Organic nanoparticles with tunable size and rigidity by hyperbranching and cross-linking using microemulsion ATRP.

Unlike inorganic nanoparticles, organic nanoparticles (oNPs) offer the advantage of "interior tailorability," thereby enabling the controlled variation of physicochemical characteristics and functionalities, for example, by incorporation of diverse functional small molecules. In this study, a unique inimer-based microemulsion approach is presented to realize oNPs with enhanced control of chemical and mechanical properties by deliberate variation of the degree of hyperbranching or cross-linking. The use of anionic cosurfactants led to oNPs with superior uniformity. Benefitting from the high initiator concentration from inimer and preserved chain-end functionality during atom transfer radical polymerization (ATRP), the capability of oNPs as a multifunctional macroinitiator for the subsequent surface-initiated ATRP was demonstrated. This facilitated the synthesis of densely tethered poly(methyl methacrylate) brush oNPs. Detailed analysis revealed that exceptionally high grafting densities (~1 nm-2) were attributable to multilayer surface grafting from oNPs due to the hyperbranched macromolecular architecture. The ability to control functional attributes along with elastic properties renders this "bottom-up" synthetic strategy of macroinitiator-type oNPs a unique platform for realizing functional materials with a broad spectrum of applications.

Synthesis of Mechanically Robust Very High Molecular Weight Polyisoprene Particle Brushes by Atom Transfer Radical Polymerization.

Linear polyisoprene (PI) and SiO2-g-PI particle brushes were synthesized by both conventional and activators regenerated by electron transfer (ARGET) atom transfer radical polymerization (ATRP). The morphology and solution state study on the particle brushes by transmission electron microscopy (TEM) and dynamic light scattering (DLS) confirmed the successful grafting of PI ligands on the silica surface. The presence of nanoparticle clusters suggests low grafting density (associated with the limited initiation efficiency of ARGET for PI). Nevertheless, particle brushes with very high molecular weights, Mn > 300,000, were prepared, which significantly improved the dispersion of silica nanoparticles and also contributed to excellent mechanical performance. The reinforcing effects of SiO2 nanofillers and very high molecular weight PI ligands were investigated by dynamic mechanical analysis (DMA) as well as computational simulation for the cured linear PI homopolymer/SiO2-g-PI particle brush bulk films.

The Importance of Bulk Viscoelastic Properties in "Self-Healing" of Acrylate-Based Copolymer Materials.

"Self-healing" has emerged as a concept to increase the functional stability and durability of polymer materials in applications and thus to benefit the sustainability of polymer-based technologies. Recently, van der Waals (vdW)-driven "self-healing" of sequence-controlled acrylate-based copolymers due to "key-and-lock"- or "ring-and-lock"-type interactions has generated considerable interest as a viable route toward engineering polymers with "self-healing" ability. This contribution systematically evaluates the time, temperature, and composition dependence of the mechanical recovery of acrylate-based copolymer and homopolymer systems subject to cut-and-adhere testing. "Self-healing" in n-butyl acrylate/methyl methacrylate (BA/MMA)- or n-butyl acrylate/styrene (BA/Sty)-based copolymers with varying composition and sequence is found to correlate with the bulk viscoelastic properties of materials and to follow a similar trend as other tested acrylate-based homo- and copolymers. This suggests that "self-healing" in this class of materials is more related to the chain dynamics of bulk materials rather than composition- or sequence-dependent specific interactions.

Composition-Orientation Induced Mechanical Synergy in Nanoparticle Brushes with Grafted Gradient Copolymers.

Gradient poly(methyl methacrylate/n-butyl acrylate) copolymers, P(MMA/BA), with various compositional ratios, were grafted from surface-modified silica nanoparticles (SiO2-g-PMMA-grad-PBA) via complete conversion surface-initiated activator regenerated by electron transfer (SI-ARGET) atom transfer radical polymerization (ATRP). Miniemulsion as the reaction medium effectively confined the interparticle brush coupling within micellar compartments, preventing macroscopic gelation and enabling complete conversion. Isolation of dispersed and gelled fractions revealed dispersed particle brushes to feature a higher Young's modulus, toughness, and ultimate strain compared with those of the "gel" counterparts. Upon purification, brush nanoparticles from the dispersed phase formed uniform microstructures. Uniaxial tension testing revealed a "mechanical synergy" for copolymers with MMA/BA = 3:2 molar ratio to concurrently exhibit higher toughness and stiffness. When compared with linear analogues of similar composition, the brush nanoparticles with gradient copolymers had better mechanical properties, attributed to the synergistic effects of the combination of composition and propagation orientation, highlighting the significance of architectural design for tethered brush layers of such hybrid materials.

Copolymer Brush Particle Hybrid Materials with "Recall-and-Repair" Capability.

The effect of sequence structure on the self-healing and shape-memory properties of copolymer-tethered brush particle films was investigated and compared to linear copolymer analogs. Poly(n-butyl acrylate-co-methyl methacrylate), P(BA-co-MMA), and linear and brush analogs with controlled gradient and statistical sequence were synthesized by atom transfer radical polymerization (ATRP). The effect of sequence on self-healing in BA/MMA copolymer brush particle hybrids followed similar trends as for linear analogs. Most rapid restoration of mechanical properties was found for statistical copolymer sequence; an increase of the high Tg (MMA) component provided a path to raise the material's modulus while retaining self-heal ability. Creep testing revealed profound differences between linear and brush systems. While linear copolymers featured substantial viscous deformation when exposed to constant stress in the linear regime, brush analogs displayed minimal permanent deformation and featured shape restoration. The reduction of flow was interpreted to be a consequence of slow cooperative relaxation due to the complex microstructure of brush particle hybrids in which long-range motions are constrained through entanglements and slow-diffusing particle cores. The rubbery-like response imparts BA/MMA copolymer brush material systems concurrent "shape-memory" and "self-heal" capability. This ability to "recall-and-repair" could find application in the design of functional hybrid materials, for example, for soft robotics.

Sequence-Enhanced Self-Healing in "Lock-and-Key" Copolymers.

Van der Waals-driven self-healing in copolymers with "lock-and-key" architecture has emerged as a concept to endow engineering-type polymers with the capacity to recover from structural damage. Complicating the realization of "lock-and-key"-enabled self-healing is the tendency of copolymers to form nonuniform sequence distributions during polymerization reactions. This limits favorable site interactions and renders the evaluation of van der Waals-driven healing difficult. Here, methods for the synthesis of lock-and-key copolymers with prescribed sequence were used to overcome this limitation and enable the deliberate synthesis of "lock-and-key" architectures most conducive to self-healing. The effect of molecular sequence on the material's recovery behavior was evaluated for the particular case of three poly(n-butyl acrylate/methyl methacrylate) [P(BA/MMA)] copolymers with similar molecular weights, dispersity, and overall composition but with different sequences: alternating (alt), statistical (stat), and gradient (grad). They were synthesized using atom transfer radical polymerization (ATRP). Copolymers with alt and stat sequence displayed a 10-fold increase of recovery rate compared to the grad copolymer variant despite a similar overall glass transition temperature. Investigation with small-angle neutron scattering (SANS) revealed that rapid property recovery is contingent on a uniform microstructure of copolymers in the solid state, thus avoiding the pinning of chains in glassy MMA-rich cluster regions. The results delineate strategies for the deliberate design and synthesis of engineering polymers that combine structural and thermal stability with the ability to recover from structural damage.

Hierarchically structured bioinspired nanocomposites.

Next-generation structural materials are expected to be lightweight, high-strength and tough composites with embedded functionalities to sense, adapt, self-repair, morph and restore. This Review highlights recent developments and concepts in bioinspired nanocomposites, emphasizing tailoring of the architecture, interphases and confinement to achieve dynamic and synergetic responses. We highlight cornerstone examples from natural materials with unique mechanical property combinations based on relatively simple building blocks produced in aqueous environments under ambient conditions. A particular focus is on structural hierarchies across multiple length scales to achieve multifunctionality and robustness. We further discuss recent advances, trends and emerging opportunities for combining biological and synthetic components, state-of-the-art characterization and modelling approaches to assess the physical principles underlying nature-inspired design and mechanical responses at multiple length scales. These multidisciplinary approaches promote the synergetic enhancement of individual materials properties and an improved predictive and prescriptive design of the next era of structural materials at multilength scales for a wide range of applications.

Alternating Methyl Methacrylate/n-Butyl Acrylate Copolymer Prepared by Atom Transfer Radical Polymerization.

Poly(methyl methacrylate/n-butyl acrylate) [P(MMA/BA)] copolymer with an alternating structure was synthesized via an activator regenerated by electron transfer (ARGET) atom transfer radical (co)polymerization (ATRP) of 2-ethylfenchyl methacrylate (EFMA) and n-butyl acrylate (BA) with subsequent postpolymerization modifications (PPM). Due to the steric hindrance of the bulky pendant group of EFMA, as well as the low reactivity ratio of BA in copolymerization with methacrylates, copolymerization of EFMA and BA generated a copolymer with a high content of alternating dyads. A subsequent PPM procedure of the alternating EFMA/BA copolymer was comprised of the hydrolysis of a tertiary ester by trifluoroacetic acid and methylation by (trimethylsilyl)diazomethane. After the modifications, the architecture of the obtained alternating MMA/BA copolymers was compared with gradient and statistical copolymers with overall similar compositions, molecular weights, and dispersities. 13C NMR indicated the absence of either MMA/MMA/MMA or BA/BA/BA sequences, in contrast to an abundance of homotriads in either the statistical or especially in the gradient copolymer. All three copolymers had similar glass transition temperatures, as measured by differential scanning calorimetry (DSC), but the alternating copolymer had the narrowest range of glass transition.

Facile Entropy-Driven Segregation of Imprinted Polymer-Grafted Nanoparticle Brush Blends by Solvent Vapor Annealing Soft Lithography.

Polymer-grafted nanoparticles (PGNPs) have attracted extensive research interest due to their potential for enhancing mechanical and electrical properties of both bulk polymer composite materials, as well as thin polymer films incorporating these nanoparticles (NPs). In previous studies, we have shown that an entropic driving force serves to organize low-molecular-mass PGNPs in imprinted blend films of PGNPs with low-molecular-mass homopolymers. In this work, we developed a novel solvent vapor annealing soft lithography (SVA-SL) method to overcome the technical difficulties in processing the high-molecular-mass PGNP blends due to the intrinsically sluggish melt annealing kinetics found in the phase separation of these blend PGNP materials. In particular, we utilized SVA-SL to create nanopatterns in blends of PGNPs having relatively high-molecular-mass-grafted layers but with cores of NPs having greatly different sizes. The minimization of the entropic free energy in the present system corresponded to larger PGNPs partitioning almost exclusively into the "mesa" regions of the imprinted PGNP blend films, as quantified by the estimation of the partition coefficient, Kp. The use of the SVA-SL processing method is important because it allows facile imprint patterning of PGNP materials and large-scale organization of the PGNPs even when the grafted chain lengths are long enough for the chains to be highly entangled, allowing enhanced thermo-mechanical property enhancements of the resulting films and a corresponding extended range of potential nanotech applications.

Internal Microstructure Dictates Interactions of Polymer-grafted Nanoparticles in Solution.

Understanding the effects of polymer brush architecture on particle interactions in solution is requisite to enable the development of functional materials based on self-assembled polymer-grafted nanoparticles (GNPs). Static and dynamic light scattering of polystyrene-grafted silica particle solutions in toluene reveals that the pair interaction potential, inferred from the second virial coefficient, A 2, is strongly affected by the grafting density, σ, and degree of polymerization, N, of tethered chains. In the limit of intermediate σ (∼0.3 to 0.6 nm-2) and high N, A 2 is positive and increases with N. This confirms the good solvent conditions and can be qualitatively rationalized on the basis of a pair interaction potential derived for grafted (brush) particles. In contrast, for high σ > 0.6 nm-2 and low N, A 2 displays an unexpected reversal to negative values, thus indicating poor solvent conditions. These findings are rationalized by means of a simple analysis based on a coarse-grained brush potential, which balances the attractive core-core interactions and the excluded volume interactions imparted by the polymer grafts. The results suggest that the steric crowding of polymer ligands in dense GNP systems may fundamentally alter the interactions between brush particles in solution and highlight the crucial role of architecture (internal microstructure) on the behavior of hybrid materials. The effect of grafting density also illustrates the opportunity to tailor the physical properties of hybrid materials by altering geometry (or architecture) rather than a variation of the chemical composition.

Control of Phase Morphology of Binary Polymer Grafted Nanoparticle Blend Films via Direct Immersion Annealing.

While the phase separation of binary mixtures of chemically different polymer-grafted nanoparticles (PGNPs) is observed to superficially resemble conventional polymer blends, the presence of a "soft" polymer-grafted layer on the inorganic core of these nanoparticles qualitatively alters the phase separation kinetics of these "nanoblends" from the typical pattern of behavior seen in polymer blends and other simple fluids. We investigate this system using a direct immersion annealing method (DIA) that allows for a facile tuning of the PGNPs phase boundary, phase separation kinetics, and the ultimate scale of phase separation after a sufficient "aging" time. In particular, by switching the DIA solvent composition from a selective one (which increases the interaction parameter according to Timmerman's rule) to an overall good solvent for both PGNP components, we can achieve rapid switchability between phase-separated and homogeneous states. Despite a relatively low and non-classical power-law coarsening exponent, the overall phase separation process is completed on a time scale on the order of a few minutes. Moreover, the roughness of the PGNP blend film saturates at a scale that is proportional to the in-plane phase separation pattern scale, as observed in previous blend and block copolymer film studies. The relatively low magnitude of the coarsening exponent n is attributed to a suppression of hydrodynamic interactions between the PGNPs. The DIA method provides a significant opportunity to control the phase separation morphology of PGNP blends by solution processing, and this method is expected to be quite useful in creating advanced materials.

Observation of General Entropy-Enthalpy Compensation Effect in the Relaxation of Wrinkled Polymer Nanocomposite Films.

Surface-textured polymer nanocomposite (PNC) films are utilized in many device applications, and therefore understanding the relaxation behavior of such films is important. By extending an in situ wrinkle relaxation method, we observed that the thermal stability of wrinkled PNC films, both above and below the glass transition temperature (Tg), is proportional to a film's nanoparticle (polymer grafted and bare) concentration, with a slope that changes sign at a compensation temperature (Tcomp) that is determined to be in the vicinity of the film's Tg. This provides unambiguous confirmation of entropy-enthalpy compensation (EEC) as a general feature of PNC films, implying that the stability of PNC films changes from being enhanced to becoming diminished by simply passing through this characteristic temperature, a phenomenon having evident practical ramifications. We suggest EEC will also arise in films where residual stresses are associated with the film fabrication process, which is relevant to nanotech device applications.

Enhanced resistance to decay of imprinted nanopatterns in thin films by bare nanoparticles compared to polymer-grafted nanoparticles.

We extend a previous study on the influence of nanoparticles on the decay of nanoimprinted polymer film patterns to compare the effects of "bare" silica (SiO2) nanoparticles and SiO2 nanoparticles with grafted polymer layers having the same chemical composition as the polymer matrix. This method involves nanoimprinting substrate-supported polymer films using a pattern replicated from a digital versatile disc (DVD), and then annealing the patterned polymer nanocomposite films at elevated temperatures to follow the decay of the topographic surface pattern with time by atomic force microscopy imaging after quenching. We quantified the relaxation of the pattern height ("slumping") and determined the relaxation time τ for this pattern decay process as a function of nanoparticle filler type and concentration to determine how nanoparticle additives influence relative film stability. Attractive interactions between the bare nanoparticles and the polymer matrix significantly enhance the thermal resilience of the nanopatterns to decay, compared to those of the particle brushes, wherein the particle core interactions are screened from the matrix via the brush layer. A novel aspect of this method is that it readily lends itself to in situ film relaxation measurements in a manufacturing context. We observe that the relaxation time of the pattern relaxation exhibits entropy-enthalpy compensation in the free energy parameters governing the pattern relaxation process as a function of temperature, irrespective of the NP system used, consistent with our previous experimental and computational studies.

Transparent Hybrid Opals with Unexpected Strong Resonance-Enhanced Photothermal Energy Conversion.

Photothermal energy conversion is of fundamental importance to applications ranging from drug delivery to microfluidics and from ablation to fabrication. It typically originates from absorptive processes in materials that-when coupled with non-radiative dissipative processes-allow the conversion of radiative energy into heat. Microstructure design provides versatile strategies for controlling light-matter interactions. In particular, the deliberate engineering of the band structure in photonic materials is known to be an effective approach to amplify absorption in materials. However, photonic amplification is generally tied to high optical contrast materials which limit the applicability of the concept to metamaterials such as microfabricated metal-air hybrids. This contribution describes the first observation of pronounced amplification of absorption in low contrast opals formed by the self-assembly of polymer-tethered particles. The dependence of the amplification factor on the length scale and degree of order of materials as well as the angle of incidence reveal that it is related to the slow photon effect. A remarkable amplification factor of 16 is shown to facilitate the rapid "melting" of opal films even in the absence of "visible" absorption. The results point to novel opportunities for tailoring light-matter interactions in hybrid materials that can benefit the manipulation and fabrication of functional materials.

Enhancing the Performance of Rubber with Nano ZnO as Activators.

The vulcanization of rubber is a chemical process to improve the mechanical properties by cross-linking unsaturated polymer chains. Zinc oxide (ZnO) acts as an activator, boosting the rubbers' sulfur vulcanization. Maintaining the level of ZnO content in the rubber compounds as low as possible is desirable, not only for economic reasons but also to reduce the environmental footprint of the process. In this contribution, octylamine (OA) capped ZnO nanoparticles (5 nm diameter), prepared through a thermal decomposition method, were demonstrated to be efficient activators for the sulfur vulcanization of natural rubber, enabling the reduction of the required amount of ZnO as compared to commercial systems. The effect of different ZnO activators (OA capped ZnO/commercial indirect process ZnO) on the curing characteristics, cross-linking densities, and mechanical performance, as well as the thermal behavior of rubber compounds, were investigated. Compared to the commercial indirect process ZnO, OA capped ZnO nanoparticles not only effectively enhanced the curing efficiency of natural rubber but also improved the mechanical performance of the composites after vulcanization. This was interpreted as, by applying the OA capped ZnO nanoparticles, the ZnO levels in rubber compounding were significantly reduced under the industrial vulcanization condition (151 °C, 30 min).

Click-Chemistry Approach toward Antibacterial and Degradable Hybrid Hydrogels Based on Octa-Betaine Ester Polyhedral Oligomeric Silsesquioxane.

An efficient process for the synthesis of degradable hydrogels containing octa-betaine ester polyhedral oligomeric silsesquioxane (POSS) through efficient thiol-ene and Menschutkin click reactions was developed. The hydrogels exhibited a yield strength of 0.36 MPa and a compressive modulus of 4.38 MPa and displayed excellent flexibility as well as torsion resistance. Antibacterial efficacy of hydrogels (and degradation products) was evaluated using Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive). Efficacy was found to increase with the concentration of cetyl chloroacetate (CCA) in the hydrogel network, reaching 93% and 99% for Escherichia coli and Staphylococcus aureus, respectively. Degradation of hydrogels was observed in weak alkali conditions (pH = 8) and at physiological conditions (pH = 7.4). The degradation time of the hydrogels could be finely tuned by variation of the CCA content in the hydrogel and environmental stimulus. The tunable degradation behavior under physiological conditions combined with high antibacterial efficacy could render the presented materials interesting for tissue engineering applications.

Acid Mine Drainage Remediation: Aluminum Chelation Using Functional Graphenic Materials.

Acid mine drainage (AMD) is a pervasive source of metal pollution that severely impacts freshwater ecosystems and has a direct impact on human health. Conventional active and passive methods work very well for removing iron in AMD remediation, which is typically the highest metallic impurity. However, conventional passive remediation fails to remove all aluminum, which has severe ecological implications. Removal of aluminum ions using chelation, which traditionally uses small molecules that bind metals tightly for sequestration, holds promise. Yet, chelation strategies are limited because once introduced into surface water, small molecules are difficult to reclaim and often persist in the environment as pollutants. To address this, we have designed six unique scaffolds based on functional graphenic materials (FGMs) to create nonsoluble materials that could be placed at the end of a passive remediation process to remove persistent aluminum. When tested for efficacy, all six FGMs successfully demonstrated a reversible capacity to remove aluminum from acidic water, chelating up to 21 µg of Al/mg of FGM. Furthermore, when they were exposed to E. coli as an approximation for environmental compatibility, viability was unaffected, even at high concentrations, suggesting these FGMs are nontoxic and viable candidates for passive chelation-based remediation.

Assembly of Conductive Polyaniline Microstructures by a Laser-Induced Microbubble.

Micropatterns of conductive polymers are key for various applications in the fields of flexible electronics and sensing. A bottom-up method that allows high-resolution printing without additives is still lacking. Here, such a method is presented based on microprinting by the laser-induced microbubble technique (LIMBT). Continuous micropatterning of polyaniline (PANI) was achieved from a dispersion of the emeraldine base form of PANI (EB-PANI) in n-methyl-2-pyrrolidone (NMP). A focused laser beam is absorbed by the EB-PANI nanoparticles and leads to formation of a microbubble, followed by convection currents, which rapidly pin EB-PANI nanoparticles to the bubble/substrate interface. Micro-Raman spectra confirmed that the printed patterns preserve the molecular structure of EB-PANI. A simple transformation of the printed lines to the conducting emeraldine salt form of PANI (ES-PANI) was achieved by doping with various acid solutions. The hypothesized deposition mechanism was verified, and the resulting structures were characterized by microscopic methods. The microstructures displayed conductivities of 3.8 × 10-1 S/cm upon HCl doping and 1.5 × 10-1 S/cm upon H2SO4 doping, on par with state-of-the-art patterning methods. High fidelity control over the width of the printed lines down to ∼650 nm was accomplished by varying the laser power and microscope stage velocity. This straightforward bottom-up method using low-power lasers offers an alternative to current microfabrication techniques.

Nanoscale Pattern Decay Monitored Line by Line via In Situ Heated Atomic Force Microscopy.

We combine in situ heated atomic force microscopy (AFM) with automated line-by-line spectral analysis to quantify the relaxation or decay phenomenon of nanopatterned composite polymer films above the glass-transition temperature of the composite material. This approach enables assessment of pattern fidelity with a temporal resolution of ≈1 s, providing the necessary data density to confidently capture the short-time relaxation processes inaccessible to conventional ex situ measurements. Specifically, we studied the thermal decay of nanopatterned poly(methyl methacrylate) (PMMA) and PMMA nanocomposite films containing unmodified and PMMA-grafted silica nanoparticles (SiO2 NP) of varying concentrations and film thicknesses using this new approach. Features imprinted on neat PMMA films were seen to relax at least an order of magnitude faster than the NP-filled films at decay temperatures above the glass transition of the PMMA matrix. It was also seen that patterned films with the lowest residual thickness (34 nm) filled with unmodified SiO2 NP decayed the slowest. The effect of nanoparticle additive was almost negligible in reinforcing the patterned features for films with the highest residual thickness (257 nm). Our in situ pattern decay measurement and the subsequent line-by-line spectral analysis enabled the investigation of various parameters affecting the pattern decay such as the underlying residual thickness, type of additive system, and temperature in a timely and efficient manner.

Nanosized Organo-Silica Particles with "Built-In" Surface-Initiated Atom Transfer Radical Polymerization Capability as a Platform for Brush Particle Synthesis.

A facile synthetic method was developed to prepare sub-5 nm organo-silica (oSiO2) nanoparticles through the self-condensation of atom transfer radical polymerization (ATRP)-initiator-containing silica precursors. The obtained oSiO2 nanoparticles were characterized by a combination of nuclear magnetic resonance (NMR), thermogravimetric analysis (TGA), transmission electron microscopy (TEM), dynamic light scattering (DLS), and small-angle neutron scattering (SANS). The accessibility of the surface-Br initiating sites was evaluated by the polymerization of poly(methyl methacrylate) (PMMA) ligands from the surface of the oSiO2 nanoparticles using surface-initiated atom transfer radical polymerization (SI-ATRP). The ultrasmall size, tunable composition, and ease of surface modification may render these organo-silica nanoparticle systems with built-in SI-ATRP capability an interesting alternative to conventional silica nanoparticles for functional material design.