Although advances have been reported to mimic the mechanically excellent structure of natural nacre, larger-scale applications are still limited due to time and energy-intensive preparation pathways. Herein, we demonstrate that simple high-shear homogenization of dispersions containing biobased high molecular weight sodium carboxymethyl cellulose (700 kg/mol, CMC) and natural sodium montmorillonite (MTM), serving as the soft energy-dissipating phase and reinforcing platelets, respectively, can be used to prepare large-area and thick films with well-aligned hard/soft nacre-mimetic mesostructure. During this process, core-shell nanoplatelets with intrinsic hard/soft structure form, which then self-assemble into a layered nanocomposite during water removal. The nanoscale periodicities of the alternating hard/soft layers can be precisely tuned by changing the ratio of CMC to MTM, which allows studying the evolution of mechanical properties as a function of the lamellar nanoscale periodicity and fractions of hard to soft material. Remarkable mechanical stiffness (25 GPa) and strength (320 MPa) can be obtained placing these materials among the top end of nacre-inspired materials reported so far. Mechanical homogenization also allows direct preparation of concentrated, yet homogeneous, gel-like dispersions of high nanoclay content, suited to doctor-blade large-area and thick films with essentially the same properties as films cast from dilute dispersions. In terms of functional properties, we report high-transparency, shape-persistent fire-blocking and the ability to surface-pattern via inkjet printing. Considering the simple, fully scalable, waterborne preparation pathway, and the use of nature-based components, we foresee applications as ecofriendly, bioinspired materials to promote sustainable engineering materials and novel types of functional barrier coatings and substrates.
Nature regulates complex structures in space and time via feedback loops, kinetically controlled transformations, and under energy dissipation to allow non-equilibrium processes. Although man-made static self-assemblies realize excellent control over hierarchical structures via molecular programming, managing their temporal destiny by self-regulation is a largely unsolved challenge. Herein, we introduce a generic concept to control the time domain by programming the lifetimes of switchable self-assemblies in closed systems. We conceive dormant deactivators that, in combination with fast promoters, enable a unique kinetic balance to establish an autonomously self-regulating, transient pH-state, whose duration can be programmed over orders of magnitude-from minutes to days. Coupling this non-equilibrium state to pH-switchable self-assemblies allows predicting their assembly/disassembly fate in time, similar to a precise self-destruction mechanism. We demonstrate a platform approach by programming self-assembly lifetimes of block copolymers, nanoparticles, and peptides, enabling dynamic materials with a self-regulation functionality.
Designing the reversible interactions of biopolymers remains a grand challenge for an integral mimicry of mechanically superior biological composites. Yet, they are the key to synergistic combinations of stiffness and toughness by providing sacrificial bonds with hidden length scales. To address this challenge, dynamic polymers were designed with low glass-transition temperature T(g) and bonded by quadruple hydrogen-bonding motifs, and subsequently assembled with high-aspect-ratio synthetic nanoclays to generate nacre-mimetic films. The high dynamics and self-healing of the polymers render transparent films with a near-perfectly aligned structure. Varying the polymer composition allows molecular control over the mechanical properties up to very stiff and very strong films (E≈45 GPa, σ(UTS)≈270 MPa). Stable crack propagation and multiple toughening mechanisms occur in situations of balanced dynamics, enabling synergistic combinations of stiffness and toughness. Excellent gas barrier properties complement the multifunctional property profile.
Cellulose nanofibrils (CNFs) are considered next generation, renewable reinforcements for sustainable, high-performance bioinspired nanocomposites uniting high stiffness, strength and toughness. However, the challenges associated with making well-defined CNF/polymer nanopaper hybrid structures with well-controlled polymer properties have so far hampered to deduce a quantitative picture of the mechanical properties space and deformation mechanisms, and limits the ability to tune and control the mechanical properties by rational design criteria. Here, we discuss detailed insights on how the thermo-mechanical properties of tailor-made copolymers govern the tensile properties in bioinspired CNF/polymer settings, hence at high fractions of reinforcements and under nanoconfinement conditions for the polymers. To this end, we synthesize a series of fully water-soluble and nonionic copolymers, whose glass transition temperatures (Tg) are varied from -60 to 130 °C. We demonstrate that well-defined polymer-coated core/shell nanofibrils form at intermediate stages and that well-defined nanopaper structures with tunable nanostructure arise. The systematic correlation between the thermal transitions in the (co)polymers, as well as its fraction, on the mechanical properties and deformation mechanisms of the nanocomposites is underscored by tensile tests, SEM imaging of fracture surfaces and dynamic mechanical analysis. An optimum toughness is obtained for copolymers with a Tg close to the testing temperature, where the soft phase possesses the best combination of high molecular mobility and cohesive strength. New deformation modes are activated for the toughest compositions. Our study establishes quantitative structure/property relationships in CNF/(co)polymer nanopapers and opens the design space for future, rational molecular engineering using reversible supramolecular bonds or covalent cross-linking.
Natural composites are hierarchically structured by combination of ordered colloidal and molecular length scales. They inspire future, biomimetic, and lightweight nanocomposites, in which extraordinary mechanical properties are in reach by understanding and mastering hierarchical structure formation as tools to engineer multiscale deformation mechanisms. Here we describe a hierarchically self-assembled, cholesteric nanocomposite with well-defined colloid-based helical structure and supramolecular hydrogen bonds engineered on the molecular level in the polymer matrix. We use reversible addition-fragmentation transfer polymerization to synthesize well-defined hydrophilic, nonionic polymers with a varying functionalization density of 4-fold hydrogen-bonding ureidopyrimidinone (UPy) motifs. We show that these copolymers can be coassembled with cellulose nanocrystals (CNC), a sustainable, stiff, rod-like reinforcement, to give ordered cholesteric phases with characteristic photonic stop bands. The dimensions of the helical pitch are controlled by the ratio of polymer/CNC, confirming a smooth integration into the colloidal structure. With respect to the effect of the supramolecular motifs, we demonstrate that those regulate the swelling when exposing the biomimetic hybrids to water, and they allow engineering the photonic response. Moreover, the amount of hydrogen bonds and the polymer fraction are decisive in defining the mechanical properties. An Ashby plot comparing previous ordered CNC-based nanocomposites with our new hierarchical ones reveals that molecular engineering allows us to span an unprecedented mechanical property range from highest inelastic deformation (strain up to ∼13%) to highest stiffness (E ∼ 15 GPa) and combinations of both. We envisage that further rational design of the molecular interactions will provide efficient tools for enhancing the multifunctional property profiles of such bioinspired nanocomposites.
Atomic-layer-deposition (ALD) of In2O3 nano-films has been investigated using cyclopentadienyl indium (InCp) and hydrogen peroxide (H2O2) as precursors. The In2O3 films can be deposited preferentially at relatively low temperatures of 160–200 °C, exhibiting a stable growth rate of 1.4–1.5 Å/cycle. The surface roughness of the deposited film increases gradually with deposition temperature, which is attributed to the enhanced crystallization of the film at a higher deposition temperature. As the deposition temperature increases from 150 to 200 °C, the optical band gap (Eg) of the deposited film rises from 3.42 to 3.75 eV. In addition, with the increase of deposition temperature, the atomic ratio of In to O in the as-deposited film gradually shifts towards that in the stoichiometric In2O3, and the carbon content also reduces by degrees. For 200 °C deposition temperature, the deposited film exhibits an In:O ratio of 1:1.36 and no carbon incorporation. Further, high-performance In2O3 thin-film transistors with an Al2O3 gate dielectric were achieved by post-annealing in air at 300 °C for appropriate time, demonstrating a field-effect mobility of 7.8 cm2/V⋅s, a subthreshold swing of 0.32 V/dec, and an on/off current ratio of 107. This was ascribed to passivation of oxygen vacancies in the device channel.
Sustainable alternatives for high-performance and functional materials based on renewable resources are intensely needed as future alternatives for present-day, fossil-based materials. Nanochitin represents an emerging class of highly crystalline bionanoparticles with high intrinsic mechanical properties and the ability for conjugation into functional materials owing to reactive amine and hydroxyl groups. Herein we demonstrate that hydrogels containing surface-deacetylated chitin nanofibrils of micrometer length and average diameters of 9 nm, as imaged by cryogenic transmission electron microscopy, can be wet-spun into macrofibers via extrusion in a coagulation bath, a simple low energy and large-scale processing route. The resulting biofibers display attractive mechanical properties with a large plastic region of about 12% in strain, in which frictional sliding of nanofibrils allows dissipation of fracture energy and enables a high work-of-fracture of near 10 MJ/m3. We further show how to add functionality to these macrofibers by exploiting the amine functions of the surface chitosan groups to host catalytically active noble metal nanoparticles, furnishing biobased, renewable catalytic hybrids. These inorganic/organic macrofibers can be used repeatedly for fast catalytic reductions of model compounds without loss of activity, rendering the concept of hybridized chitin materials interesting as novel bioderived supports for nanoparticle catalysts.
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