While ∼75% of commercially utilized polymers are semicrystalline, the generally low mechanical modulus these materials, especially for those possessing a glass transition temperature below room temperature, restricts their use structural applications. Our focus in this paper is to address deficiency through controlled, multiscale assembly nanoparticles (NPs), particular by leveraging kinetics polymer crystallization. This process yields NP structure that templated lamellar semicrystalline...

Understanding the structure and dynamics of bound polymer layer (BL) that forms on favorably interacting nanoparticles (NPs) is critical to revealing mechanisms responsible for material property enhancements in nanocomposites (PNCs). Here we use small angle neutron scattering probe temporal persistence this BL canonical case poly(2-vinylpyridine) (P2VP) mixed with silica NPs at two representative temperatures. We have observed almost no long-term reorganization 150 °C (∼Tg,P2VP + 50 °C), but...

Abstract The mass production and disposal of non‐degradable fossil‐based plastics is responsible for alarming environmental social issues when not managed responsibly. Towards manufacturing environmentally‐friendly materials, biopolymers , that is, polymers synthesized by living organisms, emerge as promising sustainable alternatives they combine attractive mechanical properties, compostability, renewable sourcing. In this review, we analyze the structural properties three most studied...

The increasing consumption of nonrenewable materials urgently calls for the design and fabrication sustainable alternatives. New generations should be derived from renewable sources, processed using environmentally friendly methods, designed considering their full life cycle, especially end-of-life fate. Here, we review recent advances in developing polymers biological matter (biomatter), including progress extraction utilization bioderived monomers polymers, as well emergence produced...

Abstract Since the 1950s, 8.3 billion tonnes (Bt) of virgin plastics have been produced, which around 5 Bt accumulated as waste in oceans and other natural environments, posing severe threats to entire ecosystems. The need for sustainable bio‐based alternatives traditional petroleum‐derived is evident. Bioplastics produced from unprocessed biological materials thus far suffered heterogeneous non‐cohesive morphologies, lead weak mechanical properties lack processability, hindering their...

Polyethylene and nanosilica represent the most ubiquitous commodity plastic nanocomposite filler, respectively. Despite their potential utility, few examples exist in literature of successfully combining these two materials to form polyethylene nanocomposites. Synthesizing well-defined grafted a surface is significant challenge nanocomposites community. Presented here synthetic approach toward nanoparticles with controllable graft density molecular weight polymer. The variably were then...

We study the slowing down of polymer dynamics in canonical nanocomposites made strongly interacting mixtures poly-2-vinyl pyridine and silica nanoparticles (radius R = 7 ± 2 nm) by means low-field NMR relaxometry. demonstrate that this technique enables accurate quantification fraction immobilized (irreversibly adsorbed) on to filler surface, a manner complements data from broadband dielectric spectroscopy (BDS) differential scanning calorimetry (DSC). rationalize using two previously...

We previously showed that nanoparticles (NPs) could be ordered into structures by using the growth rate of polymer crystals as control variable. In particular, for slow enough spherulitic fronts, NPs grafted with amorphous chains are selectively moved interlamellar, interfibrillar, and interspherulitic zones a lamellar morphology, specifically going from interlamellar to progressively decreasing crystal rates. Here, we examine effect NP grafting density on crystallization kinetics. find...

We investigate the crystallization-induced ordering of C18 grafted 14 nm diameter spherical silica nanoparticles (NPs) in a short chain (Mw = 4 kDa, ĐM ≈ 2.3) polyethylene and commercial high-density 152 3.2) matrix. For slow isothermal crystallization low molecular weight matrix, NPs segregate into interlamellar regions. This result establishes generality our earlier work on poly(ethylene oxide) based materials suggests that can be used to control NP dispersion across different polymer...

We explore the role of nanoparticle (NP) size and loading on kinetics polymer crystallization, in particular, crystal growth rate (G), under conditions where NPs polymers are uniformly mixed. While there significant differences with variations NP loading, measured G data fall into an apparently universal curve when we consider them basis confinement. In find that ratio volume, VPEO, to surface area, SANP, is most appropriate confinement metric 10–100 nm range, which includes typical lamellar...

We control nanoparticle (NP) dispersion by leveraging the entropic and enthalpic effects associated with mixing silica NPs grafted polyisoprene (PI) chains into matrices of varying degrees chemical dissimilarity. Previous work in this area has primarily focused on factors alone, hence, represents a significant advance over current state-of-the-art. show using combination transmission electron microscopy/small-angle X-ray scattering that particles PI identical microstructure yields states as...

We systematically examine the role of self-assembly state polymer-grafted silica nanoparticles (GNPs) on spherulitic growth kinetics a poly(ethylene oxide) (PEO) matrix. The (NPs) are functionalized with either unimodal or bimodal polymer brushes to control their within semicrystalline In former case, we employ poly(methyl methacrylate) (PMMA) brush (miscible PEO), while latter has short dense polystyrene (PS carpet) brush, which is immiscible PEO matrix, and long, sparse PMMA brush. GNPs...

There is great interest in controlling the spatial dispersion of inorganic nanoparticles (NPs) an organic polymer matrix because this centrally underpins property enhancements obtained from these hybrid materials. Currently, qualitative information on NP distribution by visual inspection transmission electron microscopy (TEM) images. Quantitative only indirectly through use scattering probes such as small-angle X-ray/neutron (SAXS/SANS). While main challenge, that operate reciprocal space,...

Abstract With material consumption increasing, the need for biodegradable materials derived from renewable resources becomes urgent, particularly in popular field of 3D‐printing. Processed natural fibers have been used as fillers 3D‐printing filaments and slurries, yet reports utilizing pure biomass to 3D‐print structures that reach mechanical properties comparable synthetic plastics are scarce. Here, we develop characterize slurries extrusion‐based comprised unprocessed spirulina varying...

We find that the initial, solvent-cast state of nanoparticles (NPs) in a polymer matrix temporally evolves during thermal annealing such that, at steady state, NPs maximize their distance from each other subject to mass balance constraints. The observed timescales for this unexpected structural reorganization, as probed by small-angle X-ray scattering, are temperature-dependent and can be prohibitively large, especially temperatures around below 1.2Tg. photon correlation spectroscopy...

The incorporation of carbon-fixing materials such as photosynthetic algae in concrete formulations offers a promising strategy toward mitigating the concerningly high carbon footprint cement. Prior literature suggests that introduction up to 0.5 wt % chlorella biological matter (biomatter) ordinary Portland cement induces retardation composite cement's strength evolution while enabling long-term compressive comparable pure at lower footprint. In this work, we provide insights into...

Abstract It is demonstrated that the addition of nanoparticles can decrease viscosity an entangled polymer matrix (plasticization). While there has been considerable effort in understanding role bare on viscosity, corresponding study grafted particles nascent. Two nanometer radius zirconia fillers with a bimodal population PDMS used. are considered: one chains molecular weight, M g , less than entanglement M, < e (ZrO 2 1k 10k), and other filler > c (the critical ) 36k). The ZrO 10k...

The self-assembly of diblock copolymers (BCPs) comprising flexible polymer chains, driven by a balance enthalpic and entropic forces, is well understood. If one the blocks polyelectrolyte, forming charge-neutral BCP (CN-BCP), Coulombic interactions can play significant role in self-assembly. Here, electron microscopy small-angle X-ray scattering, combination with free-energy arguments scaling model inspired surfactant self-assembly, are used to investigate microphase segregation CN-BCPs...

Zone annealing, a directional crystallization technique originally used for the purification of semiconductors, is applied here to crystalline polymers. Tight control over final lamellar orientation and thickness semicrystalline polymers can be obtained by directionally solidifying material under optimal conditions. It has previously been postulated Lovinger Gryte that, at steady state, crystal growth rate polymer undergoing zone annealing equal velocity which sample drawn through...

It has recently been established that polymer crystallization can preferentially place nanoparticles (NPs) into the amorphous domains of a lamellar semicrystalline morphology. The phenomenology this process is clear: when time for NP diffusion shorter than crystal growth time, then NPs are rejected by growing crystals and placed in domains. However, since there no quantitative characterization ordered state, we develop correlation function analysis small-angle X-ray scattering data, inspired...

Unaltered biological matter (biomatter) can be harnessed to fabricate cohesive, sustainable bioplastics. However, controlling the material properties of these bioplastics is challenging as contributions different macromolecular building blocks processability and performance are unknown. To deconvolute roles classes biomolecules, we developed experimental computational methods construct analyze biomatter analogues comprised carbohydrates, proteins, lipids. Spectroscopic analyses suggest that...

This study aims to describe and evaluate the mechanism for increased strain-at-break of composites made cellulose nanofibrils (CNFs) reinforced with nanoscopic latex particles (<200 nm) stabilized by a cationic polyelectrolyte as corona.