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The effects of molecular weight (Mw) of polystyrene (PS) latex particles on optical and electrical percolations of multi-walled carbon nanotube (MWCNT)-added nanocomposite films were reported. Thre...

Solvents have an essential association with polymer solution behavior. However, few researches have been deeply done on this respect. In recent years, our research group focus on the study on effect of solvent properties on solution behavior and film condensed state structure for semi-rigid conjugated polymer up till to apply for optoelectronic device. Herein, influence of solvent properties including solubility of solvent, aromaticity, polarity and hydrogen bonds on semi-rigid polymer chain solution behavior, i.e., single chain conformation, chain shape, size and chains aggregated density were studied by means of static/dynamic laser light scattering (DLS/SLS) and exponential law etc. Effect of solvent properties on condensed state structure of the semi-rigid conjugated polymer film was studied by UV absorption spectroscopy, PL spectroscopy and electron microscopy etc. The essential reasons for the influence were discovered and the mechanism was revealed. It was found that solution behavior with different solvent properties had an essential physical relationship with chains condensed state structure of the semi-rigid conjugated polymers. More importantly, there was a quantitative structure-activity relationship between solution and film. The key to this relationship depended on the interaction between solvent molecules and the semi-rigid conjugated polymer chains. This interaction could also affect optoelectronic devices performance. This study is of great significance to effectively control the condensed state structure of the semirigid conjugated polymers in the process of dynamic evolution from solutions to films. It not only enriches the knowledge and understanding of both semi-rigid conjugated polymer solution behaviors and film condensed state physics based on polymer physics, but also is meaningful to practical application for conjugated polymer and other traditional polymer systems.

Conformation and dynamical evolution of block copolymers in shear flow is an important topic in polymer physics that underscores the forming process of various materials. We explored deformation and dynamics of copolymers composed of rigid or flexible blocks in simple shear flow by employing multiparticle collision dynamics integrated with molecular dynamics simulations. We found that compared with the proportion between rigid and flexible blocks, the type of the central blocks plays more important role in the conformational and dynamical evolution of copolymers. That is, if the central block is a coil, the copolymer chain takes end-over-end tumbling motion, while if the central block is a rod, the copolymer chain undergoes U-shape or S-shape deformation at mid shear rate. As the shear strength increases, all copolymers behave similar to flexible polymers at high shear rate. This can be attributed to the fact that shear flow is strong enough to overcome the buckling force of the rigid blocks. These results provide a deeper understanding of the roles played by rod and coil blocks in copolymers for phase interface during forming processing.

One of the most celebrated achievements in polymer physics is the finding of simple scaling laws that correlate molecular behaviors with molecular size. Scaling relations of 2D macromolecules betwe...

Conformation statistics of macromolecules in dilute solution is one of the fundamental issues in polymer physics. Herein, we experimentally explore the average conformation of model randomly hyperb...

We study the phase behavior of a block copolymer and ionic liquid mixture using the Landau theory of Leibler and field-theoretic techniques in polymer physics. Our weak-segregation theory of microp...

The intrinsic coupling effect between the multiscale microstructure and macroscopic performance is a fundamental issue in polymer engineering and polymer physics. Combing the tensile testing and in...

Internal dynamics of polymer chains is one of the most important fundamental problems in polymer physics. This work reports the first example of a dynamic light scattering (DLS) study of internal m...

We have quantified the structure of the colloidal gas-liquid interface using synchrotron X-ray reflectivity measurements on a model colloid-polymer mixture. The interfacial width shows mean-field scaling with the colloid density difference, and the density profiles appear to be monotonic. Furthermore, our measurements allow us to distinguish between different theoretical polymer descriptions commonly used to model colloid-polymer mixtures. Our results highlight the importance of capturing the correct polymer physics in obtaining a quantitative theoretical description of the colloidal gas-liquid interface.

Particles suspended in a Newtonian fluid may lead to non-Newtonian behaviour, depending on their shape and flexibility. Particles can now be precisely engineered from linked, double-stranded DNA sequences or rods. To design functional nano-materials from these systems, it is important to predict the suspension properties for a given particle specification. We study this question theoretically, focusing on two classes of DNA particles; nano-stars and nun-chucks. Nano-stars are constructed from straight, rigid rods joined at fixed angles, to form e.g. Y-shapes. Nun-chucks are two rods linked at their ends by a flexible joint. We determine a set of sufficient symmetry conditions on the particle shape for a dilute suspension to be Newtonian. We demonstrate these for nano-stars and further show that the lengths of their constituent rods may be engineered so that the suspension is Newtonian, despite the particles not possessing the appropriate symmetries. We present a simple geometric method to determine the magnitude of the elastic response of concentrated nano-star suspensions. We find that the linear elastic response for bent and branched particles increases proportional to the concentration cubed whereas for rods it increases only linearly. The non-linear response is also different; concentrated thin rod suspensions always shear thin, but suspensions of bent/branched particles can shear thicken, depending on the bending modulus of the particles. These properties are very sensitive to the shape of the particle. The diffusion of branched particles in concentrated suspensions is also discussed through a simple, two-dimensional model, which indicates a glass transition in these systems. We develop a formalism describing the dynamics of the nun-chuck particles in dilute suspensions. We address problems ranging from the motion of the particles under shear flow in the absence of Brownian motions to the steady state non-linear elasticity. We discuss briefly how our approach may be extended to concentrated suspensions and the transition to liquid crystalline states for these particles.

In this chapter, we outline a simple physical description of polymers, first as a single chain, explaining the concepts of an ideal chain and a real chain, and then in a solution with many chains where the enthalpic interactions with solvent molecules corroborate with the configurational entropy of the polymer chain to give rise to the rich properties we observe on a macroscopic level. The Flory-Huggins theory will be introduced in describing polymers in solution, and a discussion on some of its limitations is presented. We conclude with a brief introduction to polymer brushes and some examples of application of polymers in nanoscience.

We present computer simulations of a dynamic Monte Carlo algorithm for polymer chains on the FCC lattice which takes explicitly into account the possibility to overcome topological constraints by controlling the rate at which nearby polymer strands may cross through each other. By applying the method to systems of interacting ring polymers at melt conditions, we characterize their structure and dynamics by measuring, in particular, the amounts of knots and links which are formed during the relaxation process. In comparison to standard melts of unknotted and unconcatenated rings, our simulations demonstrate that the mechanism of strand crossing is responsible for fluidizing the melt provided the time scale of the process is faster than the internal relaxation of the chain, in agreement with recent experiments employing solutions of DNA rings in the presence of the type II topoisomerase enzyme. In the opposite case of slow rates the melt is shown to become slower, and this prediction may be easily validated experimentally., 12 pages, 9 figures in the main text, 8 supplementary figures. Submitted for publication

The dynamics of polymer-nanoparticle (NP) mixtures, which involves multiple scales and system-specific variables, has posed a long-standing challenge on its theoretical description. In this paper, we construct a microscopic theory for polymer diffusion in the mixtures based on a combination of generalized Langevin equation, mode-coupling approach, and polymer physics ideas. The parameter-free theory has an explicit expression and remains tractable on pair correlation level with system-specific equilibrium structures as input. Taking a minimal polymer-NP mixture as an example, our theory correctly captures the dependence of polymer diffusion on NP concentration and average interparticle distance. Importantly, the polymer diffusion exhibits a power law decay as the polymer length increases at dense NPs and/or long chain, which marks the emergence of entanglement-like motion. The work provides a first-principle theoretical foundation to investigate dynamic problems in diverse polymer nanocomposites., 10 pages, 6 figures

The random motion of a flexible molecular chain floating in a solvent or a melt can itself be quite complex. The discussion in this chapter starts with some basic concepts of an ideal polymer chain. It is then followed by classical models describing the dynamics and diffusion of polymer chains applicable to polymer melts. This chapter’s main objective is to contrast the differences between the mobility of polymer chains in melts (or solvents) and the kinetically trapped glassy state.

The static light scattering (SLS) method is introduced with key equations used to extract quantitative information such as weight-average molecular weight, osmotic second virial coefficient, and radius of gyration from the experimental data. The use of Zimm plots to obtain visual cues of the polymer's characteristics is presented. A treatise of the thermodynamic process (modified by structural parameters) sensed by light scattering from a single atom, multiple atoms, fluids, small and large polymers is presented with reliance on a plethora of equations. The design of the SLS instrument as well as a few case studies of SLS applications are summarized to help the user understand the experiment better and to discern compromises in commercial instruments. The opportunity in combining DLS and SLS to obtain a complete picture of polymer characterization and polymer physics closes the loop on these light scattering techniques.

Since chemical shift interaction was discovered in 1953, nuclear magnetic resonance (NMR) spectroscopy has emerged as one of the most promising tools in polymer chemistry as well as polymer physics. In this chapter, basic principles of solution- and solid-state NMR spectroscopy will be introduced and recent NMR applications to polymer structure and dynamics will be reviewed.

From the model of interstitial alloy AB with FCC structure and the condition of absolute stability for crystalline state we derive analytic expression for the temperature of absolute stability for crystalline state, the melting temperature and the equation of melting curve of this alloy by the way of applying the statistical moment method. The obtained results allow us to determine the melting temperature of alloy AB at zero pressure and under pressure. In limit cases, we obtain the melting theory of main metal A with FCC structure. The theoretical results are numerically applied for alloys AuSi and AgSi.

The origin of the unique properties of a polymer material is the large entropic term of a single molecule, which has a chain-like structure with a large molecular weight. From the viewpoint of understanding the fundamental polymer physics, conformation of the single polymer chain is one of the most important matters; however, it has been difficult to examine the behavior of a single chain because of the limitation of conventional experimental methods. Recent developments in optical microscopy allow the fluorescence imaging beyond the diffraction limit of light, and the author's group showed that the conformation and the dynamics of a single polymer chain can be examined by the high-resolution fluorescence imaging. This review presents the application of optical microscopy with nanometric spatial resolution to study the polymer materials at the single-chain level.

We directly track the tubelike motion of individual fluorescently labeled polymer molecules in a concentrated solution of unlabeled polymers. We use a single molecule wide-field fluorescence microscopy technique that is able to determine characteristic properties of the polymer dynamics, such as the confining potential, the tube diameter, and the Rouse time. The use of synthetic polymers allows us to investigate the confined motion of the polymer chains not only as a function of polymer concentration (mesh size) but also versus the persistence length of the matrix polymers. Although the polymers used have a persistence length much smaller than their contour length, our experimental results lead to a dependence of the tube diameter on both the mesh size and the persistence length, which follows the theoretically predicted relation for semiflexible chains.

Bottlebrushes are an emerging class of polymers, characterized by a high density of side chains grafted to a linear backbone that offer promise in creating materials with unusual combinations of mechanical, chemical, and optoelectronic properties. Understanding the role of molecular architecture in the organization and assembly of bottlebrushes is of fundamental importance in polymer physics, but also enabling in applications. Here, we apply field-theoretic simulations to study the effect of grafting density, backbone length, and side-chain (SC) length on the structure and thermodynamics of bottlebrush homopolymer melts. Our results provide evidence for a phase transition from an isotropic to a nematic state with increasing grafting density and side-chain length. Variation in the backbone length is also observed to influence the location of the transition, primarily for short polymers just above the star to bottlebrush transition.

In polymer theory, computer-generated polymer configurations, by either Monte Carlo simulations or molecular dynamics simulations, help us to establish the fundamental understanding of the conformational properties of polymers. Here, we introduce a different method, exploiting the properties of a machine-learning algorithm, the restricted Boltzmann machine network, to generate independent polymer configurations for self-avoiding walks (SAWs), for studying the conformational properties of polymers. We show that with adequate training data and network size, this method can capture the underlying polymer physics simply from learning the statistics in the training data without explicit information on the physical model itself. We critically examine how the trained Boltzmann machine can generate independent configurations that are not in the original training data set of SAWs.

The backbone conformations of individual, unperturbed synthetic macromolecules have so far not been observed directly in spite of their fundamental importance to polymer physics. Here we report the dilute solution conformations of two types of linear dendronized polymers, obtained by cryogenic transmission electron stereography and tomography. The three-dimensional trajectories show that the wormlike chain model fails to adequately describe the scaling of these thick macromolecules already beyond a few nanometers in chain length, in spite of large apparent persistence lengths and long before a signature of self-avoidance appears. This insight is essential for understanding the limitations of polymer physical models, and it motivated us to discuss the advantages and disadvantages of this approach in comparison to the commonly applied scattering techniques.

A key assumption of polymer physics is that the random chain polymers extend in flow. Recent experimental evidence has shown that polymer chains compress in Couette flow in a manner counter to expectation. Here, scaling arguments and experimental evidence from the literature are used to determine the relationship between the viscosity, η, and chain radius of gyration, RG. The viscosity-radius of gyration relationship is found to be $${\boldsymbol{\eta }}{\boldsymbol{ \sim }}{{\boldsymbol{R}}}_{{\boldsymbol{G}}}^{{\boldsymbol{m}}{\boldsymbol{(}}\dot{{\boldsymbol{\gamma }}}{\boldsymbol{)}}}$$ η ~ R G m ( γ ˙ ) where m($$\dot{{\boldsymbol{\gamma }}}$$ γ ˙ ) is the power law exponent of the viscosity-temperature relationship that depends on the specific polymer-solvent system and the shear rate, $$\dot{{\boldsymbol{\gamma }}}$$ γ ˙ . The viscosity is shown to be a power law function of the radius, and to decrease with decreasing radius under conditions where the chains are ideal random walks in concentrated solution. Furthermore, this relationship is consistent with both the widely observed viscosity-temperature and viscosity-shear rate behavior observed in polymer rheology. The assumption of extension is not consistent with these observations as it would require that the chains increase in size with increasing temperature. Shear thinning is thus a result of a decreasing radius with increasing shear rate as $${{\boldsymbol{R}}}_{{\boldsymbol{G}}} \sim {\dot{{\boldsymbol{\gamma }}}}^{-{\boldsymbol{n}}{\boldsymbol{/}}{\boldsymbol{m}}{\boldsymbol{(}}\dot{{\boldsymbol{\gamma }}}{\boldsymbol{)}}}$$ R G ~ γ ˙ − n / m ( γ ˙ ) where n is the power law exponent. Furthermore, the thermal expansion coefficients determine the variation in the power law exponents that are measured for different polymer systems. Typical values of n enable the measured reduction in coils size behavior to be fitted. Furthermore, the notion that polymer chains extend to reduce the viscosity implies that an increasing chain size results in a reduced viscosity is addressed. This assumption would require that the viscosity increases with reducing coil radius which is simply unphysical.

Summary Conventional EOR polymers are acrylamide-based copolymers. Their viscosity in aqueous solution depends on various physicochemical parameters such as: monomer composition, concentration, average molecular weight, polydispersity, salinity level and ionic composition, temperature… Moreover, solutions are non-Newtonian, they exhibit a Low shear Newtonian plateau viscosity at low shear rate followed by a shear thinning region at higher shear rate. In the absence of predictive model, for any new polymer grade or lot, any new or slightly varying field conditions, it is necessary to perform a whole set of viscosity measurements at varying concentrations which is tedious, time consuming and not valuable. Flow curves (Viscosity vs. Shear rate) were measured on a great number of polymers solutions in various physicochemical conditions (variation of the polymer microstructure, monomer composition, molecular weight, brine salinity and temperature). The flow curves in both dilute, semidilute non-entangled and semidilute entangled regimes were modelled by only two adjustable parameters: the intrinsic viscosity [η] and the relaxation time in the diluted regime λd. The low shear plateau viscosity η0 (more specifically, the specific viscosity ηspe) and the shear thinning index n obey mastercurves which are solely function of the overlap parameter C[η]. The relaxation time λ depends on C[η] and the relaxation time in the diluted regime λd. All these results are consistent with predictions for a neutral polymer in good solvent. By using these mastercurves, intrinsic viscosity of any polymer/brine system can be easily obtained at various temperatures from a single measurement in the semi-dilute regime in which viscosity is higher than water, and classic rheometers are very sensitive. The whole flow curve (η=f(γ)) can be predicted at any concentration, temperature and molecular weight. For any unknown polymer/brine system, the determination of λd enables to determine the viscosimetric average molecular weight M of the polymer. Finally, by using the additive property of the intrinsic viscosity of binary solutions, a method is proposed to evaluate molecular weight of field samples. Polymer physics is today considered as well described and well known. However, the beauty and the usefulness of this physics have been partly ignored by the EOR community up to now. This study gives a methodology to predict the viscosifying behavior and the molecular weight of any acrylamide based copolymer/brine system. By attributing molecular weight rather than a viscosity value, on-site and lab QA/QC will be greatly improved.

One of the most intriguing properties of rod-like polymers is the ability to form a nematic phase. Among a broad variety of external stimuli to promote the isotropic (I)-nematic (N) transition, a shear-induced nematic phase represents one of the most fascinating phenomena in polymer physics. Here, after reviewing some relevant findings on quiescent and shear-induced nematics, we present the novel shear-induced isotropic-nematic transition exhibited by poly(ether ether ketone) (PEEK) melts of various chain lengths. The key factor is the significant rigidity of the PEEK chain that makes it a rod-like polymer. The molecular weight (Mw) dependence of the zero-shear viscosity ( η 0 ) of PEEK in the isotropic phase, follows the Doi-Edwards theoretical prediction for rod-like polymers in the entangled regime; η 0 ∼ M w 6 . The shear-induced I-N transition manifests in the apparent shear viscosity dependence on the shear rate (flow curves) with three regimes: I) an isotropic response with no measurable birefringence at low shear rates, II) an I-N transition with an isotropic-nematic biphase, two steady state values of apparent viscosity and mild birefringence at intermediate shear rates, and III) a continuous nematic phase with strong birefringence at high shear rates with η ∼ γ ˙ − 1 / 2 . Additionally, the observed threshold shear rates for regimes II and III for the four PEEK samples were used to construct a dynamic phase diagram of PEEK at 370°C, revealing that such a transition is stress-controlled.

Polymer films on solid substrates present significant interest for fundamental polymer physics and industrial applications. For their mesoscale study, we develop a hybrid particle-based representation where polymers are modeled as worm-like chains and non-bonded interactions are introduced through a simple density functional. The mesoscale description is parameterized to match a generic microscopic model, which nevertheless can represent real materials. Choosing poly (methyl methacrylate) adsorbed on silica as a case study, the consistency of both models in describing conformational and structural properties in polymer films is investigated. We compare selected quantifiers of chain-shape, the structure of the adsorbed layer, as well as the statistics of loops, tails, and trains. Overall, the models are found to be consistent with each other. Some deviations in conformations and structure of adsorbed layer can be attributed to the simplified description of polymer/surface interactions and local liquid packing in the mesoscale model. These results are encouraging for a future development of pseudo-dynamical schemes, parameterizing the kinetics in the hybrid model via the dynamics of the generic microscopic model.

In this article we study, through extensions of the generalized Gaussian scheme, the dynamics of semiflexible treelike polymers under the influence of external forces acting on particular (say, charged) monomers. Semiflexibility is introduced following our previous work (Dolgushev and Blumen, 2009 [15]), a procedure which allows one to study treelike structures with arbitrary stiffness and branching. Exemplarily, we illustrate the procedure using linear chains and hyperbranched polymers modeled through Vicsek fractals, and obtain in every case the monomer displacement averaged over the structure. Anomalous behavior manifests itself in the intermediate time region, where the different fractal architectures show distinct scaling behaviors. These behaviors are due to the power law behavior of the spectral density and lead, for arbitrary pulling forces, based on causality and the linear superposition principle, to fractional calculus expressions, in accordance to former phenomenological fractional laws in polymer physics.

We develop a deep neural network (DNN) that accounts for the phase behaviors of polymer-containing liquid mixtures. The key component in the DNN consists of a theory-embedded layer that captures the characteristic features of the phase behavior via coarse-grained mean-field theory and scaling laws and substantially enhances the accuracy of the DNN. Moreover, this layer enables us to reduce the size of the DNN for the phase diagrams of the mixtures. This study also presents the predictive power of the DNN for the phase behaviors of polymer solutions and salt-free and salt-doped diblock copolymer melts.

We present our personal appraisal of a few recent trends in polymer physics and theory. The four main themes discussed are crystallization and melting of polymers, memory in polymer systems, topologically frustrated polymer dynamics, and phase behavior of polyelectrolyte solutions.

A brush-like structure emerges from stretching of long polymer chains, densely grafted on to the surface of an impermeable substrate. The structure arises due to the competition between conformational entropic elasticity of polymer chains and excluded volume interactions leading to intra and interchain monomer repulsions. Recently, soft materials based on stimuli responsive polymer brushes have been developed to produce controllable and reversible large bending deformation of the host substrates. To understand such systems and improve their functional properties, we study the stress distribution in a brush, and develop surface stress-curvature relation for an elastic beam of a soft material grafted with a neutral polymer brush. In the strongly stretched brush regime, we combine mean field theory from polymer physics with a continuum mechanics model and show that the residual stress variation in a brush is a quartic function of distance from the grafting surface, with a maximum occurring at the grafting surface. By idealizing a brush as a continuum elastic surface layer with residual stress, we derive a closed form expression for surface stress and surface elasticity of the layer as a function of brush parameters, such as graft density and molecular weight. A generalized continuum beam model accounts for the Young–Laplace and Steigmann–Ogden curvature elasticity correction terms, and yields a surface stress-curvature relation, that contains existing relations in the literature as special cases. Further, we report experiments on a thermoresponsive random copolymer brush, Poly(N- isopropylacrylamide)-co-Poly(N,N-Dimethylacrylamide) (PNIPAm-co-PDMA) brush, grafted on one side of a plasticized poly(vinyl chloride) (pPVC) thin film. Estimated surface stress from measured curvature is on the order of − 10 N/m , and its magnitude decreases gradually, and reversibly, on increasing ambient temperature from 15 °C to 55 °C.

Single-molecule measurements of polymer elasticity are powerful, direct probes of both biomolecular structure and principles of polymer physics. Recent work has revealed low-force regimes in which biopolymer elasticity is understood through blob-based scaling models. However, the small tensions required to observe these regimes have the potential to create measurement biases, particularly due to the increased interactions of the polymer chain with tethering surfaces. Here, we examine one experimentally observed bias, in which fluctuation-based estimates of elasticity report an unexpectedly low chain compliance. We show that the effect is in good agreement with predictions based on quantifying the exclusion effect of the surface through an image-method calculation of available polymer configurations. The analysis indicates that the effect occurs at an external tension inversely proportional to the polymer's zero-tension radius of gyration. We exploit this to demonstrate a self-consistent scheme for estimating the radius of gyration of the tethered polymer. This is shown in measurements of both hyaluronic acid and poly(ethylene glycol) chains.

Understanding properties of polymer alloys with computer simulations frequently requires equilibration of samples comprised of microscopically described long molecules. We present the extension of an efficient hierarchical backmapping strategy, initially developed for homopolymer melts, to equilibrate high-molecular-weight binary blends. These mixtures present significant interest for practical applications and fundamental polymer physics. In our approach, the blend is coarse-grained into models representing polymers as chains of soft blobs. Each blob stands for a subchain with N b microscopic monomers. A hierarchy of blob-based models with different resolution is obtained by varying N b. First the model with the largest N b is used to obtain an equilibrated blend. This configuration is sequentially fine-grained, reinserting at each step the degrees of freedom of the next in the hierarchy blob-based model. Once the blob-based description is sufficiently detailed, the microscopic monomers are reinserted. The hard excluded volume is recovered through a push-off procedure and the sample is re-equilibrated with molecular dynamics (MD), requiring relaxation on the order of the entanglement time. For the initial method development we focus on miscible blends described on microscopic level through a generic bead-spring model, which reproduces hard excluded volume, strong covalent bonds, and realistic liquid density. The blended homopolymers are symmetric with respect to molecular architecture and liquid structure. To parameterize the blob-based models and validate equilibration of backmapped samples, we obtain reference data from independent hybrid simulations combining MD and identity exchange Monte Carlo moves, taking advantage of the symmetry of the blends. The potential of the backmapping strategy is demonstrated by equilibrating blend samples with different degree of miscibility, containing 500 chains with 1000 monomers each. Equilibration is verified by comparing chain conformations and liquid structure in backmapped blends with the reference data. Possible directions for further methodological developments are discussed.

Micro-scale hydrogel particles, known as microgels, are used in industry to control the rheology of numerous different products, and are also used in experimental research to study the origins of jamming and glassy behavior in soft-sphere model systems. At the macro-scale, the rheological behaviour of densely packed microgels has been thoroughly characterized; at the particle-scale, careful investigations of jamming, yielding, and glassy-dynamics have been performed through experiment, theory, and simulation. However, at low packing fractions near jamming, the connection between microgel yielding phenomena and the physics of their constituent polymer chains has not been made. Here we investigate whether basic polymer physics scaling laws predict macroscopic yielding behaviours in packed microgels. We measure the yield stress and cross-over shear-rate in several different anionic microgel systems prepared at packing fractions just above the jamming transition, and show that our data can be predicted from classic polyelectrolyte physics scaling laws. We find that diffusive relaxations of microgel deformation during particle re-arrangements can predict the shear-rate at which microgels yield, and the elastic stress associated with these particle deformations predict the yield stress.

We study the properties of the classical Ising model with nearest-neighbor interaction for spins located at the monomers of long polymer chains in 2 and 3 dimensions. We compare results for two ensembles of polymers with very different single chain properties: 1) swollen, self-avoiding linear polymer chains in good solvent conditions and 2) compact, space-filling randomly branching polymers in melt. By employing a mean-field approach and Monte Carlo computer simulations, we show that swollen polymers cannot sustain an ordered phase. On the contrary, compact polymers may indeed produce an observable phase transition. Finally, we briefly consider the statistical properties of the ordered phase by comparing polymer chains within the same universality class but characterized by very different shapes.

We show that thin rectangular ribbons, defined as energy-minimising configurations of the Sadowsky functional for narrow developable elastic strips, have a propensity to form spherical shapes in the sense that forceless solutions lie on a sphere. This has implications for ribbonlike objects in (bio)polymer physics and nanoscience that cannot be described by the classical wormlike chain model. A wider class of functionals with this property is identified., Comment: 15 pages, 4 figures

The swelling of biopolymer gels is analysed with scaling laws from polymer physics, as an alternative for the classical Flory-Rehner theory. With these scaling laws, holding for polymer concentrations in the semi-dilute regime, experimental data on deswelling of gels can be collapsed to a single universal master curve. The predictions made with the scaling laws are similar to those made with the modified Flory-Rehner, where the osmotic pressure is described with a composition-dependent interaction parameter. For gels in the semi-dilute regime we recommend the use of the scaling laws, because their compact, and universal character.

What are the fundamental laws for the adsorption of charged polymers onto oppositely charged surfaces, for convex, planar, and concave geometries? This question is at the heart of surface coating applications, various complex formation phenomena, as well as in the context of cellular and viral biophysics. It has been a long-standing challenge in theoretical polymer physics; for realistic systems the quantitative understanding is however often achievable only by computer simulations. In this study, we present the findings of such extensive Monte-Carlo in silico experiments for polymer-surface adsorption in confined domains. We study the inverted critical adsorption of finite-length polyelectrolytes in three fundamental geometries: planar slit, cylindrical pore, and spherical cavity. The scaling relations extracted from simulations for the critical surface charge density $\sigma_c$-defining the adsorption-desorption transition-are in excellent agreement with our analytical calculations based on the ground-state analysis of the Edwards equation. In particular, we confirm the magnitude and scaling of $\sigma_c$ for the concave interfaces versus the Debye screening length $1/\kappa$ and the extent of confinement $a$ for these three interfaces for small $\kappa a$ values. For large $\kappa a$ the critical adsorption condition approaches the planar limit. The transition between the two regimes takes place when the radius of surface curvature or half of the slit thickness $a$ is of the order of $1/\kappa$. We also rationalize how $\sigma_c(\kappa)$ gets modified for semi-flexible versus flexible chains under external confinement. We examine the implications of the chain length onto critical adsorption-the effect often hard to tackle theoretically-putting an emphasis on polymers inside attractive spherical cavities., Comment: 12 pages, 10 figures, RevTeX

Randomly branched polymer chains (or trees) are a classical subject of polymer physics with connections to the theory of magnetic systems, percolation and critical phenomena. More recently, the model has been reconsidered for RNA, supercoiled DNA and the crumpling of topologically-constrained polymers. While solvable in the ideal case, little is known exactly about randomly branched polymers with volume interactions. Flory theory provides a simple, unifying description for a wide range of branched systems, including isolated trees in good and θ-solvent, and tree melts. In particular, the approach provides a common framework for the description of randomly branched polymers with quenched connectivity and for randomly branching polymers with annealed connectivity. Here we review the Flory theory for interacting trees in the asymptotic limit of very large polymerization degree for good solvent, θ-solutions and melts, and report its predictions for annealed connectivity in θ-solvents. We compare the predictions of Flory theory for randomly branched polymers to a wide range of available analytical and numerical results and conclude that they are qualitatively excellent and quantitatively good in most cases.

When cooled or pressurized, polymer melts exhibit a tremendous reduction in molecular mobility. If the process is performed at a constant rate, the structural relaxation time of the liquid eventually exceeds the time allowed for equilibration. This brings the system out of equilibrium, and the liquid is operationally defined as a glass - a solid lacking long-range order. Despite almost 100 years of research on the (liquid/)glass transition, it is not yet clear which molecular mechanisms are responsible for the unique slow-down in molecular dynamics. In this review, we first introduce the reader to experimental methodologies, theories, and simulations of glassy polymer dynamics and vitrification. We then analyse the impact of connectivity, structure, and chain environment on molecular motion at the length scale of a few monomers, as well as how macromolecular architecture affects the glass transition of non-linear polymers. We then discuss a revised picture of nanoconfinement, going beyond a simple picture based on interfacial interactions and surface/volume ratio. Analysis of a large body of experimental evidence, results from molecular simulations, and predictions from theory supports, instead, a more complex framework where other parameters are relevant. We focus discussion specifically on local order, free volume, irreversible chain adsorption, the Debye-Waller factor of confined and confining media, chain rigidity, and the absolute value of the vitrification temperature. We end by highlighting the molecular origin of distributions in relaxation times and glass transition temperatures which exceed, by far, the size of a chain. Fast relaxation modes, almost universally present at the free surface between polymer and air, are also remarked upon. These modes relax at rates far larger than those characteristic of glassy dynamics in bulk. We speculate on how these may be a signature of unique relaxation processes occurring in confined or heterogeneous polymeric systems.

We have extended an existing hybrid MD-SCF simulation technique that employs a coarsening step to enhance the computational efficiency of evaluating non-bonded particle interactions. This technique is conceptually equivalent to the single chain in mean-field (SCMF) method in polymer physics, in the sense that non-bonded interactions are derived from the non-ideal chemical potential in self-consistent field (SCF) theory, after a particle-to-field projection. In contrast to SCMF, however, MD-SCF evolves particle coordinates by the usual Newton's equation of motion. Since collisions are seriously affected by the softening of non-bonded interactions that originates from their evaluation at the coarser continuum level, we have devised a way to reinsert the effect of collisions on the structural evolution. Merging MD-SCF with multi-particle collision dynamics (MPCD), we mimic particle collisions at the level of computational cells and at the same time properly account for the momentum transfer that is important for a realistic system evolution. The resulting hybrid MD-SCF/MPCD method was validated for a particular coarse-grained model of phospholipids in aqueous solution, against reference full-particle simulations and the original MD-SCF model. We additionally implemented and tested an alternative and more isotropic finite difference gradient. Our results show that efficiency is improved by merging MD-SCF with MPCD, as properly accounting for hydrodynamic interactions considerably speeds up the phase separation dynamics, with negligible additional computational costs compared to efficient MD-SCF. This new method enables realistic simulations of large-scale systems that are needed to investigate the applications of self-assembled structures of lipids in nanotechnologies.

We have investigated the collapse transition of aqueous solutions of gradient copolymers from poly(iso-propyl-2oxazoline)s (PiPrOx), which contain few hydrophobic moieties (n-nonyl-2-oxazoline (NOx) monomers). We extend our previous investigations (Salzinger et al., Colloid Polym Sci 290:385–400, 2012), where, for the gradient copolymers, an intermediate regime right above the cloud point was identified where small aggregatesare predominant.Largeaggregatesare present in significant numbers only at higher temperatures. To investigate the stability of the intermediate regime, we performed time-resolved small-angle neutron scattering (SANS) experiments during temperature jumps starting below the cloud point and ending in the intermediate regime or in the high-temperature regime. We found that the intermediate regime is stable during the time investigated (∼1 h). Moreover, the collapse of the small aggregates and the surface structure of the large aggregates are related to the number of hydrophobic moieties and the quench depth. The present results elucidate the structural evolution of these polymers and relate them to their final state as well as to their macroscopic behavior.

The theoretical description of how entangled polymers undergo large deformation has been at the heart of polymer dynamics. Over the years, the polymer physics community has adopted the tube model as the standard paradigm for describing polymer deformation and flow in both the linear and nonlinear regimes. The tube model envisions an ensemble of chains that undergo reptation and fluctuation inside smooth confining tubes on time scales of the Rouse relaxation time. It provides a reasonable and appealing description of the equilibrium and near equilibrium dynamics of entangled polymer melts and concentrated solutions. Some of the predictions based on this paradigm are also in apparent agreement with macroscopic rheological measurements for large deformations. However, some discrepancies with the tube model have been noted in the literature. For example, the time for the onset of time-strain superposibility in experiments has been shown to be much longer than the Rouse time anticipated based on the tube model. More recently, S.-Q. Wang’s group using particle-tracking velocimetry reported a number of nonlinear rheological phenomena that questioned the validity of the tube-model assumptions. The theoretical implications of the reported phenomena have been controversial.

By the so-called wormlike chain (WLC) model in polymer physics envisioning an isotropic rod that is continuously flexible, the force-extension relations of semi-flexible polymer chains strongly constrained by various confinements are theoretically investigated, including a slab-like confinement where the polymer chains are sandwiched between two parallel impenetrable walls, and a capped nanochannel confinement with a circular or rectangular cross-section where the chains are bounded in three directions. The Brownian dynamics (BD) simulations based on the generalized bead-rod (GBR) model are performed to verify the theoretical predictions.

Polydispersity plays an important role in polymer physics influencing both processing approaches and final properties. Despite the obvious physical importance of polydispersity, studies usually simulate monodisperse chains or occasionally, a few different chain lengths. This work presents a comprehensive methodology for mapping various molecular weight distributions onto a finite number of lattice chains. The use of a lattice in the present derivation enables a variety of lattice-based simulations to incorporate polydispersity. Examples are provided by extending the cooperative motion (COMOTION) algorithm for polydispersity to create the “polydisperse cooperative motion algorithm” (p-COMOTION). The dynamic version of p-COMOTION captures the dynamics of entangled polydisperse melts. For the same weight-averaged molecular weight, polydispersity gives a lower Rouse time and introduces a broadening of the reptation transition. In addition, when adapted into the cooperative motion with flow (COMOFLO) algorithm...

By performing molecular dynamics simulations, we investigate the structural and dynamical properties of polymer melts containing probe spherical nanoparticles. Generally speaking, the behavior of these polymer nanocomposites is strongly affected by the interaction strength established between the nanoparticles and the chain monomers and by the nanoparticle sizes. We highlight that this dependence is not always evident and some intriguing properties, such as the heterogeneous dynamics of both polymer chains and nanoparticles and their nonGaussian behavior at short and long timescales, are not particularly influenced by the degree of attraction between nanoparticles and polymer for the range of interactions we study (up to 6 kBT). We find the existence of weakly ordered interdigitated structures with sequential arrangements of particles and polymer chains, which separate each other and hence inhibit the formation of nanoparticle clusters. This is especially evident with big nanoparticles, being less prone to aggregate than small ones, even when their interaction with the polymer chain is as low as 0.5 kBT. Moreover, by integrating the stress-tensor autocorrelation functions, we estimate the shear viscosity and determine its dependence on the strength of the polymer-nanoparticle interactions and on the nanoparticle size. By acting as plasticizers, small nanoparticles decrease the viscosity, especially at low-to-moderate interactions with the polymer. By contrast, big nanoparticles that establish strongly attractive interactions with the polymer chains behave as thickening agents and significantly increase the viscosity. This complex and perhaps still scantily understood balance between the geometry of nanoparticles and their interaction with the polymer is key to predict and fully control the macroscopic response of nanocomposite materials and hence suitably tailor their mechanical properties.

Nowadays, achieving a uniform dispersion of rod-like molecules (like carbon nanotube) in a polymer matrix is still a complicated and unsettled issue in polymer physics and chemical physics. It is very significant to fully understand the effects of deterministic factors on dispersion and aggregation processes of nanorods in the polymer matrix. Here, we adopt a coarse-grained molecular dynamics simulation to investigate the nanorod- filled polymer nanocomposites. It is found that the characteristic relaxation time of the end-to-end vector correlation exhibits an Arrhenius-like temperature-dependent behavior and both the rotational and translational diffusion coefficients have a linear relationship with temperature. By tuning the polymer–nanorod interaction in a wide range, we obtain the spatial organization of nanorods and the best dispersion state at the intermediate interfacial interaction. Meanwhile, we observe that grafting polymer chains on the nanorod surface could promote the dispersion. Moreover, a lower or higher temperature than glassy transition temperature can prevent the nanorod aggregation. The aggregation of nanorods can be significantly accelerated by nanorod–nanorod attraction, while inhibited by cross-linking of polymer chains and external shear fields. In short, by tailoring the deterministic factors above, we can effectively control the dispersion or even spatial organization of one-dimensional nanorods in polymer nanocomposites.

One of the great goals in polymer physics is to relate the various macroscopic features of polymeric fluids with the microscopic behavior of single chains. Here, we directly visualize the conformational dynamics of individual semiflexible polymers in a semidilute solution above the overlap concentration under shear. We observe that the tumbling dynamics are significantly slowed down, in marked contrast to the case of a dilute solution, due to steric interactions with neighboring filaments. The observed macroscopic shear thinning effect can be rationalized by a simple model based on the single filament dynamics.

In order to understand the moisture diffusion, we combine the obstruction-scaling model with the moisture clustering in confined spaces of the polymer hydrogel, with relevance to the performance of the super desiccant polymer. Special attention is focused on elucidating the effect of chain stiffness by considering the conformation of polymer chain on the basis of polymer physics. Relevant parameters for calculations are determined from literature information as well as the best fits for reported data performed with the copolymer. Our results exhibit the moisture diffusion decreases with increasing chain stiffness represented by the persistence length. Note that the larger persistence length provides smaller radius of openings in void spaces, resulting in the stronger hindrance effect on the moisture diffusion. Higher temperature makes the water molecules to be easier to form clusters, which provides the decrease in diffusivity. The increase of moisture diffusion at low humidity is attributed to the swelling of the chain, whereas its decrease at high humidity results from the water clustering.

We report a new methodology for studying diffusion of individual polymer chains in a melt state, with special emphasis on the effect of chain topology. A perylene diimide fluorophore was incorporated into the linear and cyclic poly(THF)s, and real-time diffusion behavior of individual chains in a melt of linear poly(THF) was measured by means of a single-molecule fluorescence imaging technique. The combination of mean squared displacement (MSD) and cumulative distribution function (CDF) analysis demonstrated the broad distribution of diffusion coefficient of both the linear and cyclic polymer chains in the melt state. This indicates the presence of spatiotemporal heterogeneity of the polymer diffusion which occurs at much larger time and length scales than those expected from the current polymer physics theory. We further demonstrated that the cyclic chains showed marginally slower diffusion in comparison with the linear counterparts, to suggest the effective suppression of the translocation through the threading-entanglement with the linear matrix chains. This coincides with the higher activation energy for the diffusion of the cyclic chains than of the linear chains. These results suggest that the single-molecule imaging technique provides a powerful tool to analyze complicated polymer dynamics and contributes to the molecular level understanding of the chain interaction.

A procedure is introduced for measuring the radius of spherical colloid particles from the curvature of upper parts of their central cross-sectional profiles obtained by atomic force microscopy (AFM). To minimize the possible compression and displacement of the spheres, AFM is operated in a mode rendering a constant ultralow pN force on the tip. The procedure allows us to evaluate the mean radius of nearly monodisperse submicrometer spheres of silica in their natively hydrated state in aqueous electrolyte solutions, irrespective of whether they are coagulated or not. A variation in the volume (swelling degree) of layers delimited by the AFM mean radii of these spheres in KCl solutions and their invariable mean radius in vacuum is obtained that follows a scaling power law derived in polymer physics for swellable polyelectrolyte gels and deduced previously by us from coagulation tests. This supports our former suggestion about the existence of soft polyelectrolyte gel-like layer developed spontaneously around silica surfaces and colloids. We discuss this finding in the context of recent knowledge about the structure of the silica/water interface obtained from direct surface force measurements between macroscopic silica surfaces and from particle size measurements of silica colloids and highlight its importance for colloid chemistry and condensed mattter physics.