Project description:The viscous flow of polymer chains in dense melts is dominated by topological constraints whenever the single-chain contour length, N, becomes larger than the characteristic scale Ne, defining comprehensively the macroscopic rheological properties of the highly entangled polymer systems. Even though they are naturally connected to the presence of hard constraints like knots and links within the polymer chains, the difficulty of integrating the rigorous language of mathematical topology with the physics of polymer melts has limited somehow a genuine topological approach to the problem of classifying these constraints and to how they are related to the rheological entanglements. In this work, we tackle this problem by studying the occurrence of knots and links in lattice melts of randomly knotted and randomly concatenated ring polymers with various bending stiffness values. Specifically, by introducing an algorithm that shrinks the chains to their minimal shapes that do not violate topological constraints and by analyzing those in terms of suitable topological invariants, we provide a detailed characterization of the topological properties at the intrachain level (knots) and of links between pairs and triplets of distinct chains. Then, by employing the Z1 algorithm on the minimal conformations to extract the entanglement length Ne, we show that the ratio N/Ne, the number of entanglements per chain, can be remarkably well reconstructed in terms of only two-chain links.
Project description:The reversible and dynamic nature of non-covalent interactions between the constituting building blocks renders many supramolecular polymers stimuli-responsive. This was previously exploited to create thermally and optically healable polymers, but it proved challenging to achieve high stiffness and good healability. Here we present a glass-forming supramolecular material that is based on a trifunctional low-molecular-weight monomer ((UPyU)3TMP). Carrying three ureido-4-pyrimidinone (UPy) groups, (UPyU)3TMP forms a dynamic supramolecular polymer network, whose properties are governed by its cross-linked architecture and the large content of the binding motif. This design promotes the formation of a disordered glass, which, in spite of the low molecular weight of the building block, displays typical polymeric behaviour. The material exhibits a high stiffness and offers excellent coating and adhesive properties. On account of reversible dissociation and the formation of a low-viscosity liquid upon irradiation with ultraviolet light, rapid optical healing as well as (de)bonding on demand is possible.
Project description:We investigate nanoparticle (NP) dispersion, polymer conformations, entanglements and dynamics in ionic nanocomposites. To this end, we study nanocomposite systems with various spherical NP loadings, three different molecular weights, two different Bjerrum lengths, and two types of charge-sequenced polymers by means of molecular dynamics simulations. NP dispersion can be achieved in either oligomeric or entangled polymeric matrices due to the presence of electrostatic interactions. We show that the overall conformations of ionic oligomer chains, as characterized by their radii of gyration, are affected by the presence and the amount of charged NPs, while the dimensions of charged entangled polymers remain unperturbed. Both the dynamical behavior of polymers and NPs, and the lifetime and amount of temporary crosslinks, are found to depend on the ratio between the Bjerrum length and characteristic distance between charged monomers. Polymer-polymer entanglements start to decrease beyond a certain NP loading. The dynamics of ionic NPs and polymers is very different compared with their non-ionic counterparts. Specifically, ionic NP dynamics is getting enhanced in entangled matrices and also accelerates with the increase of NP loading.
Project description:Conformations, entanglements and dynamics in attractive polymer nanocomposites are investigated in this work by means of coarse-grained molecular dynamics simulation, for both weak and strong confinements, in the presence of nanoparticles (NPs) at NP volume fractions φ up to 60%. We show that the behavior of the apparent tube diameter dapp in such nanocomposites can be greatly different from nanocomposites with nonattractive interactions. We find that this effect originates, based on a mean field argument, from the geometric confinement length dgeo at strong confinement (large φ) and not from the bound polymer layer on NPs (interparticle distance ID <2Rg) as proposed recently based on experimental measurements. Close to the NP surface, the entangled polymer mobility is reduced in attractive nanocomposites but still faster than the NP mobility for volume fractions beyond 20%. Furthermore, entangled polymer dynamics is hindered dramatically by the strong confinement created by NPs. For the first time using simulations, we show that the entangled polymer conformation, characterized by the polymer radius of gyration Rg and form factor, remains basically unperturbed by the presence of NPs up to the highest volume fractions studied, in agreement with various experiments on attractive nanocomposites. As a side-result we demonstrate that the loose concept of ID can be made a microscopically well defined quantity using the mean pore size of the NP arrangement.
Project description:We synthesized luminescent coordination polymer glasses composed of d10 metal cyanides and triphenylphosphine through melt-quenching and mechanical milling protocols. Synchrotron X-ray total scattering measurements and solid-state NMR revealed their one-dimensional chain structures and high structural dynamics. Thermodynamic and photoluminescence properties were tunable by the combination of heterometallic ions (Ag+, Au+, and Cu+) in the structures. The glasses are moldable and thermally stable, and over centimeter-sized glass monoliths were fabricated by the hot-press technique. They showed high transparency over 80% from the visible to near-infrared region and strong green emission at room temperature. Furthermore, the glass-to-crystal transformation was demonstrated by laser irradiation through the photothermal effect of the glasses.
Project description:Highly stretchable and self-healing polymer gels formed solely by physical entanglements of ultrahigh-molecular weight (UHMW) polymers were fabricated through a facile one-step process. Radical polymerization of vinyl monomers in ionic liquids under very low initiator concentration conditions produced UHMW polymers of more than 106 g/mol with nearly 100% yield, resulting in the formation of physically entangled transparent polymer gels. The UHMW gels showed excellent properties, such as high stretchability, high ionic conductivity, and recyclability. Furthermore, the UHMW gel exhibited room temperature self-healing ability without any external stimuli. The tensile experiments and molecular dynamics simulations indicate that the nonequilibrium state of the fractured surfaces and microscopic interactions between the polymer chains and solvents play a vital role in the self-healing ability. This study provides a physical approach for fabricating stretchable and self-healing polymer gels based on UHMW polymers.
Project description:Human footprint fossils have provided essential evidence about the evolution of human bipedalism as well as the social dynamics of the footprint makers, including estimates of speed, sex and group composition. Generally such estimates are made by comparing footprint evidence with modern controls; however, previous studies have not accounted for the variation in footprint dimensions coming from load bearing activities. It is likely that a portion of the hominins who created these fossil footprints were carrying a significant load, such as offspring or foraging loads, which caused variation in the footprint which could extend to variation in any estimations concerning the footprint's maker. To identify significant variation in footprints due to load-bearing tasks, we had participants (N = 30, 15 males and 15 females) walk at a series of speeds carrying a 20kg pack on their back, side and front. Paint was applied to the bare feet of each participant to create footprints that were compared in terms of foot length, foot width and foot area. Female foot length and width increased during multiple loaded conditions. An appreciation of footprint variability associated with carrying loads adds an additional layer to our understanding of the behavior and morphology of extinct hominin populations.
Project description:Ceramic prostheses often fail from fracture and wear. We hypothesize that these failures may be substantially mitigated by an appropriate grading of elastic modulus at the ceramic surface. In this study, we elucidate the effect of elastic modulus profile on the flexural damage resistance of functionally graded materials (FGMs), providing theoretical guidelines for designing FGMs with superior load-bearing property. The Young's modulus of the graded structure is assumed to vary in a power-law relation with a scaling exponent n; this is in accordance with experimental observations from our laboratory and elsewhere. Based on the theory for bending of graded beams, we examine the effect of n value and bulk-to-surface modulus ratio (E(b)/E(s)) on stress distribution through the graded layer. Theory predicts that a low exponent (0.15<n<0.5), coupled with a relatively small modulus ratio (3<E(b)/E(s)<6), is most desirable for reducing the maximum stress and transferring it into the interior, while keeping the surface stress low. Experimentally, we demonstrate that elastically graded materials with various n values and E(b)/E(s) ratios can be fabricated by infiltrating alumina and zirconia with a low-modulus glass. Flexural tests show that graded alumina and zirconia with suitable values of these parameters exhibit superior load-bearing capacity, 20-50% higher than their homogeneous counterparts. Improving load-bearing capacity of ceramic materials could have broad impacts on biomedical, civil, structural, and an array of other engineering applications.
Project description:PurposeImmobilization osteopenia is a major healthcare problem in clinical and social medicine. However, the mechanisms underlying this bone pathology caused by immobilization under load-bearing conditions are not yet fully understood. This study aimed to evaluate sequential changes to the three-dimensional microstructure of bone in load-bearing immobilization osteopenia using a fixed-limb rat model.Materials and methodEight-week-old specific-pathogen-free male Wistar rats were divided into an immobilized group and a control group (n = 60 each). Hind limbs in the immobilized group were fixed using orthopedic casts with fixation periods of 1, 2, 4, 8, and 12 weeks. Feeding and weight-bearing were freely permitted. Length of the right femur was measured after each fixation period and bone microstructure was analyzed by micro-computed tomography. The architectural parameters of cortical and cancellous bone were analyzed statistically.ResultsFemoral length was significantly shorter in the immobilized group than in the control group after 2 weeks. Total area and marrow area were significantly lower in the immobilized group than in the control group from 1 to 12 weeks. Cortical bone area, cortical thickness, and polar moment of inertia decreased significantly after 2 weeks. Some cancellous bone parameters showed osteoporotic changes at 2 weeks after immobilization and the gap with the control group widened as the fixation period extended (P < 0.05).ConclusionThe present results indicate that load-bearing immobilization triggers early deterioration of microstructure in both cortical and cancellous bone after 2 weeks.
Project description:Articular cartilage is a load-bearing tissue found in animal and human joints. It is a composite gel-like material in which a fibrous collagen network encapsulates large proteoglycan assemblies that imbibe fluid and "inflate" the network. Here we describe a composite hydrogel consisting of a cross-linked polyvinyl alcohol matrix filled with poly(acrylic acid) microparticles that mimics functional properties and biomechanical behavior of cartilage. The swelling and mechanical behaviors of this biomimetic model system are strikingly similar to that of human cartilage. The development of synthetic composite gel-based articular cartilage analog suggests new avenues to explore material properties, and their change in disease and degeneration, as well as novel strategies for developing composite tissue-engineered cartilage constructs for regenerative medicine applications.