Ultralight and Mechanically Robust Ti3C2Tx Hybrid Aerogel Reinforced by Carbon Nanotubes for Electromagnetic Interference Shielding.

Lightweight materials with high electrical conductivity and robust mechanical properties are highly desirable for electromagnetic interference (EMI) shielding in modern portable and highly integrated electronics. Herein, a three-dimensional (3D) porous Ti3C2Tx/carbon nanotube (CNT) hybrid aerogel was fabricated via a bidirectional freezing method for lightweight EMI shielding application. The synergism of the lamellar and porous structure of the MXene/CNT hybrid aerogels contributed extensively to their excellent electrical conductivity (9.43 S cm-1) and superior electromagnetic shielding effectiveness (EMI SE) value of 103.9 dB at 3 mm thickness at the X-band frequency, the latter of which is the best value reported for synthetic porous nanomaterials. The CNT reinforcement in the MXene/CNT hybrid aerogels enhanced the mechanical robustness and increased the compressional modulus by 9661% relative to that of the pristine MXene aerogel. The hybrid aerogel with high electrical conductivity, good mechanical strength, and superior EMI shielding performance is a promising material for inhibiting EMI pollution.

Shaping micro-clusters via inverse jamming and topographic close-packing of microbombs.

Designing topographic clusters is of significant interest, yet it remains challenging as they often lack mobility or deformability. Here we exploit the huge volumetric expansion (up to 3000%) of a new type of building block, thermally expandable microbombs. They consist of a viscoelastic polymeric shell and a volatile gas core, which, within structural confinement, create micro-clusters via inverse jamming and topographical close-packing. Upon heating, microbombs anchored in rigid confinement underwent balloon-like blowing up, allowing for dense clusters via soft interplay between viscoelastic shells. Importantly, the confinement is unyielding against the internal pressure of the microbombs, thereby enabling self-assembled clusters, which can be coupled with topographic inscription to introduce structural hierarchy on the clusters. Our strategy provides densely packed yet ultralight clusters with a variety of complex shapes, cleavages, curvatures, and hierarchy. In turn, these clusters will enrich our ability to explore the assemblies of the ever-increasing range of microparticle systems.Self-assembled systems are normally composed of incompressible building blocks, which constrain their space filling efficiency. Yu et al. show programmable, densely packed clusters using thermally expandable soft microparticles, whereby the self-assembling process is realized via a jamming transition.

Multidirectional Wrinkle Patterns Programmed by Sequential Uniaxial Strain with Conformal yet Nontraceable Masks.

Surface wrinkling is a promising route to control the mechanical, electrical, and optical properties of materials in a wide range of applications. However, previous artificial wrinkles are restricted to single or random orientation and lacks selectivity. To address this challenge, this study presents multidirectional wrinkle patterns with high selectivity and orientation through sequential uniaxial strain with conformal polymeric shadow masks. The conformal but nontraceable polymeric stencil with microapertures are adhered to a flat substrate prior to oxidation, which forms discrete and parallel wrinkles in confined domains without any contamination. By fully investigating the process, this study displays compound topography of wrinkles consisting of wrinkle islands and surrounding secondary wrinkles on the same surface. With this topography, various diffusion properties are presented: from semi-transparent yet diffusive films to multidirectional diffusive films, which will be available for new types of optical diffuser applications.

Density-tunable lightweight polymer composites with dual-functional ability of efficient EMI shielding and heat dissipation.

Lightweight dual-functional materials with high EMI shielding performance and thermal conductivity are of great importance in modern cutting-edge applications, such as mobile electronics, automotive, aerospace, and military. Unfortunately, a clear material solution has not emerged yet. Herein, we demonstrate a simple and effective way to fabricate lightweight metal-based polymer composites with dual-functional ability of excellent EMI shielding effectiveness and thermal conductivity using expandable polymer bead-templated Cu hollow beads. The low-density Cu hollow beads (ρ ∼ 0.44 g cm-3) were fabricated through electroless plating of Cu on the expanded polymer beads with ultralow density (ρ ∼ 0.02 g cm-3). The resulting composites that formed a continuous 3D Cu network with a very small Cu content (∼9.8 vol%) exhibited excellent EMI shielding (110.7 dB at 7 GHz) and thermal conductivity (7.0 W m-1 K-1) with isotropic features. Moreover, the densities of the composites are tunable from 1.28 to 0.59 g cm-3 in accordance with the purpose of their applications. To the best of our knowledge, the resulting composites are the best lightweight dual-functional materials with exceptionally high EMI SE and thermal conductivity performance among synthetic polymer composites.

Multifunctional Mesoporous Ionic Gels and Scaffolds Derived from Polyhedral Oligomeric Silsesquioxanes.

A new methodology for fabrication of inorganic-organic hybrid ionogels and scaffolds is developed through facile cross-linking and solution extraction of a newly developed ionic polyhedral oligomeric silsesquioxane with inorganic core. Through design of various cationic tertiary amines, as well as cross-linkable functional groups on each arm of the inorganic core, high-performance ionogels are fabricated with excellent electrochemical stability and unique ion conduction behavior, giving superior lithium ion battery performance. Moreover, through solvent extraction of the liquid components, hybrid scaffolds with well-defined, interconnected mesopores are utilized as heterogeneous catalysts for the CO2-catalyzed cycloaddition of epoxides. Excellent catalytic performance, as well as highly efficient recyclability are observed when compared to other previous literature materials.

Nonlinear Frameworks for Reversible and Pluripotent Wetting on Topographic Surfaces.

Soft, ultrathin frameworks nonlinearly organized in tandem are presented to realize both reversible and pluripotent wetting on topographic surfaces. A design rule is introduced by establishing and proving the theoretical model upon hierarchical textures. Nonlinear frameworks can be conformally and reversibly wet upon complex topography in nature, thereby overcoming the wetting problems in previous conventional solid systems.

Facilitated Ion Transport in Smectic Ordered Ionic Liquid Crystals.

A novel ionic mixture of an imidazolium-based room-temperature ionic liquid containing ethylene-oxide-functionalized phosphite anions is fabricated, which, when doped with lithium salt, self-assembles into a smectic-ordered ionic liquid crystal through Coulombic interactions between the ion species. Interestingly, the smectic order in the ionic-liquid-crystal ionogel facilitates ionic transport.

Lithium Dendrite Suppression with UV-Curable Polysilsesquioxane Separator Binders.

For the first time, an inorganic-organic hybrid polymer binder was used for the coating of hybrid composites on separators to enhance thermal stability and to prevent formation of lithium dendrite in lithium metal batteries. The fabricated hybrid-composite-coated separators exhibited minimal thermal shrinkage compared with the previous composite separators (<5% change in dimension), maintenance of porosity (Gurley number ∼400 s/100 cm(3)), and high ionic conductivity (0.82 mS/cm). Lithium metal battery cell examinations with our hybrid-composite-coated separators revealed excellent C-rate and cyclability performance due to the prevention of lithium dendrite growth on the lithium anode even after 200 cycles under 0.2-5C (charge-discharge) conditions. The mechanism for lithium dendrite prevention was attributed to exceptional nanoscale surface mechanical properties of the hybrid composite coating layer compared with the lithium metal anode, as the elastic modulus of the hybrid-composite-coated separator far exceeded those of both the lithium metal anode and the required threshold for lithium metal dendrite prevention.

Biomass-Derived Thermally Annealed Interconnected Sulfur-Doped Graphene as a Shield against Electromagnetic Interference.

Electrically conductive thin carbon materials have attracted remarkable interest as a shielding material to mitigate the electromagnetic interference (EMI) produced by many telecommunication devices. Herein, we developed a sulfur-doped reduced graphene oxide (SrGO) with high electrical conductivity through using a novel biomass, mushroom-based sulfur compound (lenthionine) via a two-step thermal treatment. The resultant SrGO product exhibited excellent electrical conductivity of 311 S cm(-1), which is 52% larger than 205 S cm(-1) for undoped rGO. SrGO also exhibited an excellent EMI shielding effectiveness of 38.6 dB, which is 61% larger than 24.4 dB measured for undoped rGO. Analytical examinations indicate that a sulfur content of 1.95 atom % acts as n-type dopant, increasing electrical conductivity and, therefore, EMI shielding of doped graphene.

High through-plane thermal conduction of graphene nanoflake filled polymer composites melt-processed in an L-shape kinked tube.

Design of materials to be heat-conductive in a preferred direction is a crucial issue for efficient heat dissipation in systems using stacked devices. Here, we demonstrate a facile route to fabricate polymer composites with directional thermal conduction. Our method is based on control of the orientation of fillers with anisotropic heat conduction. Melt-compression of solution-cast poly(vinylidene fluoride) (PVDF) and graphene nanoflake (GNF) films in an L-shape kinked tube yielded a lightweight polymer composite with the surface normal of GNF preferentially aligned perpendicular to the melt-flow direction, giving rise to a directional thermal conductivity of approximately 10 W/mK at 25 vol % with an anisotropic thermal conduction ratio greater than six. The high directional thermal conduction was attributed to the two-dimensional planar shape of GNFs readily adaptable to the molten polymer flow, compared with highly entangled carbon nanotubes and three-dimensional graphite fillers. Furthermore, our composite with its density of approximately 1.5 g/cm(3) was mechanically stable, and its thermal performance was successfully preserved above 100 °C even after multiple heating and cooling cycles. The results indicate that the methodology using an L-shape kinked tube is a new way to achieve polymer composites with highly anisotropic thermal conduction.

Self-assembled block copolymer micelles with silver-carbon nanotube hybrid fillers for high performance thermal conduction.

The development of polymer-filled composites with an extremely high thermal conductivity (TC) that is competitive with conventional metals is in great demand due to their cost-effective process, light weight, and easy shape-forming capability. A novel polymer composite with a large thermal conductivity of 153 W m(-1) K(-1) was prepared based on self-assembled block copolymer micelles containing two different fillers of micron-sized silver particles and multi-walled carbon nanotubes. Simple mechanical mixing of the components followed by conventional thermal compression at a low processing temperature of 160 °C produced a novel composite with both structural and thermal stability that is durable for high temperature operation up to 150 °C as well as multiple heating and cooling cycles of ΔT = 100 °C. The high performance in thermal conduction of our composite was mainly attributed to the facile deformation of Ag particles during the mixing in a viscous thermoplastic medium, combined with networked carbon nanotubes uniformly dispersed in the nanoscale structural matrix of block copolymer micelles responsible for its high temperature mechanical stability. Furthermore, micro-imprinting on the composite allowed for topographically periodic surface micropatterns, which offers broader suitability for numerous micro-opto-electronic systems.

Fouling-tolerant nanofibrous polymer membranes for water treatment.

Nafion/polyvinylidene fluoride (PVDF) nanofibrous membranes with electrostatically negative charges on the fiber surface were fabricated via electrospinning with superior water permeability and antifouling behaviors in comparison with the conventional microfiltration membranes. The fiber diameter and the resultant pore size in the nanofibrous membranes were easily controlled through tailoring the properties of the electrospinning solutions. The electrospun Nafion/PVDF nanofibrous membranes revealed high porosities (>80%) and high densities of sulfonate groups on the membrane surface, leading to praiseworthy water permeability. Unexpectedly, the water permeability was observed as proportional to the fiber diameter and pore size in the membrane. The presence of sulfonate groups on the membrane improved the antifouling performance against negatively charged oily foulants.

RTA-treated carbon fiber/copper core/shell hybrid for thermally conductive composites.

In this paper, we demonstrate a facile route to produce epoxy/carbon fiber composites providing continuous heat conduction pathway of Cu with a high degree of crystal perfection via electroplating, followed by rapid thermal annealing (RTA) treatment and compression molding. Copper shells on carbon fibers were coated through electroplating method and post-treated via RTA technique to reduce the degree of imperfection in the Cu crystal. The epoxy/Cu-plated carbon fiber composites with Cu shell of 12.0 vol % prepared via simple compression molding, revealed 18 times larger thermal conductivity (47.2 W m(-1) K(-1)) in parallel direction and 6 times larger thermal conductivity (3.9 W m(-1) K(-1)) in perpendicular direction than epoxy/carbon fiber composite. Our novel composites with RTA-treated carbon fiber/Cu core/shell hybrid showed heat conduction behavior of an excellent polymeric composite thermal conductor with continuous heat conduction pathway, comparable to theoretical values obtained from Hatta and Taya model.

Copper shell networks in polymer composites for efficient thermal conduction.

Thermal management of polymeric composites is a crucial issue to determine the performance and reliability of the devices. Here, we report a straightforward route to prepare polymeric composites with Cu thin film networks. Taking advantage of the fluidity of polymer melt and the ductile properties of Cu films, the polymeric composites were created by the Cu metallization of PS bead and the hot press molding of Cu-plated PS beads. The unique three-dimensional Cu shell-networks in the PS matrix demonstrated isotropic and ideal conductive performance at even extremely low Cu contents. In contrast to the conventional simple melt-mixed Cu beads/PS composites at the same concentration of 23.0 vol %, the PS composites with Cu shell networks indeed revealed 60 times larger thermal conductivity and 8 orders of magnitude larger electrical conductivity. Our strategy offers a straightforward and high-throughput route for the isotropic thermal and electrical conductive composites.

Thermal annealing effects on the physical properties of styrenic pentablock ionomers and their electromechanical responses.

Thermal annealing effect on the physical properties of two ionic (poly((t-butyl-styrene)-b-(ethylene-r-propylene)-b-(styrene-r-styrene sulfonate)-b-(ethylene-r-propylene)-b-(t-butyl-styrene (SSPB) pentablock copolymers with different ion exchange capacities (IEC; 1.5 and 2.0 meq/g) and their electromechanical responses in ionic polymer-metal composite (IPMC) devices have been investigated. The ionic SSPB formed the microphase-separated morphology on the several tens nanometer scale and the selectively sulfonated styrene middle blocks formed the ionic channels through which ions can pass in the membrane. The thermal annealing at a high temperature led to the well developed interconnectivity between adjacent ionic channels, and thus enhanced the ion conductivity and mechanical strength of membranes, resulting in an actuation enhancement of the SSPB-based ionic actuator.

Dispersion and reaggregation of nanoparticles in the polypropylene copolymer foamed by supercritical carbon dioxide.

For the preparation of nanocomposites, we conducted environmentally benign foaming processing on polypropylene (PP) copolymer/clay nanocomposites via a batch process in an autoclave. We investigated the dispersion and the exfoliation of the nanoclay particles. Full exfoliation was achieved by the foamability of the matrix PP copolymer using supercritical carbon dioxide (sc CO2) and subcritical carbon dioxide (sub CO2). More and smaller cells were observed when the clay was blended as heterogeneous nuclei and sc CO2 was used. Small angle X-ray scattering showed that highly dispersed states (exfoliation) of the clay particles were obtained by the foaming process. Since the clay particles provided more nucleating sites for the foaming of the polymer, a well dispersed (or fully exfoliated) nanocomposite exhibited a higher cell density and a smaller cell size at the same clay particle concentration. Expansion of the adsorbed CO2 facilitated the exfoliation of the clay platelets; thus, sc CO2 at lower temperature was more efficient for uniform foaming-cell production. Fully dispersed clay platelets were, however, re-aggregated when subjected to a further melting processing. The reprocessed nanocomposites still had some exfoliated platelets as well as some aggregated intercalates. The dual role of the nanoclay particles as foaming nucleus and a crystallization nucleus was confirmed by cell growth observation and nonisothermal crystallization kinetics analysis. A low foaming temperature and a high saturation pressure were more favorable for obtaining a uniform foam. The PP copolymer was found to be foamed more easily than polypropylene. A small amount of other olefin moieties in the backbone of the polymer facilitated better foamability than the neat polypropylene.

A facile route to fabricate stable reduced graphene oxide dispersions in various media and their transparent conductive thin films.

In this paper, we demonstrate an easy way to prepare a stable reduced graphene oxide (RGO) dispersion in aqueous or organic media by simple adjustment of the degree of reduction and pH of RGO dispersion, and a subsequent fabrication of transparent conductive RGO thin films on various substrates using a spray coating technique. RGOs were prepared using a hydrazine reducing agent from graphene oxide (GO), which was oxidized from graphite via a modified Hummers' method. The degree of reduction determined the surface properties, such as atomic composition, surface polarity, and potential of RGO platelets. In addition, pH significantly affected the surface potential of graphene dispersion. The fine adjustment of degree of reduction and pH of RGO dispersion made production of fine RGO dispersions in aqueous and organic media such as ethanol and DMF possible without any aid of dispersing agents. The stable RGO dispersion using volatile ethanol medium provided a unique advantage to be spray-coated into uniform transparent conductive RGO thin films on various substrates including silicon wafer, flexible polycarbonate film regardless of their surface properties, and even on non-planar substrates such as round-shaped glassware at room temperature.

Enhanced interfacial adhesion between an amorphous polymer (polystyrene) and a semicrystalline polymer [a polyamide (nylon 6)].

We studied enhanced interfacial adhesion between an amorphous polymer (polystyrene, PS) and a semicrystalline polymer (a polyamide, Ny6). The fracture mechanism for this system was investigated to elicit a universal description on the fracture mechanism. The surface modification of PS to provide functional groups that can react with the functional groups of Ny6 was carried out with ion-beam and/or plasma treatment. These surface modifications were found to alter the interfacial adhesion strength between PS and Ny6. A remarkable enhancement was found with the surface functionalization of PS. Though the fracture toughness was varied depending on the process, its overall behavior was quite similar to that of others; the fracture toughness increased with increasing bonding temperature and bonding time, passed through a peak, and then decreased with a further increase of the bonding time or temperature. The variation of the fracture toughness with the bonding time and temperature can be plausibly explained in terms of two different failure mechanisms of adhesive failure and cohesive failure. This change appears more evidently for the interface between an amorphous polymer and a semicrystalline polymer than the interface between semicrystalline polymer pairs. Surface functionalization could exclude the effect of diffusion, thus clarifying the failure mechanisms occurring at the interface.

Physical properties of nanocomposites prepared by in situ polymerization of high-density polyethylene on multiwalled carbon nanotubes.

In situ metallocence polymerization was used to prepare nanocomposites of multiwalled carbon nanotubes (MWCNT) and high density polyethylene (HDPE). This polymerization method consists of attaching a metallocene catalyst complex onto the surface of MWCNT followed by surface-initiated polymerization to generate polymer brushes on the surface. All the procedures of polymerization made progress with one-pot process. The morphological observation of nanocomposites using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that the nanotubes are uniformly dispersed throughout HDPE matrix. Physical properties of thermal and electrical conductivities and rheological response have been characterized. Since the carbon nanotubes are wrapped by PE molecules, the large interface provided by MWCNT's lead to strong phonon boundary scattering. Thus, the enhancement of thermal conductivity by the inclusion of nanotubes was quite restrictive. On the other hand, electrical conductivity and rheological properties show the property transition at the critical concentration of carbon nanotubes (percolation threshold). The DC conductivity increased with increasing weight fraction of MWCNT from 1.0 x 10(-13) S cm(-1) (neat HDPE) to 1.3 x 10(-2) S cm(-1) (HDPE/7.3 wt% of MWCNT) at room temperature and the electrical percolation threshold was ca. 7.3 wt%. The percolation threshold concentration of MWCNT for the rheological properties was ca. 8.7 wt%, similar to that of the electrical conductivity. Difference in the percolation behaviors between the MWCNT mixed nanocomposites and the PE-coated MWCNT nanocomposites is discussed in terms of the dispersion and the tube-tube distance of MWCNT.

Piezoelectric properties of poly(vinylidene fluoride) and carbon nanotube blends: beta-phase development.

In order to get poly(vinylidene fluoride) (PVDF) films containing high beta-phase content, multiwalled carbon nanotubes (MWCNTs) were blended with PVDF. For drawn samples, the content of piezoelectric beta-form crystal was increased with MWCNT addition due to the rapid crystallization rate offered by the nucleating action of MWCNT, but soon reached a plateau. Poling on the drawn samples helps additional beta-phase formation when the added MWCNT content was less than 0.2 wt%; at this MWCNT amount, almost pure beta-phase crystal was obtained. More MWCNT addition induced depolarization to reduce the beta-phase content. Undrawn samples show monotonous increase of beta-phase content with MWCNT amount when subjected to poling.