erosion front width to the polymer specimen thickness is a parameter that determines whether the specimen undergoes surface or bulk erosion. Theoretical results are compared with experimental observations from the literature, and agreement is found. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 383–397, 2005     

Preparation of polymer/silica composite nanoparticles bearing carboxyl groups on the surface via emulsifier‐free emulsion copolymerization

Polymer/silica organic/inorganic composite nanoparticles bearing carboxyl groups on the surface were prepared via the emulsifier‐free emulsion copolymerization of methyl methacrylate and sodium methacrylate (NaMA). Carboxyl groups were generated by the addition of hydrochloric acid at the end of the copolymerization. Two methods of NaMA addition were studied: batch and two‐stage procedures. The batch procedure allowed only a limited number of carboxyl groups to effectively bond to the composite nanoparticles. In contrast, the number of carboxyl groups could be altered over a wide range with the two‐stage procedure. Fourier transform infrared spectroscopy and chemical titration were independently used to quantify the number of carboxyl groups, giving values close to each other and to the feed. A kinetic study indicated that the copolymerization followed a mechanism different than that found earlier. The average size of the composite nanoparticles was approximately 40 nm, as measured by both transmission electron microscopy (TEM) and laser scattering, and their polydispersity index was close to 1, indicating a fairly narrow size distribution. TEM photographs of the composite nanoparticles showed a multilayered core–shell structure with one silica bead as the core and with poly(methacrylate acid) as the outmost shell. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 2826–2835, 2005