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.

Pressure Indicator Composite Films via Compressive Deformation of a Translucent Matrix Containing a Contrasting Filler.

A neglected mechanism for pressure-responsive color change is demonstrated using cellulose acetate composites prepared by direct (solvent) immersion annealing (DIA), with different loadings of activated charcoal filler. Namely, compressive plastic deformation of the translucent cellulose acetate leads to a decrease in the optical path length and a concomitant increase in the visibility of the opaque contrasting filler. Composites bearing 1-7 wt% activated charcoal exhibited a linear relationship between applied pressure and resulting pressure mark brightness in the range of 12-56 MPa. Comparison of pressure mark patterns with cross-sectional scanning electron microscopy (SEM) supports the importance of the porous morphology arising from DIA for the tuning of the pressure indicator sensitivity. A simple ball drop test is used to illustrate the robustness and utility of these indicators in optical impact assessment.

Transient Interfacial Pattern Formation in Block Copolymer Thin Films via Sequential Thermal and Solvent Immersion Annealing.

A variety of structures encountered in nature only arise in materials under highly nonequilibrium conditions, suggesting to us that the scope for creating new functional block copolymer (BCP) structures might be significantly enlarged by embracing complex processing histories that allow for the fabrication of structures quite unlike those created under "near-equilibrium" conditions. The present work examines the creation of polymer film structures in which highly nonequilibrium processing conditions allow for the creation of entirely new types of transient BCP morphologies achieved by transitioning between different ordered states. Most previous studies of BCP materials have emphasized ordering them from their disordered state obtained from a solution film casting process, followed by a slow thermal annealing (TA) process at elevated temperatures normally well above room temperature. We have previously shown that achieving the equilibrium TA state can be accelerated by a direct solvent immersion annealing (DIA) preordering step that creates nascent ordered microstructures, followed by TA. In the present work, we examine the reverse nonequilibrium sequential processing in which we first thermally anneal the BCP film to different levels of partial (lamellar) order and then subject it to DIA to swell the lamellae. This sequential processing rapidly leads to a swelling-induced wrinkle pattern that initially grows with immersion time and can be quenched by solvent evaporation into its corresponding glassy state morphology. The article demonstrates the formation of wrinkling "defect" patterns in entangled BCP films by this sequential annealing that does not form under ordinary TA conditions. At long DIA times, these highly "defective" film structures evolve in favor of the equilibrium morphology of parallel lamellae observed with DIA alone. In conjunction with our previous study of sequential DIA + TA, the present TA + DIA study demonstrates that switching the order of these processing methods for block copolymer films gives the same final state morphology in the limit of long time as any one method alone, but with drastically different intermediate transient state morphologies. These transient morphologies could have many applications.

Self-Cross-Linking of MXene-Intercalated Graphene Oxide Membranes with Antiswelling Properties for Dye and Salt Rejection.

Membrane-based water purification is poised to play an important role in tackling the potable water crisis for safe and clean water access for the general population. Several studies have focused on near two-dimensional membranes for this purpose, which is based on an ion rejection technique. However, membrane swelling in these materials has emerged as a significant challenge because it leads to the loss of function. Herein, we report a self-cross-linked MXene-intercalated graphene oxide (GO) membrane that retains ion and dye rejection properties because the physical cross-linking interaction between Ti-O-Ti and neighboring nanosheets effectively suppresses the swelling of the membrane. In addition to the associative Ti-O-Ti bonds, C-O-C, O=C-O, and C-OH bonds are also formed, which are important for inhibiting the swelling of the membrane. To ensure the longevity of these membranes in a service context, they were subjected to heat pressurization and subsequent thermal annealing. The membrane subjected to this novel processing history exhibits minimal swelling upon immersion in solutions and retains function, rejecting salt and dyes over a wide range of salt and dye concentrations. Furthermore, these membranes successfully rejected dye and salt over a period of 72 h without a degradation of function, suggesting that these membranes have the requisite durability for water filtration applications.

Ultrahigh Capacitive Energy Density in Stratified 2D Nanofiller-Based Polymer Dielectric Films.

Dielectric capacitors are critical components in electronics and energy storage devices. The polymer-based dielectric capacitors have the advantages of device flexibility, fast charge-discharge rates, low loss, and graceful failure. Elevating the use of polymeric dielectric capacitors for advanced energy applications such as electric vehicles (EVs), however, requires significant enhancement of their energy densities. Here, we report a polymer thin film heterostructure-based capacitor of poly(vinylidene fluoride)/poly(methyl methacrylate) with stratified 2D nanofillers (Mica or h-BN nanosheets) (PVDF/PMMA-2D fillers/PVDF), that shows enhanced permittivity, high dielectric strength, and an ultrahigh energy density of ≈75 J/cm3 with efficiency over 79%. Density functional theory calculations verify the observed permittivity enhancement. This approach of using oriented 2D nanofillers-based polymer heterostructure composites is expected to be versatile for designing high energy density thin film polymeric dielectric capacitors for myriads of applications.

Comparative Study of Polymer-Grafted BaTiO3 Nanoparticles Synthesized Using Normal ATRP as Well as ATRP and ARGET-ATRP with Sacrificial Initiator with a Focus on Controlling the Polymer Graft Density and Molecular Weight.

Structurally well-defined polymer-grafted nanoparticle hybrids are highly sought after for a variety of applications, such as antifouling, mechanical reinforcement, separations, and sensing. Herein, we report the synthesis of poly(methyl methacrylate) grafted- and poly(styrene) grafted-BaTiO3 nanoparticles using activator regeneration via electron transfer (ARGET ATRP) with a sacrificial initiator, atom transfer radical polymerization (normal ATRP), and ATRP with sacrificial initiator, to understand the role of the polymerization procedure in influencing the structure of nanoparticle hybrids. Irrespective of the polymerization procedure adopted for the synthesis of nanoparticle hybrids, we noticed PS grafted on the nanoparticles showed moderation in molecular weight and graft density (ranging from 30,400 to 83,900 g/mol and 0.122 to 0.067 chain/nm2) compared to PMMA-grafted nanoparticles (ranging from 44,620 to 230,000 g/mol and 0.071 to 0.015 chain/nm2). Reducing the polymerization time during ATRP has a significant impact on the molecular weight of polymer brushes grafted on the nanoparticles. PMMA-grafted nanoparticles synthesized using ATRP had lower graft density and considerably higher molecular weight compared to PS-grafted nanoparticles. However, the addition of a sacrificial initiator during ATRP resulted in moderation of the molecular weight and graft density of PMMA-grafted nanoparticles. The use of a sacrificial initiator along with ARGET offered the best control in achieving lower molecular weight and narrow dispersity for both PS (37,870 g/mol and PDI of 1.259) and PMMA (44,620 g/mol and PDI of 1.263) nanoparticle hybrid systems.

Polymer-Grafted Nanoparticles with Variable Grafting Densities for High Energy Density Polymeric Nanocomposite Dielectric Capacitors.

Designing high energy density dielectric capacitors for advanced energy storage systems needs nanocomposite-based dielectric materials, which can utilize the properties of both inorganic and polymeric materials. Polymer-grafted nanoparticle (PGNP)-based nanocomposites alleviate the problems of poor nanocomposite properties by providing synergistic control over nanoparticle and polymer properties. Here, we synthesize "core-shell" barium titanate-poly(methyl methacrylate) (BaTiO3-PMMA) grafted PGNPs using surface-initiated atom transfer polymerization (SI-ATRP) with variable grafting densities of (0.303 to 0.929) chains/nm2 and high molecular masses (97700 g/mL to 130000 g/mol) and observe that low grafted density and high molecular mass based PGNP show high permittivity, high dielectric strength, and hence higher energy densities (≈ 5.2 J/cm3) as compared to the higher grafted density PGNPs, presumably due to their "star-polymer"-like conformations with higher chain-end densities that are known to enhance breakdown. Nonetheless, these energy densities are an order of magnitude higher than their nanocomposite blend counterparts. We expect that these PGNPs can be readily used as commercial dielectric capacitors, and these findings can serve as guiding principles for developing tunable high energy density energy storage devices using PGNP systems.

Hiking down the Free Energy Landscape Using Sequential Solvent and Thermal Processing for Versatile Ordering of Block Copolymer Films.

The kinetics and morphology of the ordering of block copolymer (BCP) films are highly dependent on the processing pathway, as the enthalpic and entropic forces driving the ordering processes can be quite different depending on process history. We may gain some understanding and control of this variability of BCP morphology with processing history through a consideration of the free energy landscape of the BCP material and a consideration of how the processing procedure moves the system through this energy landscape in a way that avoids having the system becoming trapped into well-defined metastable minima having a higher free energy than the target low free energy ordered structure. It is well known that standard thermal annealing (TA) of BCPs leads to structures corresponding to a well-defined stable free energy minimum; however, the BCP must be annealed for a very long time before the target low free energy structures can be achieved. Herein, we show that the same target low-energy structure can be achieved relatively quickly by subjecting as-cast films to an initial solvent annealing [direct immersion annealing (DIA) or solvent vapor annealing (SVA)] procedure, followed by a short period of TA. This process relies on lowering the activation energy barrier by reducing the glass-transition temperature through DIA (or SVA), followed by a multi-interface chain rearrangement through sequential TA. This energy landscape approach to ordering should be applicable to the process design for ordering many other complex materials.

Antibacterial flexible triboelectric nanogenerator via capillary force lithography.

Increasing the surface contact area (SCA) between active materials of triboelectric nanogenerator (TENG) can effectively enhance energy harvesting performance. In the meantime, owing to potential intimate contacts between skin and wearables, hygienic aspects of TENG devices with high SCA become important. Herein, we present a robust route to fabricate flexible TENGs with antimicrobial capability realized by nano-patterning thermoplastic polyurethane (TPU) thin films. Without involving sophisticated equipment and time-consuming technique, simply tuning curing conditions of capillary force lithography could precisely control the nanostructure geometry. Our topographically designed TENGs could promote higher power generation while preventing biofilm formation without adding any chemical additives. Analysis of pattern amplitude and wavelength correlation to output power is uniquely provided for a deeper understanding of how patterns enable peak performance of TENGs. Furthermore, a prototype TENG was innovatively applied to a smart device as a transparent screen sensor. Specific finger trajectories could be recognized by different electric responses, and as-generated electricity can be directly charged into comercial capacitors. Our proposed TENGs with critical hygienic advancements are expected to open avenues for TENG-incorporated wearables in the post-pandemic era.

Nanobrick Wall Multilayer Thin Films with High Dielectric Breakdown Strength.

Current thermally conductive and electrically insulating insulation systems are struggling to meet the needs of modern electronics due to increasing heat generation and power densities. Little research has focused on creating insulation systems that excel at both dissipating heat and withstanding high voltages (i.e., have both high thermal conductivity and a high breakdown strength). Herein, a polyelectrolyte-based multilayer nanocomposite is demonstrated to be a thermally conductive high-voltage insulation. Through inclusion of both boehmite and vermiculite clay, the breakdown strength of the nanocomposite was increased by ≈115%. It was also found that this unique nanocomposite has an increase in its breakdown strength, modulus, and hydrophobicity when exposed to elevated temperatures. This readily scalable insulation exhibits a remarkable combination of breakdown strength (250 kV/mm) and thermal conductivity (0.16 W m-1 K-1) for a polyelectrolyte-based nanocomposite. This dual clay insulation is a step toward meeting the needs of the next generation of high-performance insulation systems.

Enhanced Dielectric Strength and Capacitive Energy Density of Cyclic Polystyrene Films.

The maximum capacitive energy stored in polymeric dielectric capacitors, which are ubiquitous in high-power-density devices, is dictated by the dielectric breakdown strength of the dielectric polymer. The fundamental mechanisms of the dielectric breakdown, however, remain unclear. Based on a simple free-volume model of the polymer fluid state, we hypothesized that the free ends of linear polymer chains might act as "defect" sites, at which the dielectric breakdown can initiate. Thus, the dielectric breakdown strength of cyclic polymers should exhibit enhanced stability in comparison to that of their linear counterparts having the same composition and similar molar mass. This hypothesis is supported by the ∼50% enhancement in the dielectric breakdown strength and ∼80% enhancement in capacitive energy density of cyclic polystyrene melt films in comparison to corresponding linear polystyrene control films. Furthermore, we observed that cyclic polymers exhibit a denser packing density than the linear chain melts, an effect that is consistent with and could account for the observed property changes. Our work demonstrates that polymer topology can significantly influence the capacitive properties of polymer films, and correspondingly, we can expect polymer topology to influence the gas permeability, shear modulus, and other properties of thin films dependent on film density.

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.

Drawn-on-Skin Sensors from Fully Biocompatible Inks toward High-Quality Electrophysiology.

The need to develop wearable devices for personal health monitoring, diagnostics, and therapy has inspired the production of innovative on-demand, customizable technologies. Several of these technologies enable printing of raw electronic materials directly onto biological organs and tissues. However, few of them have been thoroughly investigated for biocompatibility of the raw materials on the cellular, tissue, and organ levels or with different cell types. In addition, highly accurate multiday in vivo monitoring using such on-demand, in situ fabricated devices has yet to be done. Presented herein is the first fully biocompatible, on-skin fabricated electronics for multiple cell types and tissues that can capture electrophysiological signals with high fidelity. While also demonstrating improved mechanical and electrical properties, the drawn-on-skin ink retains its properties under various writing conditions, which minimizes the variation in electrical performance. Furthermore, the drawn-on-skin ink shows excellent biocompatibility with cardiomyocytes, neurons, mice skin tissue, and human skin. The high signal-to-noise ratios of the electrophysiological signals recorded with the DoS sensor over multiple days demonstrate its potential for personalized, long-term, and accurate electrophysiological health monitoring.

Manipulation of coacervate droplets with an electric field.

Many biopolymers are highly charged, and as in the case of many polymer mixtures, they tend to phase separate as a natural consequence of chain connectivity and an associated relatively low entropy of polymer mixing. Recently, it has become appreciated that the phase-separated structures formed by such polyelectrolyte blends, called "complex coacervates," underlie numerous biological structures and processes essential to living systems, and there has been intense interest in understanding the unique physical features of this type of phase-separation process. In the present work, we are particularly concerned with the field responsiveness of stabilized coacervate droplets formed after the phase separation of polyelectrolyte blend solution and then exposed to deionized water, making the droplet interfacial layer acquire a viscoelastic character that strongly stabilizes it against coalescence. We show that we can precisely control the positions of individual droplets and arrays of them with relatively low-voltage electric fields (on the order of 10 V/cm) and that the imposition of an oscillatory field gives rise to chain formation with coarsening of these chains into long fibers. Such a phase-separation-like process is generally observed in electrorheological fluids of solid colloidal particles subjected to much larger field strengths. The key to these coacervates' electrorheological properties is the altered interfacial viscoelastic properties when the droplets are introduced into deionized water and the associated high polarizability of the droplets, similar to the properties of many living cells. Since many different molecular payloads can be incorporated into these stable droplets, we anticipate many applications.

Soft-Shear-Aligned Vertically Oriented Lamellar Block Copolymers for Template-Free Sub-10 nm Patterning and Hybrid Nanostructures.

The template-free unidirectional alignment of lamellar block copolymers (l-BCPs) for sub-10 nm high-resolution patterning and hybrid multicomponent nanostructures is important for technological applications. We demonstrate a modified soft-shear-directed self-assembly (SDSA) approach for aligning pristine l-BCPs and l-BCPs with incorporated polymer-grafted nanoparticles (PGNPs), as well as the l-BCP conversion to aligned gold nanowires, and hybrid of metallic gold nanowire and dielectric silica nanoparticle in the form of line-dot nanostructures. The smallest patterns have a half-pitch as small as 9.8 nm. In all cases, soft-shear is achieved using a high-molecular-mass polymer topcoat layer, with support on a neutral bottom layer. We also show that the hybrid line-dot nanostructures have a red-shifted plasmonic response in comparison to neat gold nanowires. These template-free aligned BCPs and nanowires have potential use in nanopatterning applications, and the line-dot nanostructures should be useful in the sensing of biomolecules and other molecular species based on the plasmonic response of the nanowires.

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.

Recent Advances in the Synthesis of Polymer-Grafted Low-K and High-K Nanoparticles for Dielectric and Electronic Applications.

The synthesis of polymer-grafted nanoparticles (PGNPs) or hairy nanoparticles (HNPs) by tethering of polymer chains to the surface of nanoparticles is an important technique to obtain nanostructured hybrid materials that have been widely used in the formulation of advanced polymer nanocomposites. Ceramic-based polymer nanocomposites integrate key attributes of polymer and ceramic nanomaterial to improve the dielectric properties such as breakdown strength, energy density and dielectric loss. This review describes the "grafting from" and "grafting to" approaches commonly adopted to graft polymer chains on NPs pertaining to nano-dielectrics. The article also covers various surface initiated controlled radical polymerization techniques, along with templated approaches for grafting of polymer chains onto SiO2, TiO2, BaTiO3, and Al2O3 nanomaterials. As a look towards applications, an outlook on high-performance polymer nanocomposite capacitors for the design of high energy density pulsed power thin-film capacitors is also presented.

Multifunctional Oil Absorption with Macroporous Polystyrene Fibers Incorporating Silver-Doped ZnO.

Hydrophobic microporous polystyrene (PS) fibers are fabricated by a solvent-induced phase-separation-assisted electrospinning method. Zinc oxide (ZnO) and silver-doped zinc oxide (Ag-ZnO) nanomaterials with variable morphologies are added to the PS fibers, to investigate the influence of multifunctional nanofiller addition on the porosity and consequent oil-adsorbing properties for different oil types. The doping of silver as well as the uniformity in particle distribution are confirmed by scanning electron microscopy and the energy-dispersive spectral analyses. The porosity of the fibers and their crystallinity effect depend on the hydrophobicity and surface properties of these microporous nanofilled fibers. Ag-ZnO, specifically in 2 wt %, enhanced the pore size and distribution in PS porous fibers, thereby enhancing the oil-adsorbing property and its hydrophobicity. In-depth analysis of the oil adsorption mechanism is done for the fibers, both qualitatively and quantitatively, to demonstrate its correlation with the structural integrity of the fibers. The PS/2Ag-ZnO composite also exhibits the highest antibacterial performance against Staphylococcus aureus, a general indication of antibiological fouling properties of these oil-separating films. The antifouling/antibacterial activity of the nanoparticles and high oil sorption capacity of the highly porous PS composites show great potential for use in water-treatment-related applications.

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.