Search Results (18)

Hydrogels are widely used in the field of adhesive materials. However, hydrogel adhesion has previously required the covalent graft of supramolecular groups on polymeric chains. In contrast to that, here, a hydrogel adhesion induced by covalent polymer entanglement between two hydrogel networks was reported. Hydrogels G1 and G2 contain the monomers M1, with diazonium groups, and M2, with sulfonate groups, respectively. When the two hydrogels come into contact, the monomers diffuse into each other’s networks and assemble into supramolecular polymers (SPs) based on electrostatic interactions, threading the two hydrogel networks. Subsequently, SPs convert into covalent polymers (CPs) under UV light stimulation due to the reaction between the diazonium groups and sulfonate groups, leading to the entanglement of the two hydrogel networks and the production of an adhesive effect. This finding provides a novel strategy for hydrogel adhesion. Full article

The viscosity and viscoelasticity of polyelectrolyte solutions with a single electrostatic interaction have been carefully studied experimentally and theoretically. Despite some theoretical models describe experimental results well, the influence of multiple interactions (electrostatic and hydrophobic) on rheological scaling is not yet fully resolved. Herein, we systematically study the microstructures and rheological properties of short-side-chain perfluorosulfonic acid (S-PFSA), the most promising candidate of a proton exchange membrane composed of a hydrophobic backbone with hydrophilic side-chains, in water/2-propanol. Small-angle X-ray scattering confirms that semiflexible S-PFSA colloidal particles with a length of ~38 nm and a diameter of 1–1.3 nm are formed, and the concentration dependence of the correlation length (ξ) obeys the power law ξ~c^−0.5 consistent with the prediction of Dobrynin et al. By combining macrorheology with diffusing wave spectroscopy microrheology, the semidilute unentangled, semidilute entangled, and concentrated regimes corresponding to the scaling relationships η_sp~c^0.5, η_sp~c^1.5, and η_sp~c^4.1 are determined. The linear viscoelasticity indicates that the entanglement concentration (c_e) obtained from the dependence of η_sp on the polymer concentration is underestimated owing to hydrophobic interaction. The true entanglement concentration (c_te) is obtained by extrapolating the plateau modulus (G_e) to the terminal modulus (G_t). Furthermore, G_e and the plateau width, τ_r/τ_e (τ_r and τ_e denote reptation time and Rouse time), scale as G_e~c^2.4 and τ_r/τ_e~c^4.2, suggesting that S-PFSA dispersions behave like neutral polymer solutions in the concentrated regime. This work provides mechanistic insight into the rheological behavior of an S-PFSA dispersion, enabling quantitative control over the flow properties in the process of solution coating. Full article

The rheological properties of macromolecules represent one of the fundamental features of polymer systems which expand the possibilities of using and developing new materials based on them. In this work, we studied the shear-stress relaxation of the second generation PAMAM and PPI dendrimer melts by atomistic molecular dynamics simulation. The time dependences of relaxation modulus G(t) and the frequency dependences of the storage G′(ω) and loss G″(ω) moduli were obtained. The results were compared with the similar dependences for the polycarbosilane (PCS) dendrimer of the same generation. The chemical structure of the dendrimer segments has been found to strongly influence their mechanical relaxation. In particular, it has been shown that hydrogen bonding in PAMAM dendrimers leads to an entanglement of macromolecules and the region is observed where G′(ω) > G″(ω). This slows down the mechanical relaxation and rotational diffusion of macromolecules. We believe that our comprehensive research contributes to the systematization of knowledge about the rheological properties of dendrimers. Full article

The way to theoretically approach dynamic and static topological constraints of polymer entanglements still presents a great challenge in polymer physics. So far, only the problem of static entanglement with multiple simple objects has been solved in theory by a superspace approach in our previous work. This work is devoted to extending the superspace approach to study a polymer chain entangled with a relatively complicated object—a ring-shaped object with genus one. Taking advantage of the axial symmetry of the model setup, the 3D diffusion equations in the superspace can be numerically solved within the 2D coordinates using a specially designed alternating-direction implicit (ADI) scheme. A series of numerical calculations reveal that the topological entanglement effect of the ring will exert a topological entropy attractive force on the linear chain, which can be used to explain the viscosity-increase phenomenon observed in recent simulations and experiments. Furthermore, the influences of the ring size and the entangling modes on the topological entropy force are also investigated by examining the corresponding force-extension curves. This work, together with our previous work, might pave the path toward the complete formulation of static topological constraints. Full article

Owing to the fact that heat transfer during the thermally induced phase separation process is limited, a quench rate is inevitably entailed, which leads to the existence of temporal and spatial variations in temperature. Hence, it is of great importance to take into account the nonisothermality during the phase separation process, especially in high viscosity polymer solutions. In this study, the influence of conductive heat transfer on the morphology formation during the thermally induced phase separation process was investigated theoretically in terms of quench depth, boundary conditions, and enthalpy of demixing to elucidate the interaction between temperature and concentration through incorporating the nonlinear Cahn-Hilliard equation and the Fourier heat transfer equation in two dimensions. The Flory-Huggins free energy theory for the thermodynamics of phase separation, slow mode theory, and Rouse law for polymer diffusion without entanglements were taken into account in the model development. The simulation results indicated a strong interaction between heat transfer and phase separation, which impacted the morphology formation significantly. Results confirmed that quench depth had an indispensable impact on phase separation in terms of higher characteristic frequency by increasing the driving force for heat transfer. Applying quench from various boundaries led to a difference in the quench rate due to the high viscosity of the polymer solution. This led to a gradation in pore size and anisotropic morphology formation. The degree and direction of anisotropy depended on quench depth and rate, quench time, heat conduction rate inside the solution, solution viscosity, temperature evolution, and the enthalpy of demixing. It was also verified that the influence of enthalpy of demixing on phase separation could not be neglected as it increased the solution temperature and led to phase separation being accomplished at a higher temperature than the initial quench temperature. Full article

Retrogradation of cooked rice happens in two ways: one is by the formation of ordered structures, and the other is through intra- and inter-chain entanglement and inter-chain overlap, which in turn are affected by the amylose chain-length distribution. Both entanglement and overlap could affect rice texture. Here, four amylose samples were isolated from starch by precipitation from a dimethyl sulfoxide solution with butan-1-ol and isoamyl alcohol. Following enzymatic debranching, they were then characterized using size-exclusion chromatography. Amylose solutions (10%, m/v) were made by dissolving amylose in 90% (v/v) DMSO. Amylose gels (10%, w/v) were made by dissolving amylose powders into hot water, followed by cooling. The rigidity of the amylose gels and the structural order were measured using a texture analyzer and X-ray diffractometer, respectively. In the amylose solution, for a given mass of polymer in a fixed amount of solvent, the total occupied volume was reduced when the polymer molecular weight was smaller, resulting in less inter-chain overlap and a lower viscosity of the amylose solution. The overall mobility and diffusion of the molecules were inversely related to the square of the molecular weight until the gelation concentration. Thus, amylose gels in which amylose had a lower molecular weight had a greater chance to permeate into other molecules, which counterintuitively led to more inter-chain entanglement and more rigid amylose gels during retrogradation. This information could help rice breeders improve rice quality by using the molecular structure of starch as a guide. Full article

Reactive compounding of terminally phenolic OH-functionalized polycarbonate (PC) with epoxy-functionalized polymethylmethacrylate (PMMA) prepared by copolymerization with glycidyl methacrylate was investigated. It was spectroscopically demonstrated that a PC/PMMA copolymer was formed during the melt reaction of the functional groups. Zirconium acetylacetonate could catalytically accelerate this reaction. Correlations of the phenomenological (optical and mechanical) properties with the molecular level and mesoscopic (morphological) structure were discussed. By the investigated reactive compounding process, transparent PC/PMMA blends with two-phase morphologies were obtained in a continuous twin-screw extruder, which, for the first time, combined the high transmission of visible light with excellent mechanical performance (e.g., synergistically improved tensile and flexural strength and high scratch resistance). The transparency strongly depended on (a) the degree of functionalization in both PC and PMMA, (b) the presence of the catalyst, and (c) the residence time of the compounding process. The in-situ-formed PC/PMMA copolymer influenced the observed macroscopic properties by (a) a decrease in the interphase tension, leading to improved and stabilized phase dispersion, (b) the formation of a continuous gradient of the polymer composition and thus of the optical refractive indices in a diffuse mesoscopic interphase layer separating the PC and PMMA phases, and (c) an increase in the phase adhesion between PC and PMMA due to mechanical polymer chain entanglement in this interphase. Full article

Renewable polymers with self-healing ability, excellent elongation, hydrophobicity, and selective oil absorption attributes are of interest for an extensive range of applications, such as e-skin, soft robots, wearable devices, and cleaning up oil spills. Herein, two fully renewable eco-friendly polyamide (PA)-based self-healing elastomers (namely, PA36,IA, and PA36,36) were prepared by a facile and green one-pot melt polycondensation of itaconic acid (IA), Pripol^TM 1009, and Priamine^TM 1075 monomers. The molecular structures of these PAs were analyzed by FITR, ¹H NMR, and ¹³C NMR. The distinct structure of these PAs shows superior strain values (above 2300%) and high ambient temperature autonomous self-healing ability. Interestingly, the synthesized renewable PA36,36 showed zero water absorption values and hydrophobic properties with a contact angle of θ = 91° compared to the synthesized PA36,IA and other previously reported PAs. These excellent attributes are due to the low concentration of amide groups, the highly entangled main chains, the intermolecular diffusion, the manifold dangling chains, and the numerous reversible physical bonds within the renewable PAs. Furthermore, the hydrophobic properties may aid in the selective oil absorption of the PA36,36-based foam, for which PA36,36 foam is produced by the green supercritical carbon dioxide (scCO₂) batch foaming process. The PA36,36 foam with a microporous cellular structure showed better absorption capacity and high stability in repeated use. Due to these advantages, these bio-based PAs have potential for the production of eco-friendly self-healing materials, superabsorbent foams, and other polymeric materials. Full article

Improving the processability of ultrahigh molecular weight polyethylene (UHMWPE) and understanding the effect of the polymeric chain mobility has long been a challenging task. Herein, we show that UHMWPE without any processing aids can be processed at a lower temperature of 180 °C compared to conventional processing temperatures (~250 °C) under a continuous elongational flow (CEF) by using an eccentric rotor extruder (ERE). By probing the effect of the residence time of UHMWPE samples under a CEF on the morphology, rheological behavior and molecular orientation, we find that the long polymer chains of UHMWPE are apt to orientate under a consecutive volume elongational deformation, thereby leading to a higher residual stress for the extruded sample. Meanwhile, the residence time of samples can regulate the polymeric chain mobility, giving rise to the simultaneous decrease of the melting defects and residual stress as well as Hermans orientation function with increasing residence time from 0 to 60 s. This also engenders the enhanced diffusion of UHMWPE segments, resulting in a defect-free morphology and higher entanglement with lower crystallinity but without causing obvious thermal oxidative degradation of UHMWPE. This interesting result could originate from the fast chain entanglement and particle welding enabled by a desirably short residence time, which could be explained by the empirical, entropy-driven melting explosion mechanism. Full article

Organogels have recently been considered as materials for transdermal drug delivery media, wherein their transport and mechanical properties are among the most important considerations. Transport through organogels has only recently been investigated and findings highlight an inextricable link between gels’ transport and mechanical properties based upon the formulated polymer concentration. Here, organogels composed of styrenic triblock copolymer and different aliphatic mineral oils, each with a unique dynamic viscosity, are characterized in terms of their quasi-static uniaxial mechanical behavior and the internal diffusion of two unique solute penetrants. Mechanical testing results indicate that variation of mineral oil viscosity does not affect gel mechanical behavior. This likely stems from negligible changes in the interactions between mineral oils and the block copolymer, which leads to consistent crosslinked network structure and chain entanglement (at a fixed polymer concentration). Conversely, results from diffusion experiments highlight that two penetrants—oleic acid (OA) and aggregated aerosol-OT (AOT)—diffuse through gels at a rate inversely proportional to mineral oil viscosity. The inverse dependence is theoretically supported by the hydrodynamic model of solute diffusion through gels. Collectively, our results show that organogel solvent variation can be used as a design parameter to tailor solute transport through gels while maintaining fixed mechanical properties. Full article

A set of criteria to enhance mechanical performances of standard specimens (Type V, ANSI D368) made of polylactic acid (PLA) were proposed. Fused PLA deposition was conducted with nozzle temperature ranging from 180 to 230 °C and deposition plate temperature ranging from 70 to 110 °C. Optical microscopy, elastic modulus analysis and density measurement allowed emphasizing the effect of temperature field, also measured during the process, on the morphology and the mechanical characteristics of the specimen. Atomic force microscopy revealed a morphology typical of amorphous samples with globular structures. Poor interlayer adhesion was detected in the part of the specimen located at larger distance from the deposition plate, showing an elastic modulus lower than those measured in the central part (220 MPa vs. 500 MPa). The specimen crystallinity degree was below 3%. The molecular weight between entanglements was adopted as a measure of the interlayer molecular diffusion. A successful diffusion and re-entanglement of the polymer melt at the interface was the key to improving mechanical performance. A mathematical model describing the transient heat transfer during the fused PLA deposition and accounting for solidification and the nonisothermal crystallization kinetics was introduced. Simulated temperature evolutions were consistent with the experimental ones. They were related to the mechanical performances, the morphology, and the molecular weight between entanglements of the parts. Full article

In this work, biodegradable films based on poly (lactic acid) (PLA) and corn thermoplastic starch (TPS), additivated with epoxidized cardoon oil plasticizer (ECO) at 3% by weight with respect to PLA mass fraction, were prepared by melt extrusion process and compression molding. The effect of ECO on structural, thermal, mechanical, barrier, and spectral optical properties of the films was investigated. Spectroscopic analysis evidenced the development of physical interaction between oil and polymers, mainly PLA. In addition, no oil migration occurrence was detected after six months of film preparation, as evidenced by oil mass evaluation by precipitation as well as by ¹H-NMR methods, thus highlighting the good inclusion of oil inside the polymeric network. The plasticizing action of the oil induced a lean improvement of the interfacial adhesion between hydrophobic PLA and hydrophilic TPS, particularly accentuated in PLA80_ECO composition, as evidenced by morphological analysis of blend fracture surfaces. TGA data underlined that, differently from TPS-based films, PLA-based systems followed one degradative thermal profile suggesting a slight compatibilization effect of epoxidized oil in these films. The shifting of Tg values, by differential scanning calorimetry (DSC) analysis, indicated a weak miscibility at molecular level. Generally, in the investigated blends, the phase separation between PLA and TPS polymers was responsible for the mechanical properties failing; in particular, the tensile strength evidenced a negative deviation from the rule of mixtures, particularly marked in TPS-based blends, where no physical entanglements occurred between the polymers since their immiscibility even in presence of ECO. The epoxidized oil strongly improved the barrier properties (water vapor permeability (WVP) and oxygen permeability (O₂P)) of all the films, likely developing a physical barrier to water and oxygen diffusion and solubilization. With respect to neat PLA, PL80 and PL80_ECO films evidenced the improvement of surface wettability, due to the presence of polar groups both in TPS (hydroxyl residues) and in epoxidized oil (oxirane rings). Finally, following to the conditioning in climatic chamber at T = 25 °C and RH = 50%, PLA80 film became opaque due to TPS water absorption, causing a light transmittance decreasing, as evidenced by spectral optical analysis. Full article

We probe the influence of branching on the configurational, packing, and density correlation function properties of polymer melts of linear and star polymers, with emphasis on molecular masses larger than the entanglement molecular mass of linear chains. In particular, we calculate the conformational properties of these polymers, such as the hydrodynamic radius $R_{\mathrm{h}}$ , packing length p, pair correlation function $g\left(r\right)$ , and polymer center of mass self-diffusion coefficient, D, with the use of coarse-grained molecular dynamics simulations. Our simulation results reproduce the phenomenology of simulated linear and branched polymers, and we attempt to understand our observations based on a combination of hydrodynamic and thermodynamic modeling. We introduce a model of “entanglement” phenomenon in high molecular mass polymers that assumes polymers can viewed in a coarse-grained sense as “soft” particles and, correspondingly, we model the emergence of heterogeneous dynamics in polymeric glass-forming liquids to occur in a fashion similar to glass-forming liquids in which the molecules have soft repulsive interactions. Based on this novel perspective of polymer melt dynamics, we propose a functional form for D that can describe our simulation results for both star and linear polymers, covering both the unentangled to entangled polymer melt regimes. Full article

This review concerns modeling studies of the fundamental problem of entangled (reptational) homopolymer diffusion in melts and nanocomposite materials in comparison to experiments. In polymer melts, the developed united atom and multibead spring models predict an exponent of the molecular weight dependence to the polymer diffusion very similar to experiments and the tube reptation model. There are rather unexplored parameters that can influence polymer diffusion such as polymer semiflexibility or polydispersity, leading to a different exponent. Models with soft potentials or slip-springs can estimate accurately the tube model predictions in polymer melts enabling us to reach larger length scales and simulate well entangled polymers. However, in polymer nanocomposites, reptational polymer diffusion is more complicated due to nanoparticle fillers size, loading, geometry and polymer-nanoparticle interactions. Full article

Aimed at the molding of polymer nanostructure parts, the interface model between long- and short-chain polycarbonates (PC) and nickel mold inserts was established by the molecular dynamics method. The molecular mechanism of the replication capability of polymer nanostructure part molding was discussed by analyzing the migration and diffusion of the molecular chain, concentration profile, filling morphology evolution, interface binding energy, and filling rate of conventional injection molding (CIM) and rapid heat cycle molding (RHCM). The results show that nanostructures are filled mainly during the packing stage. A short-chain PC system has a low glass transition temperature (T_g) and viscosity, good fluidity, and a high filling rate, so the replication capability of its nanostructures is good. A long-chain PC system has a fast cooling rate in CIM, its molecular chain motion is blocked, the filling rate is low, and the interface binding energy is small, and so its nanostructures have poor replication capability. However, the high temperature at the nanostructures can be maintained for a long time in RHCM, which promotes Brownian motion in the molecular chains. Under the action of packing pressure, molecular chains can overcome entanglement barriers and viscous resistance. Thus, the polymer concentration profile and filling rate increase with increasing packing pressure, which can produce more van der Waals energy. Furthermore, the evolution process of polymer filling morphology is realized by the Brownian motion of chain segments under packing pressure; that is, the diffusion motion of the molecular chain along the direction of a tube composed of other chains around it. With the increase of temperature or pressure, the migration and diffusion of the molecular chain can be promoted; thus, the replication capability of nanostructure parts for mold cavities can be enhanced. Full article