A Highly Electrostrictive Salt Cocrystal and the Piezoelectric Nanogenerator Application of Its 3D-Printed Polymer Composite.

Ionic cocrystals with hydrogen bonding can form exciting materials with enhanced optical and electronic properties. We present a highly moisture-stable ammonium salt cocrystal [CH3C6H4CH(CH3)NH2][CH3C6H4CH(CH3)NH3][PF6] ((p-TEA)(p-TEAH)·PF6) crystallizing in the polar monoclinic C2 space group. The asymmetry in (p-TEA)(p-TEAH)·PF6 was induced by its chiral substituents, while the polar order and structural stability were achieved by using the octahedral PF6- anion and the consequent formation of salt cocrystal. The ferroelectric properties of (p-TEA)(p-TEAH)·PF6 were confirmed through P-E loop measurements. Piezoresponse force microscopy (PFM) enabled the visualization of its domain structure with characteristic "butterfly" and hysteresis loops associated with ferro- and piezoelectric properties. Notably, (p-TEA)(p-TEAH)·PF6 exhibits a large electrostrictive coefficient (Q33) value of 2.02 m4 C-2, higher than those found for ceramic-based materials and comparable to that of polyvinylidene difluoride. Furthermore, the composite films of (p-TEA)(p-TEAH)·PF6 with polycaprolactone (PCL) polymer and its gyroid-shaped 3D-printed composite scaled-up device, 3DP-Gy, were prepared and evaluated for piezoelectric energy-harvesting functionality. A high output voltage of 22.8 V and a power density of 118.5 µW cm-3 have been recorded for the 3DP-Gy device. Remarkably, no loss in voltage outputs was observed for the (p-TEA)(p-TEAH)·PF6 devices even after exposure to 99% relative humidity, showcasing their utility under extremely humid conditions.

3D-printed polymer composite devices based on a ferroelectric chiral ammonium salt for high-performance piezoelectric energy harvesting.

Three-dimensional printing (3DP) is an emerging technology to fabricate complex architectures, necessary to realize state-of-the-art flexible and wearable electronic devices. In this regard, top-performing devices containing organic ferro- and piezoelectric compounds are desired to circumvent significant shortcomings of conventional piezoceramics, e.g. toxicity and high-temperature device processibility. Herein, we report on a 3D-printed composite of a chiral ferroelectric organic salt {[Me3CCH(Me)NH3][BF4]} (1) with a biodegradable polycaprolactone (PCL) polymer that serves as a highly efficient piezoelectric nanogenerator (PENG). The ferroelectric property of 1 originates from its polar tetragonal space group P42, verified by P-E loop measurements. The ferroelectric domain characteristics of 1 were further probed by piezoresponse force microscopy (PFM), which gave characteristic 'butterfly' and hysteresis loops. The PFM amplitude vs. drive voltage measurements gave a relatively high magnitude of the converse piezoelectric coefficient for 1. PCL polymer composites with various weight percentages (wt%) of 1 were prepared and subjected to piezoelectric energy harvesting tests, which gave a maximum open-circuit voltage of 36.2 V and a power density of 48.1 µW cm-2 for the 10 wt% 1-PCL champion device. Furthermore, a gyroid-shaped 3D-printed 10 wt% 1-PCL composite was fabricated to test its practical utility, which gave an excellent output voltage of 41 V and a power density of 56.8 µW cm-2. These studies promise the potential of simple organic compounds for building PENG devices using advanced manufacturing technologies.

Thermally Activated Delayed Fluorescent Solvent-free Organic Liquid Hybrids for Tunable Emission Applications.

The synthetic feasibility and excellent luminescence features of organic molecules attracted much attention and were eventually found useful in lighting applications. In this context, a solvent-free organic liquid having attractive thermally activated delayed fluorescence features in bulk along with high processability has prime importance. Herein, we report a series of naphthalene monoimide-based solvent-free organic liquids exhibiting cyan to red thermally activated delayed fluorescence with luminescence quantum yields up to 80% and lifetimes between 10 to 45 µs. An effective approach explored energy transfer between liquid donors with various emitters exhibiting tunable emission colors, including white. The high processability of liquid emitters improved the compatibility with polylactic acid and was used for developing multicolor emissive objects using 3D printing. Our demonstration of the thermally activated delayed fluorescence liquid will be much appreciated as a processable alternate emissive material suitable for large-area lighting, display, and related applications.

A Ferroelectric Aminophosphonium Cyanoferrate with a Large Electrostrictive Coefficient as a Piezoelectric Nanogenerator.

Hybrid materials possessing piezo- and ferroelectric properties emerge as excellent alternatives to conventional piezoceramics due to their merits of facile synthesis, lightweight nature, ease of fabrication and mechanical flexibility. Inspired by the structural stability of aminophosphonium compounds, here we report the first A3 BX6 type cyanometallate [Ph2 (i PrNH)2 P]3 [Fe(CN)6 ] (1), which shows a ferroelectric saturation polarization (Ps ) of 3.71 µC cm-2 . Compound 1 exhibits a high electrostrictive coefficient (Q33 ) of 0.73 m4  C-2 , far exceeding those of piezoceramics (0.034-0.096 m4  C-2 ). Piezoresponse force microscopy (PFM) analysis demonstrates the polarization switching and domain structure of 1 further confirming its ferroelectric nature. Furthermore, thermoplastic polyurethane (TPU) polymer composite films of 1 were prepared and employed as piezoelectric nanogenerators. Notably, the 15 wt % 1-TPU device gave a maximum output voltage of 13.57 V and a power density of 6.03 µW cm-2 .

Ferroelectricity and Piezoelectric Energy Harvesting of Hybrid A2BX4-Type Halogenocuprates Stabilized by Phosphonium Cations.

Perovskite-structured compounds containing organic cations and inorganic anions have gained prominence as materials for next-generation electronic and energy devices. Hybrid materials possessing ferro- and piezoelectric properties are in recent focus for mechanical energy harvesting (nanogenerator) applications. Here, we report the ferroelectric behavior of A2BX4-type halogenocuprate materials supported by heteroleptic phosphonium cations. These lead-free discrete Cu(II) halides [Ph3MeP]2[CuCl4] (1) and [Ph3MeP]2[CuBr4] (2) exhibit a remnant polarization (P r) of 17.16 and 26.02 µC cm-2, respectively, at room temperature. Furthermore, flexible polymer films were prepared with various weight percentage (wt %) compositions of 1 in thermoplastic polyurethane (TPU) and studied for mechanical energy harvesting applications. A highest peak-to-peak voltage output of 25 V and power density of 14.1 µW cm-2 were obtained for the optimal 15 wt % 1-TPU composite film. The obtained output voltages were utilized for charging a 100 µF electrolytic capacitor that reaches its maximum charging point within 30 s with sizable stored energies and accumulated charges.

A Flexible Energy Harvester from an Organic Ferroelectric Ammonium Salt.

Organic ferroelectrics due to their low cost, easy preparation, light weight, high flexibility and phase stability are gaining tremendous attention in the field of portable electronics. In this work, we report the synthesis, structure and ferroelectric behavior of a two-component ammonium salt 2, containing a bulky [Bn(4-BrBn)NMe2 ]+ (Bn=benzyl and 4-BrBn=4-bromobenzyl) cation and tetrahedral (BF4 )- anion. The structural analysis revealed the presence of rich non-classical C-H⋅⋅⋅F and C-H⋅⋅⋅Br interactions in this molecule that were quantified by Hirshfeld surface analysis. The polarization (P) vs. electric field (E) hysteresis loop measurements on 2 gave a remnant polarization (Pr ) of 14.4 µC cm-2 at room temperature. Flexible polymer composites with various (5, 10, 15 and 20) weight percentages (wt%) of 2 in thermoplastic polyurethane (TPU) were prepared and tested for mechanical energy harvesting applications. A notable peak-to-peak output voltage of 20 V, maximum current density of 1.1 µA cm-2 and power density of 21.1 µW cm-2 were recorded for the 15 wt% 2-TPU composite device. Furthermore, the voltage output generated from this device was utilized to rapidly charge a 100 µF capacitor, with stored energies and measured charges of 156 µJ and 121.6 µC, respectively.

Piezoelectric Energy Harvesting from a Ferroelectric Hybrid Salt [Ph3 MeP]4 [Ni(NCS)6 ] Embedded in a Polymer Matrix.

Organic-inorganic hybrid ferroelectrics are an exciting class of molecular materials with promising applications in the area of energy and electronics. The synthesis, ferroelectric and piezoelectric energy harvesting behavior of a 3d metal ion-containing A4 BX6 type organic-inorganic hybrid salt [Ph3 MeP]4 [Ni(NCS)6 ] (1) is now presented. P-E hysteresis loop studies on 1 show a remnant ferroelectric polarization value of 18.71 µC cm-2 , at room temperature. Composite thermoplastic polyurethane (TPU) devices with 5, 10, 15 and 20 wt % compositions of 1 were prepared and employed for piezoelectric energy harvesting studies. A maximum output voltage of 19.29 V and a calculated power density value of 2.51 mW cm-3 were observed for the 15 wt % 1-TPU device. The capacitor charging experiments on the 15 wt % 1-TPU composite device shows an excellent energy storage performance with the highest stored energies and measured charges of 198.8 µJ and 600 µC, respectively.

Influence of nanocellulose on mechanics and morphology of polyvinyl alcohol xerogels.

Xerogels are porous networks of crosslinked polymers that are useful for biomedical applications such as drug delivery, scaffold engineering, tissue regeneration, cell culture and wound dressing. However, inferior mechanical properties curtail their applications to a considerable extent. Nanocellulose fibers and crystals are often added into the polymer matrix to improve their mechanical strength. Here, nanocellulose in the mass ratios of 7%, 13% and 18% are loaded into polyvinyl alcohol (PVA) matrix followed by thermo-morpho-mechanical characterization. With increase in nanocellulose content, thermal degradation occurs at a lower temperature. It is observed that addition of higher quantity of nanocellulose crystals leads to the formation of weak cellulose-rich regions causing xerogel rupture. This is predominantly observed for xerogel loaded with 18% nanocellulose crystals. Similarly, addition of higher quantity of nanocellulose fibers increase brittleness of the xerogels causing fracture. This is predominantly observed for xerogel loaded with 18% nanocellulose fibers. Creep strain and stress relaxation is observed to decrease with addition of nanocellulose loading owing to molecular chain restriction and polymer chain immobility.

A Flexible Composite Mechanical Energy Harvester from a Ferroelectric Organoamino Phosphonium Salt.

A new binary organic salt diphenyl diisopropylamino phosphonium hexaflurophosphate (DPDP⋅PF6 ) was shown to exhibit a good ferroelectric response and employed for mechanical energy harvesting application. The phosphonium salt crystallizes in the monoclinic noncentrosymmetric space group Cc and exhibits an H-bonded 1D chain structure due to N-H⋅⋅⋅F interactions. Ferroelectric measurements on the single crystals of DPDP⋅PF6 gave a well-saturated rectangular hysteresis loop with a remnant (Pr ) polarization value of 6 µC cm-2 . Further, composite devices based on polydimethylsiloxane (PDMS) films for various weight percentages (3, 5, 7, 10 and 20 wt %) of DPDP⋅PF6 were prepared and examined for power generation by using an impact test setup. A maximum output peak-to-peak voltage (VPP ) of 8.5 V and an output peak-to-peak current (IPP ) of 0.5 µA was obtained for the non-poled composite film with 10 wt % of DPDP⋅PF6 . These results show the efficacy of organic ferroelectric substances as potential micropower generators.

Fire-Retardant, Self-Extinguishing Inorganic/Polymer Composite Memory Foams.

Polymeric foams used in furniture and automotive and aircraft seating applications rely on the incorporation of environmentally hazardous fire-retardant additives to meet fire safety norms. This has occasioned significant interest in novel approaches to the elimination of fire-retardant additives. Foams based on polymer nanocomposites or based on fire-retardant coatings show compromised mechanical performance and require additional processing steps. Here, we demonstrate a one-step preparation of a fire-retardant ice-templated inorganic/polymer hybrid that does not incorporate fire-retardant additives. The hybrid foams exhibit excellent mechanical properties. They are elastic to large compressional strain, despite the high inorganic content. They also exhibit tunable mechanical recovery, including viscoelastic "memory". These hybrid foams are prepared using ice-templating that relies on a green solvent, water, as a porogen. Because these foams are predominantly comprised of inorganic components, they exhibit exceptional fire retardance in torch burn tests and are self-extinguishing. After being subjected to a flame, the foam retains its porous structure and does not drip or collapse. In micro-combustion calorimetry, the hybrid foams show a peak heat release rate that is only 25% that of a commercial fire-retardant polyurethanes. Finally, we demonstrate that we can use ice-templating to prepare hybrid foams with different inorganic colloids, including cheap commercial materials. We also demonstrate that ice-templating is amenable to scale up, without loss of mechanical performance or fire-retardant properties.

Polyhedral Oligomeric Silsesquioxane-Containing Thiol-ene Fibers with Tunable Thermal and Mechanical Properties.

Polyhedral oligomeric silsesquioxanes (POSS) are versatile inorganic-organic hybrid building blocks that have potential applications as reinforcement nanofillers, thermal stabilizers, and catalyst supports for metal nanoparticles. However, fabrication of fibrous materials with high POSS content has been a challenge because of the aggregation and solubility limits of POSS units. In this paper, we describe a robust and environmentally friendly fabrication approach of inorganic-organic hybrid POSS fibers by integrating UV initiated thiol-ene polymerization and centrifugal fiber spinning. The use of monomeric liquids in this approach not only reduces the consumption of heat energy and solvent, but it also promotes homogeneous mixing of organic and inorganic components that allows integration of large amount of POSS (up to 80 wt %) into the polymer network. The POSS containing thiol-ene fibers exhibited enhanced thermomechanical properties compared to purely organic analogs as revealed by substantial increases in residual weight and a factor of 4 increase in modulus after thermal treatment at 1000 °C. This simple fabrication approach combined with the tunability in fiber properties afforded by tailoring monomer composition make POSS containing thiol-ene fibers attractive candidates for catalyst supports and filtration media, particularly in high-temperature and harsh environments.

Mechanically stable thermally crosslinked poly(acrylic acid)/reduced graphene oxide aerogels.

Graphene oxide (GO) aerogels, high porosity (>99%) low density (∼3-10 mg cm(-3)) porous materials with GO pore walls, are particularly attractive due to their lightweight, high surface area, and potential use in environmental remediation, superhydrophobic and superoleophilic materials, energy storage, etc. However, pure GO aerogels are generally weak and delicate which complicates their handling and potentially limits their commercial implementation. The focus of this work was to synthesize highly elastic, mechanically stable aerogels that are robust and easy to handle without substantially sacrificing their high porosity or low density. To overcome this challenge, a small amount of readily available and thermally cross-linkable poly(acrylic acid) (PAA) was intermixed with GO to enhance the mechanical integrity of the aerogel without disrupting other desirable characteristic properties. This method is a simple straightforward procedure that does not include multistep or complicated chemical reactions, and it produces aerogels with mass densities of about 4-6 mg cm(-3) and >99.6% porosity that can reversibly support up to 10,000 times their weight with full recovery of their original volume. Finally, pressure sensing capabilities were demonstrated and their oil absorption capacities were measured to be around 120 g oil per g aerogel(-1) which highlights their potential use in practical applications.

Highly stretchable thermoset fibers and nonwovens using thiol-ene photopolymerization.

In this report, we describe the preparation and characterization of a new class of thermoset fibers with high elongation and elastic recovery. Integrating UV-activated thiol-ene photopolymerization and electrospinning, we demonstrate an environmentally friendly single step approach to convert small monomeric precursor molecules into highly elastic fibers and nonwoven mats. The fibers were derived by in situ photopolymerization of a trifunctional vinyl ether monomer and a tetrafunctional thiol. Although thermosets often offer good chemical and thermal stability, these fibers also have a high average elongation at break of 62%. The elastomeric nature of these vinyl-ether based fibers can be partly attributed to their subambient Tg and partly to the cross-link density, monomer structure, and resulting network homogeneity. Nonwoven mats of these fibers were also stretchable and exhibited a much higher elongation at break of about 85%. These thermoset stretchable fibers could have potential applications as textile, biomedical, hot chemical filtration, and composite materials.

Synthesis of Amphiphilic Naturally-Derived Oligosaccharide-block-Wax Oligomers and Their Self-Assembly.

Self-assembly characteristics of amphiphilic macromolecules into micelles, nanoparticles and vesicles has been of fundamental interest for many applications including designed nanoscale therapeutic delivery systems and enzymatic reactors. In this work, a class of amphiphilic block oligomers was synthesized from naturally occurring oligosaccharides and aliphatic alcohol precursors, which are all currently prominent in the pharmaceutical, food, and supplement industries. These block oligomer materials were synthesized by functionalization of the precursor materials followed by subsequent coupling by azide-alkyne cycloaddition and their bulk self-assembly was investigated after solvent vapor annealing. Self-assembly of the amphiphilic materials into liposomes in aqueous solution was also investigated after preparing solutions using a nanoprecipitation method. Encapsulation of hydrophobic components was demonstrated and verified using dynamic light scattering, transmission electron microscopy, and fluorescence spectroscopy experiments.

Bioinspired catecholic copolymers for antifouling surface coatings.

We report here a synthetic approach to prepare poly(methyl methacrylate)-polydopamine diblock (PMMA-PDA) and triblock (PDA-PMMA-PDA) copolymers combining mussel-inspired catecholic oxidative chemistry and atom transfer radical polymerization (ATRP). These copolymers display very good solubility in a range of organic solvents and also a broad band photo absorbance that increases with increasing PDA content in the copolymer. Spin-cast thin films of the copolymer were stable in water and showed a sharp reduction (by up to 50%) in protein adsorption compared to those of neat PMMA. Also the peak decomposition temperature of the copolymers was up to 43°C higher than neat PMMA. The enhanced solvent processability, thermal stability and low protein adsorption characteristics of this copolymer makes it attractive for variety of applications including antifouling coatings on large surfaces such as ship hulls, buoys, and wave energy converters.

pH-Responsive Cellulose Nanocrystal Gels and Nanocomposites.

We show that functionalization of the surface of cellulose nanocrystals (CNCs) with either carboxylic acid (CNC-CO2H) or amine (CNC-NH2) moieties renders the CNCs pH-responsive. At low pH, where the amine groups are protonated, CNC-NH2 forms aqueous dispersions in water on account of electrostatic repulsions of the ammonium moieties inhibiting aggregation. However, a transition to hydrogels is observed at higher pH where the CNC-NH2 are neutral and the attractive forces based on hydrogen bonding dominate. The opposite behavior is observed for CNC-CO2H, which are dispersible at high pH and form gels in an acidic environment. We further show that these pH-responsive CNCs can be incorporated into a poly(vinyl acetate) matrix to yield mechanically adaptive pH-responsive nanocomposite films.

Solventless High Throughput Manufacturing of Poly(butylene terephthalate) Nanofibers.

Nanofibers possess high surface area to volume ratios and are particularly attractive for a variety of applications including tissue regeneration, drug delivery, fiber-reinforced composites, filtration, and protective clothing. Though the production of nanofibers from common thermoplastic polymers is relatively well-demonstrated, processing constraints have limited high throughput manufacturing of nanofibers from high performance polymers. This has in turn limited broad technological exploitation of polymer nanofibers in areas such as hot chemical filtration or high-performance lightweight composites for aerospace and defense applications. We report here that nanofibers can be produced in a solventless high throughput process from polymers such as poly(butylene terephthalate) (PBT) using a newly developed technology termed "Forcespinning" that employs centrifugal force to attenuate fibers. Our investigations also show that these nanofibers have a high crystallinity and enhanced molecular orientation which is important for realizing desirable physical and chemical properties of many high-performance polymer fibers.

Soybean Oil Based Fibers Made Without Solvent or Heat.

Thiol-ene chemistry was harnessed to enable production of thermochemically stable thermoset fibers containing 50-87 wt % acrylated epoxidized soybean oil and 49-72% biobased carbon without using solvent or heat. In this demonstration, the fibers were made by simultaneous electrospinning and photocuring of a liquid monomer mixture, which could be translated to other fiber manufacturing processes such as melt blowing or Forcespinning. Scanning electron micrographs illustrate the fiber quality and an average diameter of about 30 µm. Photochemical conversion kinetics of functional groups during light exposure were measured by real-time Fourier transform infrared spectroscopy, providing insight into the advantages of using high-functionality monomers and thiol-ene chemistry in this application.

Biologically inspired hierarchical design of nanocomposites based on poly(ethylene oxide) and cellulose nanofibers.

Attempts to create hierarchically structured, uniaxially oriented nanocomposites comprising cellulose nanowhiskers (CNWs), which promise anisotropic mechanical properties, are exceedingly rare. We report here the fabrication of uniaxially-oriented arrays of microfibers based on poly(ethylene oxide) (PEO) and CNWs by electrospinning. Compared with the neat PEO fibers, the incorporation of CNWs within the fibers increased the storage modulus (E') of arrays along the fiber axis of the PEO/CNW nanocomposite fibers. Successful incorporation of the CNWs within each of the as-spun PEO/CNW nanocomposite fibers in the direction parallel to the fiber axis was verified by both scanning and transmission electron microscopy.

Stress transfer in cellulose nanowhisker composites--influence of whisker aspect ratio and surface charge.

The mechanically induced molecular deformation of cellulose nanowhiskers embedded in subpercolation concentration in an epoxy resin matrix was monitored through Raman spectroscopy. Cellulose nanowhiskers isolated by sulfuric acid hydrolysis from tunicates and by sulfuric acid hydrolysis and hydrochloric acid hydrolysis from cotton were used to study how the aspect ratio (ca. 76 for tunicate and 19 for cotton) and surface charges (38 and 85 mmol SO(4)(-)/kg for sulfuric acid hydrolysis of cotton and tunicate, respectively; no detectable surface charges for hydrochloric acid hydrolysis) originating from the isolation process influence stress transfer in such systems. Atomic force microscopy confirmed that uncharged cellulose nanowhiskers produced by hydrochloric acid hydrolysis have a much higher tendency to aggregate than the charged cotton or tunicate nanowhiskers. Each of these nanowhisker types was incorporated in a concentration of 0.7 vol % in a thermosetting epoxy resin matrix. Mechanically induced shifts of the Raman peak initially located at 1095 cm(-1) were used to express the level of deformation imparted to the nanowhiskers embedded in the resin. Much larger shifts of the diagnostic Raman band were observed for nanocomposites with tunicate nanowhiskers than for the corresponding samples comprising cotton nanowhiskers. In the case of nanocomposites comprising nanowhiskers produced by hydrochloric acid hydrolysis, no significant Raman band shift was observed. These results are indicative of different modes of stress transfer, which in turn appear to originate from the different sample morphologies.