Freezing of polymer solutions has been extensively investigated from many aspects, especially the complex pattern formation. The cell/dendrite micro-structures are believed to be in the type of diffusion-induced M-S instability. However, the presence of polymer as an impurity in water is significantly different from that of small ions. The quantitative transient investigation on directional freezing of polymer solutions remains lack due to some challenges. For the first time, we observed the planar instability behaviors during unidirectional freezing of a polymer solution together with a typical ionic solution with manipulated ice orientation, and their pattern formation of S/L interface morphology as a function of time in the transient planar instability process has been revealed and compared to each other. It is found with real-time observation that the polymer solution exhibits a global instability mode instead of a local instability mode that is common in ionic solution during planar instability. W-L model was applied to quantitatively address the variation of solute recoil of ionic/polymer solution. And it is found that the W-L model can only reproduce the solute recoil of ionic solution instead of polymer solution, which indicates the complex physics behind freezing of a polymer solution. The paper provides a spectacular contrast of directional freezing process between polymer solution and ionic solution and is believed to promote relevant investigations in terms of the theoretical approach to describing the freezing behavior of polymer solution.
Freezing colloidal suspensions widely exists in nature and industry. Interface instability has attracted much attention for the understandings of the pattern formation in freezing colloidal suspensions. However, the interface instability modes, the origin of the ice banding or ice lamellae, are still unclear. In-situ experimental observation of the onset of interface instability is still absent up to now. Here, by directly imaging the initial transient stage of planar interface instability in directional freezing colloidal suspensions, we proposed three interface instability modes, Mullins-Sek…
We analyze the freezing and collapse transition of a simple model for flexible polymer chains on simple cubic and face-centered cubic lattices by means of sophisticated chain-growth methods. In contrast to bond-fluctuation polymer models in certain parameter ranges, where these two conformational transitions were found to merge in the thermodynamic limit, we conclude from our results that the two transitions remain well-separated in the limit of infinite chain lengths. The reason for this qualitatively distinct behavior is presumably due to the ultrashort attractive interaction range in the la…
We investigate the behavior of hydrated sulfonated polysulfones over a range of ion contents through differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), and molecular dynamics (MD) simulations. Experimental evidence shows that at comparable ion contents, the spacing between the ionic groups along the polymer backbone can significantly impact the amount of melting water present in the polymer. When we only consider water molecules that can hydrogen bond to four neighboring water molecules as the melting water, the MD simulation results are found to agree wit…
We analyze the crystallization and collapse transition of a simple model for flexible polymer chains on simple cubic and face-centered cubic lattices by means of sophisticated chain-growth methods. In contrast to bond-fluctuation polymer models in certain parameter ranges, where these two conformational transitions were found to merge in the thermodynamic limit, we conclude from our results that the two transitions remain well-separated in the limit of infinite chain lengths. The reason for this qualitatively distinct behavior is presumably due to the ultrashort attractive interaction range in…
Polymer-Regulated Freezing of Water Droplets Revealed by Synchrotron X-ray Imaging and Raman Spectroscopy
Ulsan National Institute of Science and Technology (UNIST)（蔚山科学技术院）；Korea Polar Research Institute (KOPRI)（韩国极地研究所）；Pohang Accelerator Laboratory, Pohang University of Science and Technology (POSTECH)（浦项科技大学波项加速器实验室）；UNIST Research Center for Soft and Living Matter, Ulsan National Institute of Science and Technology (UNIST)（蔚山科学技术院软体与生命物质研究中心）
We report Monte Carlo simulations of a lattice-polymer model that can account for both polymer crystallization and liquid-liquid demixing in solutions of semiflexible homopolymers. In our model, neighboring polymer segments can have isotropic interactions that affect demixing, and anisotropic interactions that are responsible for freezing. However, our simulations show that the isotropic interactions also have a noticeable effect on the freezing curve, as do the anisotropic interactions on demixing. As the relative strength of the isotropic interactions is reduced, the liquid-liquid demixing t…
Nafion is a perfluorosulfonated polymer, widely used in Proton Exchange Membrane Fuel Cells. This polymer adopts a complex structural organisation resulting from the microsegregation between hydrophobic backbones and hydrophilic sulfonic acid groups. Upon hydration appear water-filled channels and cavities, in which are released the acidic protons to form a solution of hydronium ions in water embedded in the polymer matrix. Below 273 K, a phenomenon of water sorption/desorption occurs, whose origin is still an open question. Performing neutron diffraction, we monitored the quantity of ice form…
The investigation of freezing transitions of single polymers is computationally demanding, since surface effects dominate the nucleation process. In recent studies we have systematically shown that the freezing properties of flexible, elastic polymers depend on the precise chain length. Performing multicanonical Monte Carlo simulations, we faced several computational challenges in connection with liquid-solid and solid-solid transitions. For this reason, we developed novel methods and update strategies to overcome the arising problems. We introduce novel Monte Carlo moves and two extensions to…
We report the results of Monte Carlo simulations investigating the effect of a spherical confinement within a simple model for a flexible homopolymer. We use the parallel tempering method combined with multi-histogram reweighting analysis and multicanonical simulations to investigate thermodynamical observables over a broad range of temperatures, which enables us to describe the behavior of the polymer and to locate the freezing and collapse transitions. We find a strong effect of the spherical confinement on the location of the collapse transition, whereas the freezing transition is hardly ef…
We study the adsorption of homogeneous or heterogeneous polymers onto heterogeneous planar surfaces with exponentially decaying site-site correlations, using a variational reference system approach. As a main result, we derive simple equations for the adsorption-desorption transition line. We show that the adsorption threshold is the same for systems with quenched and annealed disorder. The results are discussed with respect to their implications for the physics of molecular recognition.
We present in this letter an original freezing process yielding remarkably homogeneous films of chiral smectics. This optical homogeneity is observed on planar films as well as on films exhibiting various complex three-dimensional shapes.
Ice growth has attracted great attention for its capability of fabricating hierarchically porous microstructure. However, the formation of tilted lamellar microstructure during freezing needs to be reconsidered due to the limited control of ice orientation with respect to thermal gradient during in-situ observations, which can greatly enrich our insight into architectural control of porous biomaterials. This paper provides an in-situ study of solid/liquid interface morphology evolution of directionally solidified single crystal ice with its C-axis (optical axis) perpendicular to directions of …
The instability and periodic deformation of bilayer membranes during freezing processes are studied as a function of the difference of the shape energy between the high and the low temperature membrane states. It is shown that there exists a threshold stability condition, bellow which a planar configuration will be deformed. Among the deformed shapes, the periodic curved square textures are shown being one kind of the solutions of the associated shape equation. In consistency with recent expe rimental observations, the optimal ratio of period and amplitude for such a texture is found to be app…
We study the kinetics of the isotropic-smectic phase transition in a colloidal rod/polymer mixture by visualizing individual smectic layers. First, we show that the bulk isotropic-smectic phase transition is preceded by a surface freezing transition in which a quasi two-dimensional smectic phase wets the isotropic-nematic interface. Next, we identify a two step kinetic pathway for the formation of a bulk smectic phase. In the first step a metastable isotropic-nematic interface is formed. This interface is wetted by the surface induced smectic phase. In the subsequent step, smectic layers nucle…
Periodic boundary conditions for planar mixed flows are implemented in the context of a multi-chain Brownian dynamics simulation algorithm. The effect of shear rate $\dotγ$, and extension rate $\dotε$, on the size of polymer chains, $\left<R_e^2\right>$, and on the polymer contribution to viscosity, $η$, is examined for solutions of FENE dumbbells at finite concentrations, with excluded volume interactions between the beads taken into account. The influence of the mixedness parameter, $χ$, and flow strength, $\dotΓ$, on $\left<R_e^2\right>$ and $η$, is also examined, where $χ\rightarrow 0$ cor…
We study numerically a lattice model of semiflexible homopolymers with nearest neighbor attraction and energetic preference for straight joints between bonded monomers. For this we use a new algorithm, the "Pruned-Enriched Rosenbluth Method" (PERM). It is very efficient both for relatively open configurations at high temperatures and for compact and frozen-in low-T states. This allows us to study in detail the phase diagram as a function of nn-attraction epsilon and stiffness x. It shows a theta-collapse line with a transition from open coils to molten compact globules (large epsilon) and a fr…
We present exact spatio-temporal correlation functions of a Rouse polymer chain submerged in a fluid having planar mixed flow, in the steady state. Using these correlators, determination of the time scale distribution functions associated with the first-passage tumbling events is difficult in general; it was done recently in Phys. Rev. Lett.,101, 188301 (2008), for the special case of "simple shear" flow. We show here that the method used in latter paper fails for the general mixed flow problem. We also give many new estimates of the exponent $θ$ associated with the exponential tail of the ang…
Recent advances in single macromolecule experiments have sparked interest in the ensemble dependence of force-extension relations. The thermodynamic limit may not be attainable for such systems, that leads to inequivalence of the fixed-force and the fixed-extension ensemble. We consider an ideal Gaussian chain described by the Edwards Hamiltonian with one end tethered to a rigid planar substrate. We analytically calculate the force-extension relation in the two ensembles and we show their inequivalence which is caused by the confinement of the polymer to half space. The inequivalence is quite …
Strong coupling phenomena, such as the like charged macroions attraction, opposite charged macroions repulsion, charge renormalization or charge inversion, are known to be mediated by multivalent counterions. Most theories treat the counterions as point charges, and describe the system by a single coupling parameter that measures the strength of the Coulomb interactions. In many biological systems, the counterions are highly charged and have finite sizes and can be well-described by polyelectrolytes. The shapes and orientations of these polymer counterions play a major role in the thermodynami…
We study the adsorption of semiflexible polymers such as polyelectrolytes or DNA on planar and curved substrates, e.g., spheres or washboard substrates via short-range potentials using extensive Monte-Carlo simulations, scaling arguments, and analytical transfer matrix techniques. We show that the adsorption threshold of stiff or semiflexible polymers on a planar substrate can be controlled by polymer stiffness: adsorption requires the highest potential strength if the persistence length of the polymer matches the range of the adsorption potential. On curved substrates, i.e., an adsorbing sphe…
Computer simulations are used to characterize the entropic force of one or more polymers tethered to the tip of a hard conical object that interact with a nearby hard flat surface. Pruned-enriched-Rosenbluth-method (PERM) Monte Carlo simulations are used to calculate the variation of the conformational free energy, $F$, of a hard-sphere polymer with respect to cone-tip-to-surface distance, $h$, from which the variation of the entropic force, $f\equiv |dF/dh|$, with $h$ is determined. We consider the following cases: (1) a single freely-jointed tethered chain, (2) a single semiflexible tethered…
We present photoluminescence studies as a function of temperature from a series of conjugated polymers and a conjugated molecule with distinctly different backbone conformations. The organic materials investigated here are: planar methylated ladder type poly para-phenylene, semi-planar polyfluorene, and non-planar para hexaphenyl. In the longer-chain polymers the photoluminescence transition energies blue shift with increasing temperatures. The conjugated molecules, on the other hand, red shift their transition energies with increasing temperatures. Empirical models that explain the temperatur…
Using Gibbs ensemble Monte Carlo simulations and density functional theory we investigate the fluid-fluid demixing transition in inhomogeneous colloid-polymer mixtures confined between two parallel plates with separation distances between one and ten colloid diameters covering the complete range from quasi two-dimensional to bulk-like behavior. We use the Asakura-Oosawa-Vrij model in which colloid-colloid and colloid-polymer interactions are hard-sphere like, whilst the pair potential between polymers vanishes. Two different types of confinement induced by a pair of parallel walls are consider…
The interplay between concentration, flow, hydrodynamic interactions (HI), and topological interactions governing semidilute polymer dynamics in strong flows are challenging to characterize. Brownian dynamics (BD) simulations are particularly valuable as a way to direct visualize how molecular interactions arise in these systems; however, BD simulations are often computationally limited by the need to calculate the correlated Brownian noise via decomposition of the diffusion tensor. Previously we have introduced an iterative conformational averaging (CA) method for BD simulations which bypasse…
Polymer translocation in three dimensions out of planar confinements is studied in this paper. Three membranes are located at $z=-h$, $z=0$ and $z=h_1$. These membranes are impenetrable, except for the middle one at $z=0$, which has a narrow pore. A polymer with length $N$ is initially sandwiched between the membranes placed at $z=-h$ and $z=0$ and translocates through this pore. We consider strong confinement (small $h$), where the polymer is essentially reduced to a two-dimensional polymer, with a radius of gyration scaling as $R^{\tinytext{(2D)}}_g \sim N^{ν_{\tinytext{2D}}}$; here, $ν_{\ti…
The structural phase behavior of polymer brushes, single-component linear homopolymers grafted onto a planar substrate, is studied using the molecular Monte Carlo method in 3 dimensions. When simulation parameters of the system are set in regions of macrophase separation of solution for the corresponding non-grafted homopolymers, the grafted polymers also prefer segregation. However, macrophase separation is disallowed due to the spatially-fixed grafting points of the polymers. Such constraints on the grafting are similar to connecting points between blocks of non-grafted diblock copolymers at…
Extensional rheometry of mobile fluids. Part II: Comparison between the uniaxial, planar and biaxial extensional rheology of dilute polymer solutions using numerically-optimized stagnation point microfluidic devices
The surface tension of interacting polymers in a good solvent is calculated theoretically and by computer simulations for a planar wall geometry and for the insertion of a single colloidal hard-sphere. This is achieved for the planar wall and for the larger spheres by an adsorption method, and for smaller spheres by a direct insertion technique. Results for the dilute and semi-dilute regimes are compared to results for ideal polymers, the Asakura-Oosawa penetrable-sphere model, and to integral equations, scaling and renormalization group theories. The largest relative changes with density are …
The problem of charged polymer chains (polyelectrolytes) as they adsorb on a planar surface is addressed theoretically. We review the basic mechanisms and theory underlying polyelectrolyte adsorption on a single surface in two situations: adsorption of a single charged chain, and adsorption from a bulk solution in $θ$ solvent conditions. The behavior of flexible and semi-rigid chains is discussed separately and is expressed as function of the polymer and surface charges, ionic strength of the solution and polymer bulk concentration. We mainly review mean-field results and briefly comment about…
Contact freezing is a mode of atmospheric ice nucleation in which a collision between a dry ice nucleating particle (INP) and a water droplet results in considerably faster heterogeneous nucleation. The molecular mechanism of such enhancement is, however, still a mystery. While earlier studies had attributed it to collision-induced transient perturbations, recent experiments point to the pivotal role of nanoscale proximity of the INP and the free interface. By simulating heterogeneous nucleation of ice within INP-supported nanofilms of two model water-like tetrahedral liquids, we demonstrate t…
The properties of the interface in a phase-separated solution of polymers with different degrees of polymerization and Kuhn segment lengths are calculated. The starting point is the planar interface, the profile of which is calculated in the so-called 'blob model', which incorporates the solvent in an implicit way. The next step is the study of a metastable droplet phase formed by imposing a chemical potential different from that at coexistence. The pressure difference across the curved interface, which corresponds to this higher chemical potential, is used to calculate the curvature propertie…
We construct a density functional for the lattice gas / Ising model on square and cubic lattices based on lattice fundamental measure theory. In order to treat the nearest-neighbor attractions between the lattice gas particles, the model is mapped to a multicomponent model of hard particles with additional lattice polymers where effective attractions between particles arise from the depletion effect. The lattice polymers are further treated via the introduction of polymer clusters (labelled by the numbers of polymer they contain) such that the model becomes a multicomponent model of particles …
We present a generalized theory for studying phase separation in blends of polymers containing dipoles on their backbone. The theory is used to construct co-existence curves and to study the effects of dipolar interactions on interfacial tension for a planar interface between the coexisting phases. We show that a mismatch in monomeric dipole moments, or equivalently a mismatch in the dielectric constant of the pure components, leads to destabilization of the homogeneous phase. Corrections to the Flory-Huggins phase diagram are predicted using the theory. Furthermore, we show that the interfaci…
The sliding of non-Newtonian drops down planar surfaces results in a complex, entangled balance between interfacial forces and non linear viscous dissipation, which has been scarcely inspected. In particular, a detailed understanding of the role played by the polymer flexibility and the resulting elasticity of the polymer solution is still lacking. To this aim, we have considered polyacrylamide (PAA) solutions of different molecular weights, suspended either in water or glycerol/water mixtures. In contrast to drops with stiff polymers, drops with flexible polymers exhibit a remarkable elongati…
By analytically solving some simple models of phase-ordering kinetics, we suggest a mechanism for the onset of non-equilibrium behaviour in colloid-polymer mixtures. These mixtures can function as models of atomic systems; their physics therefore impinges on many areas of thermodynamics and phase-ordering. An exact solution is found for the motion of a single, planar interface separating a growing phase of uniform high density from a supersaturated low density phase, whose diffusive depletion drives the interfacial motion. In addition, an approximate solution is found for the one-dimensional e…
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 a…
The winding angle probability distribution of a planar self-avoiding walk has been known exactly since a long time: it has a gaussian shape with a variance growing as $<θ^2>\sim \ln L$. For the three-dimensional case of a walk winding around a bar, the same scaling is suggested, based on a first-order epsilon-expansion. We tested this three-dimensional case by means of Monte Carlo simulations up to length $L\approx25\,000$ and using exact enumeration data for sizes $L\le20$. We find that the variance of the winding angle scales as $<θ^2>\sim (\ln L)^{2α}$, with $α=0.75(1)$. The ratio $γ= <θ^4>…
