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Liquid mixtures composed of colloidal particles and much smaller non-adsorbing linear homopolymers can undergo a gelation transition due to polymer-mediated depletion forces. We now show that the addition of linear polymers to suspensions of soft colloids having the same hydrodynamic size yields a liquid-to-gel-to-re-entrant liquid transition. In particular, the dynamic state diagram of 1,4-polybutadiene star-linear polymer mixtures was determined with the help of linear viscoelastic and small angle X-ray scattering experiments. While keeping the star polymers below their nominal overlap concentration, a gel was formed upon increasing the linear polymer content. Further addition of linear chains yielded a re-entrant liquid. This unexpected behavior was rationalized by the interplay of three possible phenomena: (i) depletion interactions, driven by the size disparity between the stars and the polymer length scale which is the mesh size of this entanglement network; (ii) colloidal deswelling due to the increased osmotic pressure exerted onto the stars; and (iii) a concomitant progressive suppression of depletion efficiency on increasing polymer concentration due to reduced mesh size, hence a smaller range of attraction. Our results unveil an exciting new way to tailor the flow of soft colloids and highlight a largely unexplored path to engineer soft colloidal mixtures., Comment: 27 pages, 5 figures

We present a systematic experimental study of the shear rheology of metallosupramolecular assemblies based on entangled telechelic star polymers comprising one (single dynamic network) or two (double dynamics network) types of physical bonds with the aim to unravel the role of concentration and strength of these bonds on the nonlinear response. Model dynamic networks functionalized with terpyridine ligands were formed by adding different metal ions with increasing bonding strength, zinc, copper, and cobalt. The dynamics are driven by entanglement/disentanglement processes and a ligand exchange mechanism. Steady-state viscosities of single and double dynamics networks collapse onto a universal curve over a wide range of Weissenberg numbers based on terminal time (up to about 300 for single and 1000 for double), exhibiting stronger shear thinning (with an exponent of −0.76) compared to entangled neutral star polymers. Double dynamics networks consisting of two different metal ions (with different lifetimes) exhibit stronger mechanical coherence (rate-dependent fractional viscosity overshoot) and accumulate larger strain at steady-state flow compared to single-ion counterparts. The shear stress growth function signals exhibit weak, albeit unambiguous shear strain hardening, which becomes more pronounced for stronger associations. They also exhibit double overshoot, which reflects the interplay of association strength and chain deformation. Increasing the strength of associations leads to the failure of the Cox–Merz rule, which is more severe for single dynamic networks. The markedly different behavior of double dynamics networks is attributed to the fact that at sufficiently high ion content, the weaker bond acts as a sacrificial component, which provides local energy dissipation and enhances the overall deformability. This bears analogies with their linear viscoelastic response, which has revealed that the arm disentanglement (delayed due to the reversible bonds) effectively interpolates between the two single dynamic network components, depending on composition. Our results suggest ways to tailor the mechanical properties of this class of materials by judicious choice of the type and content of the ion.

A methodology to investigate the linear viscoelastic properties of complex fluids at elevated pressures (up to 120 MPa) is presented. It is based on a dynamic light scattering (DLS) setup coupled with a stainless steel chamber, where the test sample is pressurized by means of an inert gas. The viscoelastic spectra are extracted through passive microrheology. We discuss an application to hydrogen-bonding motif 2,4-bis(2-ethylhexylureido)toluene (EHUT), which self-assembles into supramolecular structures (tubes and filaments) in apolar solvents dodecane and cyclohexane. High levels of pressure (roughly above 20 MPa) are found to slow down the terminal relaxation process; however, the increases in the entanglement plateau modulus and the associated persistence length are not significant. The concentration dependence of the plateau modulus, relaxation times (fast and slow), and correlation length is practically the same for all pressures and exhibits distinct power-law behavior in different regimes. Within the tube phase in dodecane, the relative viscosity increment is weakly enhanced with increasing pressure and reaches a plateau at about 60 MPa. In fact, depending on concentration, the application of pressure in the tube regime may lead to a transition from a viscous (unentangled) to a viscoelastic (partially entangled to well-entangled) solution. For well-entangled, long tubes, the extent of the plateau regime (ratio of high- to low-moduli crossover frequencies) increases with pressure. The collective information from these observations is summarized in a temperature-pressure state diagram. These findings provide ingredients for the formulation of a solid theoretical framework to better understand and exploit the role of pressure in the structure and dynamics of supramolecular polymers.

We explore the behavior of a supramolecular polymer subjected to repeated shear-startup runs. This interesting test was proposed 50 years ago as a measure of disentanglement kinetics in linear polymers. A key experimental finding was that the recovery time (originally attributed exclusively to the relaxation of partially disentangled state) decreased with increasing imposed shear rate. Recent modeling and simulations put the work in perspective by showing that the recovery time mainly reflects chain reorientation. However, for the present supramolecular polymer, the recovery time was found to be rate independent. This drastic difference is attributed to the different mechanism of stress relaxation, which involves a combination of bond breaking/recombination and reptation processes. Hence, the repeated shear-startup protocol may serve as a sensitive indicator of (supramolecular) polymer signatures and a tool to evaluate stress relaxation models.

Dynamic mechanical oscillatory shear measurements with torsional rectangular geometry are widely carried out in order to determine the mechanical properties of soft solid materials in a quick and practical way. This technique has the advantage of avoiding slip effects, thus being particularly attractive for testing stiff elastomers such as vulcanized rubber compounds. However, one of its drawbacks is the clamping system required to keep the specimen edges in place. Since it imposes a constraint to warping deformations (i.e., out-of-plane cross-section distortions about the torsional axis), a certain increase of dynamic moduli with respect to their values in simple shear is observed and considered as an experimental artifact (i.e., de Saint-Venant's assumption of primary torsion of the specimen is no longer valid). The increase of dynamic moduli in torsion depends on the specimen's cross-section geometry and relative dimensions. We test here the capability of different torsion models to describe the constrained warping effect for an industrial rubber with rectangular specimen cross section using a wide range of different geometric parameters (length-to-width p ratio and width-to-thickness u ratio). We compare two theoretical models (Vlasov's model and Timoshenko's approach) and a phenomenological model (based on finite element simulations by Diani and Gilormini) with our experimental data set. We propose a slight modification of Vlasov's model to obtain realistic predictions of torsion over a wider parameter range. It is shown to be particularly useful in soft rubber testing, and the limitations in the choice of specimen geometry to obtain sufficient torque signal are overcome.

Presence of an ultra high molecular weight (UHMw) fraction in flowing polymer melts is known to facilitate formation of oriented crystalline structures significantly. The UHMw fraction manifests itself as a minor tail in the molar mass distribution and is hardly detectable in the canonical characterization methods. In this study, alternatively, we demonstrate how the nonlinear extensional rheology reveals to be a very sensitive characterization tool for investigating the effect of the UHMw-tail on the structural ordering mechanism. Samples containing a UHMw-tail relative to samples without, exhibit a clear increase in extensional stress that is directly correlated with the crystalline orientation of the quenched samples. Extensional rheology, particularly, in combination with linear creep measurements, thus, enables the conformational evolution of the UHMw-tail to be studied and linked to the enhanced formation of oriented structures.

Adding small amounts of ring polymers to a matrix of their linear counterparts is known to increase the zero-shear-rate viscosity because of linear-ring threading. Uniaxial extensional rheology measurements show that, unlike its pure linear and ring constituents, the blend exhibits an overshoot in the stress growth coefficient. By combining these measurements with ex-situ small-angle neutron scattering and nonequilibrium molecular dynamics simulations, this overshoot is shown to be driven by a transient threading–unthreading transition of rings embedded within the linear entanglement network. Prior to unthreading, embedded rings deform affinely with the linear entanglement network and produce a measurably stronger elongation of the linear chains in the blend compared to the pure linear melt. Thus, rings uniquely alter the mechanisms of transient elongation in linear polymers.

We combine state-of-the art synthesis, simulations, and physical experiments to explore the tunable, responsive character of telechelic star polymers as models for soft patchy particles. We focus on the simplest possible system: a star comprising three asymmetric block copolymer arms with solvophilic inner and solvophobic outer blocks. Our dilute solution studies reveal the onset of a second slow mode in the intermediate scattering functions as the temperature decreases below the θ-point of the outer block, as well as the size reduction of single stars upon further decreasing temperature. Clusters comprising multiple stars are formed and their average dimensions, akin to the single star size, counterintuitively decrease upon cooling. A similar phenomenology is observed in simulations upon increasing attraction between the outer blocks and is rationalized as a result of the interplay between interstar associations and steric repulsion between the star cores. Since our simulations are able to describe the experimental findings reliably, we can use them with confidence to make predictions at conditions and flow regimes that are inaccessible experimentally. Specifically, we employ simulations to investigate flow properties of the system at high shear rates, revealing shear thinning behavior caused by the breakup of interstar associations under flow. On the other hand, the zero-shear viscosity obtained experimentally exhibits a rather weak activation energy, which increases upon rising star concentration. These findings demonstrate the unusual properties of telechelic star polymers even in the dilute regime. They also offer a powerful toolbox for designing soft patchy particles and exploring their unprecedented responsive properties further on.

Flow-fields are typically used to intimately mix large μm-sized particles with polymer melts. Here we show, using rheology, X-ray scattering, and electron microscopy, that shear flows do not improve the spatial dispersion or ordering of spherical nanoparticles (NP) grafted with polymer chains over the ranges of flow fields realizable in our experiments in the melt state. In the absence of flow, grafted NPs robustly self-assemble into a variety of superstructures when they are added to a homopolymer matrix with the same chemistry as the NP grafts. We find that isolated particles and spherical NP clusters remain dispersed but do not flow align. On the other hand, anisotropic NP assemblies initially break and their constituent building blocks (strings or sheets) flow-align locally. At very large strains, they coarsen into large aggregates, reflecting the dominance of interparticle attractions over flow fields and thermal energy.

We report on the unusual response of a well-characterized entangled comb polymer in simple shear flow. The polymer with highly entangled backbone (about 16 entanglements) and on average 29 long branches (about 3 entanglements each) has been extensively characterized by interaction chromatography and its rheology carefully studied under controlled conditions using a special cone partitioned-plate geometry. We observe that the start-up shear stress becomes roughly rate independent above a certain critical rate, related to the relaxation time of the branches. Within the rate-independent region, the start-up shear stress displays a double overshoot. We interpret these observations in light of tube-based pompom dynamics. The key idea is that for sufficiently long branches the main stress overshoot, which reflects backbone stretching and orientation, is preceded by the withdrawal of branches into the backbone tube. The excellent quantitative comparison between the simulations and experiments supports the proposed mechanism of the double stress overshoot.

We use the impact of drops on a small solid target as a tool to investigate the behavior of viscoelastic fluids under extreme deformation rates. We study two classes of transient networks: semidilute solutions of supramolecular polymers and suspensions of spherical oil droplets reversibly linked by polymers. The two types of samples display very similar linear viscoelastic properties, which can be described with a Maxwell fluid model, but contrasting nonlinear properties due to different network structure. Upon impact, weakly viscoelastic samples exhibit a behavior qualitatively similar to that of Newtonian fluids: A smooth and regular sheet forms, expands, and then retracts. By contrast, for highly viscoelastic fluids, the thickness of the sheet is found to be very irregular, leading to instabilities and eventually formation of holes. We find that material rheological properties rule the onset of instabilities. We first provide a simple image analysis of the expanding sheets to determine the onset of instabilities. We then demonstrate that a Deborah number related to the shortest relaxation time associated to the sample structure following a high shear is the relevant parameter that controls the heterogeneities in the thickness of the sheet, eventually leading to the formation of holes. When the sheet tears-up, data suggest by contrast that the opening dynamics depends also on the expansion rate of the sheet., Comment: accepted for publication in Soft Matter

Dendronized polymers (denpols) are thick polymers comprising a linear backbone with grafted treelike structures (dendrons). The latter give rise to a molecular thickness that is a function of dendr...

We combine synthesis, physical experiments, and computer simulations to investigate self-assembly patterns of low-functionality telechelic star polymers (TSPs) in dilute solutions. In particular, in this work, we focus on the effect of the arm composition and length on the static and dynamic properties of TSPs, whose terminal blocks are subject to worsening solvent quality upon reducing the temperature. We find two populations, single stars and clusters, that emerge upon worsening the solvent quality of the outer block. For both types of populations, their spatial extent decreases with temperature, with the specific details (such as temperature at which the minimal size is reached) depending on the coupling between inter- and intra-molecular associations as well as their strength. The experimental results are in very good qualitative agreement with coarse-grained simulations, which offer insights into the mechanism of thermoresponsive behavior of this class of materials.

We investigated the linear viscoelasticity of bottlebrush polystyrenes (PSs) with total molar masses ranging from 132 to 769 kg/mol, bearing short side chains (with molar masses of 5 and 7 kg/mol, ...

We present a comprehensive experimental rheological dataset for purified entangled ring polystyrenes and their blends with linear chains in nonlinear shear and elongation. In particular, data for the shear stress growth coefficient, steady-state shear viscosity, and first and second normal stress differences are obtained and discussed as functions of the shear rate, as well as molecular parameters (molar mass, blend composition, and decreasing molar mass of linear component in the blend). Over the extended parameter range investigated, rings do not exhibit clear transient undershoot in shear, in contrast to their linear counterparts and ring-linear blends. For the latter, the size of the undershoot and respective strain appear to increase with the shear rate. The universal scaling of the strain at overshoot and fractional overshoot (the ratio of the maximum to the steady-state shear stress growth coefficient) indicates subtle differences in the shear-rate dependence between rings and linear polymers or their blends. The shear thinning behavior of pure rings yields a slope nearly identical to predictions (−4/7) of a recent shear slit model and molecular dynamics simulations. Data for the second normal stress difference are reported for rings and ring-linear blends. While N2 is negative and its absolute value stays below that of N1, as for linear polymers, the ratio –N2/N1 is unambiguously larger for rings compared to linear polymer solutions with the same number of entanglements (almost by a factor of 2), in agreement with recent nonequilibrium molecular dynamics simulations. Furthermore, –N2 exhibits slightly weaker shear rate dependence compared to N1 at high rates, and the respective power-law exponents can be rationalized in view of the slit model (3/7) and simulations (0.6), although further work is needed to unravel the molecular original of the observed behavior. The comparison of shear and elongational stress growth coefficients for blends reflects the effect of ring-linear threading, which leads to significant viscosity enhancement in elongation. Along the same lines, the elongational stress is much larger than the first normal stress in shear, and their ratio is much larger for rings and ring-linear blends compared to linear polymers. This confirms the interlocking scenario of rings and their important role in mechanically reinforcing linear matrices.

We study the linear viscoelastic properties of polymeric networks formed by poly( n-butyl acrylate) telechelic stars end-capped with 2,2:6,2″-terpyridine (Star-PnBA-tpy4) and two types of metal-ligand cross-links with different lifetimes. The influence of interactions, mediated by temperature, nature of metal ions, and ion content, on the linear viscoelastic behavior of both single and double dynamics transient networks is systematically investigated by small amplitude oscillatory shear and creep rheometry. The experimental results reveal that the dynamics of networks with two different metal-ligand cross-links is much faster than expected, characterized by the average sticker lifetime rather than a discrete contribution of each metal-ligand complex. We model the dynamics with the help of our modified tube-based time marching algorithm by accounting for both association/dissociation dynamics of metal-ligand coordination and the entanglement dynamics. Two parameters are defined in the model, namely, the proportion of dangling ends and the average time during which a sticker is free. This allows us to quantify the transient dynamics of the network and, in particular, to determine how the sticker dynamics depend on temperature and ion content.

We investigate the linear viscoelastic properties of industrial pressure sensitive adhesives comprising double networks with an entangled acrylate-based polymer and two types of intermolecular associations (crosslinking), permanent (epoxide) and reversible (metal-chelate), having different compositions. A combination of shear rheometry and an appropriately modified version of the Time Marching Algorithm (TMA) allows to probe and analyze the behavior of the different double dynamic networks, in particular, the effects of the type and amount of crosslinks on their linear viscoelastic spectra. To this end, the dynamics of the double networks are compared with the respective individual responses of the polymeric component without crosslinks and the single networks (possessing only physical or only chemical crosslinks), in order to quantify their contributions to the relaxation mechanisms, particularly the interplay between disentanglement and bond association/dissociation processes. With the help of the TMA model, we also examine the respective roles of the lifetime of stickers, polydispersity, and molar mass. Triggered by the good comparison between predictions and experimental data, we propose a framework to tune material parameters in order to obtain a desired viscoelastic behavior.

The shape, breadth, and average molecular weight of the overall molecular weight distribution (MWD) largely define polymer properties. In conventional free-radical polymerization, control over this distribution is through the many competing kinetic pathways dominated by radical termination events. "Living"radical polymerization mechanistically minimizes these termination events, providing a facile route to a desired Gaussian distribution with the distribution breadth dependent upon the activity of the catalyst or modulating agent. However, producing unusually shaped distributions can only be achieved through modeling of the complex polymerization kinetics and invoking feeding and other methods. Here, we construct square, slanted, and chair-like MWDs by blending two to four polymers made using a low-reactive RAFT agent with dispersities close to 2. The synthesis of these polymers, unlike that of polymers made with high-reactive RAFT agents, is simple, scalable, and importantly reproducible as the MWD is independent of conversion, making this polymerization method virtually and kinetically model-free. The blending method described here overcomes many of the difficulties in producing unusually shaped MWDs and allows control over the shape and breadth of the MWD. The concept further provides a general synthetic strategy for studying important structure-property relationships of polymers with desired processing and performance characteristics. This is demonstrated by measurement and modeling analysis of the linear viscoelastic properties of selected samples, which provides a way to tailor the properties of polymers by controlling the form of their MWD via blending. Unlike conventional approaches analyzing the effects of the MWD, its actual shape is considered and its effect on the properties is addressed.

High-frequency rheology is a form of mechanical spectroscopy which provides access to fast dynamics in soft materials and hence can give valuable information about the local scale microstructure. It is particularly useful for systems where time-temperature superposition cannot be used, when there is a need to extend the frequency range beyond what is possible with conventional rotational devices. This review gives an overview of different approaches to high-frequency bulk rheometry, i.e. mechanical rheometers that can operate at acoustic (20 Hz–20 kHz) or ultrasound (> 20 kHz) frequencies. As with all rheometers, precise control and know-how of the kinematic conditions are of prime importance. The inherent effects of shear wave propagation that occur in oscillatory measurements will hence be addressed first, identifying the gap and surface loading limits. Different high-frequency techniques are then classified based on their mode of operation. They are reviewed critically, contrasting ease of operation with the dynamic frequency range obtained. A comparative overview of the different types of techniques in terms of their operating window aims to provide a practical guide for selecting the right approach for a given problem. The review ends with a more forward looking discussion of selected material classes for which the use of high-frequency rheometry has proven particularly valuable or holds promise for bringing physical insights.

Two homologous series of dendronized polymers (DPs) of the second and third generations, with different degrees of polymerization of the backbone, were synthesized combining two previously reported...

We report on the linear viscoelastic properties of mixtures comprising multiarm star (as model soft colloids) and long linear chain homopolymers in a good solvent. In contrast to earlier works, we investigated symmetric mixtures (with a size ratio of 1) and showed that the polymeric and colloidal responses can be decoupled. The adopted experimental protocol involved probing the linear chain dynamics in different star environments. To this end, we studied mixtures with different star mass fraction, which was kept constant while linear chains were added and their entanglement plateau modulus ($G_p$) and terminal relaxation time ($\tau_d$) were measured as functions of their concentration. Two distinct scaling regimes were observed for both $G_p$ and $\tau_d$: at low linear polymer concentrations, a weak concentration dependence was observed, that became even weaker as the fraction of stars in the mixtures increased into the star glassy regime. On the other hand, at higher linear polymer concentrations, the classical entangled polymer scaling was recovered. Simple scaling arguments show that the threshold crossover concentration between the two regimes corresponds to the maximum osmotic star compression and signals the transition from confined to bulk dynamics. These results provide the needed ingredients to complete the state diagram of soft colloid-polymer mixtures and investigate their dynamics at large polymer-colloid size ratios. They also offer an alternative way to explore aspects of the colloidal glass transition and the polymer dynamics in confinement. Finally, they provide a new avenue to tailor the rheology of soft composites., Comment: 9 Figures

Star polymers with intermediate branching functionalities (64 and 128 arms) are known to exhibit a hybrid viscoelastic response, relaxing stress via a fast polymeric arm retraction and a slow collo...

We present a systematic investigation of the structure and dynamic properties of model soft–hard colloidal mixtures. Results of a coarse-grained theoretical model are contrasted with rheological data, where the soft and hard colloids are mimicked by large star polymers with high functionality as the soft component and smaller stars with ultrahigh functionality as the hard one. Previous work by us revealed the recovery of the ergodicity of glassy soft star solutions and subsequent arrested phase separation and re-entrant solid transition upon progressive addition of small hard depletants. Here, we use different components to show that a small variation in softness has a significant impact on the state diagram of such mixtures. In particular, we establish that rendering the soft component more penetrable and modifying the size ratio bring about a remarkable shift in both the phase separation region and the glass-melting line so that the region of restored ergodicity can be notably enhanced and extended to much higher star polymer concentrations than for pure systems. We further rationalize our findings by analyzing the features of the depletion interaction induced by the smaller component that result from the interplay between the size ratio and the softness of the large component. These results demonstrate the great sensitivity of the phase behavior of entropic mixtures to small changes in the molecular architecture of the soft stars and point to the importance of accounting for details of the internal microstructure of soft colloidal particles for tailoring the flow properties of soft composites.

International audience; When a drop of fluid hits a small solid target of comparable size, it expands radially until reaching a maximum diameter and subsequently recedes. In this work, we show that the expansion process of liquid sheets is controlled by a combination of shear (on the target) and biaxial extensional (in the air) deformations. We propose an approach toward a rational description of the phenomenon for Newtonian and viscoelastic fluids by evaluating the viscous dissipation due to shear and extensional deformations, yielding a prediction of the maximum expansion factor of the sheet as a function of the relevant viscosity. For Newtonian systems, biaxial extensional and shear viscous dissipation are of the same order of magnitude. On the contrary, for thinning solutions of supramolecular polymers, shear dissipation is negligible compared to biaxial extensional dissipation and the biaxial thinning extensional viscosity is the appropriate quantity to describe the maximum expansion of the sheets. Moreover, we show that the rate-dependent biaxial extensional viscosities deduced from drop impact experiments are in good quantitative agreement with previous experimental data and theoretical predictions for various viscoelastic liquids.

Melts of multiarm stars of 1,4-polybutadiene (dendrimer arborescent hybrids) with very high branching functionality ($f$) and small arm molar mass behave as jammed colloids and show distinct layers of segmental mobility. Three mobility layers were identified, comprising outer, intermediate, and near-core segments, all displaying a Vogel-Fulcher-Tammann temperature dependence. The respective glass temperatures increase as ${f}^{1/2}$. Our findings pave the way for further progress in this field by reconsidering previous theoretical treatments based on a single friction coefficient in hybrid nanoparticles such as densely grafted stars.

This work addresses the shear response of entangled linear polymers by assessing the current state-of-the-art model and proposing alternative directions. In particular, we examine the performance of the Graham–Likhtman–McLeish–Milner (GLaMM) nonlinear tube model in fast shear flows. Predictions are compared against experimental data for well-characterized, monodisperse, entangled linear polystyrene chains. Unlike previous works using the GLaMM model, finite extensibility is accounted for. Comparison of model predictions and data not only reveals an overall reasonable performance but also highlights limitations. For example, the predictions significantly depend on whether the contribution of contour length fluctuations to the retraction rate is accounted for or not. This specific sensitivity of the model is enhanced as the Rouse–Weissenberg number increases. Possible improvement of the model by modification of the existing mechanisms/model assumptions and/or by incorporation of overlooked mechanisms such as chain tumbling and CCR-driven disentanglement (CCR-D) is discussed. As a possible way to overcome the existing limitations, we propose an alternative approach based on the time marching algorithm (TMA) and focus on the description of the steady-state regime. Compared to the GLaMM model, this approach allows us to keep track of the relaxation state of each entanglement segment in a simple way, while ensuring consistency between chain stretch and constraint release mechanisms. Moreover, it accounts for CCR-D in an indirect manner. A key ingredient is the use of the recently advanced concept of the shear blob and its dependence on the shear rate. Our simple modification of TMA reproduces the experimental steady-state viscosities accurately for all samples and for all shear rates examined.

Hydrogels that can respond to a number of external stimuli and at the same time show impressive rheological properties are promising materials for a wide range of bioapplications. Here, we present a series of well-defined linear amphiphilic pentablock hybrid polypeptides of the ABCBA type, where A is poly(l-lysine), B is poly(l-histidine)-co-poly(γ-benzyl-l-glutamate), and C is poly(ethylene oxide) (PEO). The polymers were synthesized by the sequential primary amine ring-opening polymerization of N-carboxy anhydrides using bis amine poly(ethylene oxide) (PEO) as a bifunctional macroinitiator, and the length of all of the blocks was varied. The resulting materials formed novel extrudable in situ forming quickly self-healing hydrogels, responsive to the alteration of pH and increase of temperature. The connection between the alteration of the secondary structure of the polypeptides with the viscoelastic behavior was revealed by means of rheology and circular dichroism. Small-angle neutron scattering and scanning electron microscopy were employed to shed light on the structure of the polymers and how it affects their rheological properties. The obtained polymers were subjected to enzymatic degradation tests with trypsin and leucine aminopeptidase. The results suggest that these biomaterials have the potential to be used in a number of bioapplications like drug delivery, 3D printing, and tissue engineering.

In some recent experiments on entangled polymers of stress growth in startup of fast shear flows an undershoot in the shear stress is observed following the overshoot, i.e., before approaching the steady state. Whereas tumbling of the entangled chain was proposed to be at its origin, here we investigate another possible cause for the stress undershoot, i.e., slippage at the interface between polymer and solid wall. To this end, we extend the primitive chain network model to include slip at the interface between entangled polymeric liquids and solid walls with grafted polymers. We determine the slip velocity at the wall, and the shear rate in the bulk, by imposing that the shear stress in the bulk polymers is equal to that resulting from the polymers grafted at the wall. After confirming that the predicted results for the steady state are reasonable, we examine the transient behavior. The simulations confirm that slippage weakens the magnitude of the stress overshoot, as reported earlier. The undershoot is also weakened, or even disappears, because of a reduced coherence in molecular tumbling. In other words, the disentanglement between grafted and bulk chains, occurring throughout the stress overshoot region, does not contribute to the stress undershoot., Comment: 38 pages and 9 figures

Two different classes of hairy self-suspended nanoparticles in the melt state, polymer-grafted nanoparticles (GNPs) and star polymers, are shown to display universal dynamic behavior across a broad range of parameter space. Linear viscoelastic measurements on well-characterized silica-poly(methyl acrylate) GNPs at fixed core radius (R(core)) and grafting density (or number of arms f), but varying arm degree of polymerization (N(arm)) show two distinctly different regimes of response. A colloidal Regime I at small N(arm) (large core volume fraction), with a predominant low-frequency solid-like colloidal plateau and ultraslow relaxation, and a polymeric Regime II at large N(arm) (small core volume fractions), with a response dominated by the star-like relaxation of partially interpenetrated arms. The transition between the two regimes is marked by a cross-over where both polymeric and colloidal modes are discerned albeit without a distinct colloidal plateau. Similarly, polybutadiene multiarm stars also exhibit the colloidal response of Regime I at very large f and small N(arm). The star arm relaxation model and a simple scaling model of nanoparticle escape from the cage of neighbors by overcoming a hopping potential barrier due to their elastic deformation, describe quantitatively the linear response of the polymeric and colloidal regimes, respectively, in all these cases. The dynamic behavior of hairy nanoparticles of different chemistry and molecular characteristics, investigated here and reported in the literature, can be mapped onto a universal dynamic diagram of [Formula: see text] as a function of [Formula: see text] , where [Formula: see text] is the monomeric volume. In this diagram, the two regimes are separated by a line where the hopping potential ΔU(hop) is equal to the thermal energy, k(B)T. ΔU(hop) can be expressed as a function of the overcrowding parameter x, i.e. the ratio of f to the maximum number of unperturbed chains with N(arm) that can fill the volume occupied by the polymeric corona, hence this crossing is shown to occur when x=1. For x>1 we have colloidal Regime I with overcrowded volume, stretched arms and ΔU(hop) > k(B)T, while polymeric Regime II is linked to x

We present an investigation into the dynamic relaxation mechanisms of a polybutadiene blend composed of a four-arm star (10 wt. %) and a linear polymer matrix in the presence of an applied shear flow. Our focus was the response of the star polymer, which cannot be unambiguously assessed via linear viscoelastic measurements since the signature of the star polymer can barely be detected due to the dominant contribution of the linear matrix. By utilizing small-angle neutron scattering (SANS) coupled with a Couette shear device and a deuterated matrix polymer, we investigated the dynamics of the minority star component of the blend. Our results confirm that the stars deform anisotropically with increasing shear rate. We have compared the SANS data with predictions from the well-established scattering adaptation of the state-of-the-art tube model for entangled linear polymer melts undergoing shear, i.e., Graham, Likhtman, Milner, and McLeish (GLaMM) approach, appropriately modified following earlier studies in order to apply to the star. This modified model, GLaMM-R, includes the physics necessary to understand stress relaxation in both the linear and nonlinear flow regimes, i.e., contour length fluctuations, constraint release, convective constraint release, and chain retraction. The full scattering signal is due to the minority star component and, although the contribution of the linear chains is hidden from the neutron scattering, they still influence the star polymer molecular dynamics, with the applied shear rate ranging from approximately 8 to 24 s−1, below the inverse relaxation time of the linear component. This study provides another confirmation that the combination of rheology and neutron scattering is an indispensable tool for investigating the nonlinear dynamics of complex polymeric systems.

Nonlinear rheometry of interfaces is very challenging because of the limits of current day instrumentation and the intricate coupling of flows at interfaces and in the bulk. The use of time periodic flows may constitute a first step in addressing this issue. Fourier transform rheology (FTR) measurements with quasi-monolayers at the air-water interface are used in order to assess the suitability of the different devices to investigate nonlinear interfacial shear viscoelasticity. The probe material was a poly (methyl methacrylate) forming a soft glassy interface, whereas complementary measurements were performed with a polystyrene latex suspension forming a predominantly viscous interface at intermediate surface coverages. The obtained data with the magnetic rod rheometer (ISR) were compared against those obtained with the bicone and the double wall ring geometries attached to standard rotational rheometers. In particular, an unexpected appearance of even in addition to odd harmonics is discussed in terms of flow field asymmetry.

We combine linear viscoelastic measurements and modelling in order to explore the dynamics of blends of the same-molecular-weight ring and linear polymers in the regime of the low volume fraction (0.3 or lower) of the ring component. The stress relaxation modulus is affected by the constraint release (CR) of both rings and linear components due to the motion of linear chains. We develop a CR-based model of ring-linear blends that predicts the stress relaxation function in the low fraction regime of ring component in excellent agreement with experiments. Rings trapped by their entanglements with linear chains can only relax by linear-chain-induced constraint release, resulting in much slower relaxation of rings than of linear chains. The relative viscosity [Formula: see text] of the blend with respect to the linear melt viscosity η(L) at ring overlap volume fraction [Formula: see text] increases proportionally to the square root of ring molecular weight [Formula: see text]. Our experimental results clearly demonstrate that it is possible to enhance the viscosity and simultaneously the structural relaxation time of linear polymer melts by adding a small fraction of ring polymers. These results not only provide fundamental insights into the physics of the CR process but also suggest ways to fine-tune the flow properties of linear polymers by means of adding rings.

In this work, we subject elastomers to a fixed pre-stretch in uniaxial extension, e p , upon which a large-amplitude, e 0, oscillatory uniaxial extensional (LAOE) deformation is superposed. We find that if both e p and e 0 are large enough, the stress responds with a rich set of higher harmonics, both even and odd. We further find the Lissajous-Bowditch plots of our measured stress responses versus uniaxial strain to be without twofold symmetry and, specifically, to be shaped like convex bananas. Our new continuum model for this behavior combines a new nonlinear spring, in parallel with a Newtonian dashpot, and we call this the Voigt model with strain-hardening. We consider this three-parameter (Young’s modulus, viscosity, and strain-hardening coefficient) model to be the simplest relevant one for the observed convex bananas. We fit the parameters to both our LAOE measurements and then to our uniaxial elongation measurements at constant extension rate. We develop analytical expressions for the Fourier components of the stress response, parts both in-phase and out-of-phase with the extensional strain, for the zeroth, first, second, and third harmonics. We find that the part of the second harmonic that is out-of-phase with the strain must be negative for proper banana convexity.

We present results from very long (on the order of several microseconds) atomistic molecular dynamics (MD) simulations for the density, microscopic structure, conformation, and local and segmental dynamics of pure, strictly monodisperse ring and linear poly(ethylene oxide) (PEO) melts, ranging in molar mass from ∼5300 to ∼20 000 g/mol. The MD results are compared with recent experimental data for the chain center-of-mass self-diffusion coefficient and the normalized single-chain dynamic structure factor obtained from small-angle neutron scattering, neutron spin echo, and pulse-field gradient NMR, and remarkable qualitative and quantitative agreement is observed, despite certain subtle disagreements in important details regarding mainly internal ring motion (loop dynamics). A detailed normal-mode analysis allowed us to check the degree of consistency of ring PEO melt dynamics with the ring Rouse model and indicated a strong reduction of the normalized mode amplitudes for the smaller mode numbers (compared ...

We present a systematic investigation of static and dynamic properties of block copolymer micelles with crosslinked cores, representing model polymer-grafted nanoparticles, over a wide concentration range from dilute regime to an arrested (crystalline) state, by means of light and neutron scattering, complemented by linear viscoelasticity. We have followed the evolution of their scattering intensity and diffusion dynamics throughout the non-ergodicity transition and the observed results have been contrasted against appropriately coarse-grained Langevin Dynamics simulations. These stable model soft particles of the core-shell type are situated between ultrasoft stars and hard spheres, and the well-known star pair interaction potential is not appropriate to describe them. Instead, we have found that an effective brush interaction potential provides very satisfactory agreement between experiments and simulations, offering insights into the interplay of softness and dynamics in spherical colloidal suspensions., Comment: This version corresponds only to the Supporting Information published in "Static and Dynamic Properties of Block-Copolymer Based Grafted Nanoparticles Across the Non-Ergodicity Transition". This information has been attached to the main manuscript, identified as arXiv:2011.06373

We investigate freely expanding liquid sheets made of either simple Newtonian fluids or solutions of high molecular water-soluble polymer chains. A sheet is produced by the impact of a drop on a quartz plate covered with a thin layer of liquid nitrogen that suppresses shear viscous dissipation thanks to an inverse Leidenfrost effect. The sheet expands radially until reaching a maximum diameter and subsequently recedes. Experiments indicate the presence of two expansion regimes: the capillary regime, where the maximum expansion is controlled by surface tension forces and does not depend on the viscosity, and the viscous regime, where the expansion is reduced with increasing viscosity. In the viscous regime, the sheet expansion for polymeric samples is strongly enhanced as compared to that of Newtonian samples with comparable zero-shear viscosity. We show that data for Newtonian and non-Newtonian fluids collapse on a unique master curve where the maximum expansion factor is plotted against the relevant effective biaxial extensional Ohnesorge number that depends on fluid density, surface tension and the biaxial extensional viscosity. For Newtonian fluids, this biaxial extensional viscosity is six times the shear viscosity. By contrast, for the non- Newtonian fluids, a characteristic Weissenberg number-dependent biaxial extensional viscosity is identified, which is in quantitative agreement with experimental and theoretical results reported in the literature for biaxial extensional flows of polymeric liquids., Comment: 10 pages, 9 figures, accepted for publication in Phys. Rev. Fluids

Anionic polymerization techniques along with functional initiation and/or functional termination reactions were employed for the synthesis of end-functionalized polymers composed from polystyrene (PS), polyisoprene-1,4 (PI), and polybutadiene-1,4 (PBd) chains bearing –OH end groups. Specifically, PS-OH, HO-PS-OH homopolymers, PS-b-PI-OH and PI-b-PS-OH block copolymers, HO-PS-b-PI-b-PS-OH triblock copolymers, and PS(PBd-OH)2 miktoarm star copolymers were prepared. The –OH functions were transformed into 2–ureido–4–pyrimidone, UPy, groups leading to the synthesis of the corresponding functionalized polymers. The UPy groups interact through the formation of strong hydrogen bonds. The aggregation behavior of selected samples was studied by a variety of techniques, such as size exclusion chromatography, dilute solution viscometry, dynamic light scattering, differential scanning calorimetry, thermogravimetric analysis, melt rheology, small angle X-ray scattering, and atomic force microscopy. It was found that in the solid state and in non-polar solvents, the UPy-terminated chains associate leading to the formation of dimers and larger aggregates. This systematic study presents a library of useful materials for potential applications and for fundamental studies linking associations, molecular structure, and macroscopic properties.

Polymer membranes are critical to many sustainability applications that require the size-based separation of gas mixtures. Despite their ubiquity, there is a continuing need to selectively affect the transport of different mixture components while enhancing mechanical strength and hindering aging. Polymer-grafted nanoparticles (GNPs) have recently been explored in the context of gas separations. Membranes made from pure GNPs have higher gas permeability and lower selectivity relative to the neat polymer because they have increased mean free volume. Going beyond this ability to manipulate the mean free volume by grafting chains to a nanoparticle, the conceptual advance of the present work is our finding that GNPs are spatially heterogeneous transport media, with this free volume distribution being easily manipulated by the addition of free polymer. In particular, adding a small amount of appropriately chosen free polymer can increase the membrane gas selectivity by up to two orders of magnitude while only moderately reducing small gas permeability. Added short free chains, which are homogeneously distributed in the polymer layer of the GNP, reduce the permeability of all gases but yield no dramatic increases in selectivity. In contrast, free chains with length comparable to the grafts, which populate the interstitial pockets between GNPs, preferentially hinder the transport of the larger gas and thus result in large selectivity increases. This work thus establishes that we can favorably manipulate the selective gas transport properties of GNP membranes through the entropic effects associated with the addition of free chains.