High‐Nanofiller‐Content Graphene Oxide–Polymer Nanocomposites via Vacuum‐Assisted Self‐Assembly

Highly ordered, homogeneous polymer nanocomposites of layered graphene oxide are prepared using a vacuum‐assisted self‐assembly (VASA) technique. In VASA, all components (nanofiller and polymer) are pre‐mixed prior to assembly under a flow, making it compatible with either hydrophilic poly(vinyl alcohol) (PVA) or hydrophobic poly(methyl methacrylate) (PMMA) for the preparation of composites with over 50 wt% filler. This process is complimentary to layer‐by‐layer assembly, where the assembling components are required to interact strongly (e.g., via Coulombic attraction). The nanosheets within the VASA‐assembled composites exhibit a high degree of order with tunable intersheet spacing, depending on the polymer content. Graphene oxide–PVA nanocomposites, prepared from water, exhibit greatly improved modulus values in comparison to films of either pure PVA or pure graphene oxide. Modulus values for graphene oxide–PMMA nanocomposites, prepared from dimethylformamide, are intermediate to those of the pure components. The differences in structure, modulus, and strength can be attributed to the gallery composition, specifically the hydrogen bonding ability of the intercalating species     

Microstructural Origins of High Piezoelectric Performance: A Pathway to Practical Lead‐Free Materials

Piezoelectric materials interconvert between electrical energy and mechanical strain and are widely used for electronic and electromechanical devices. Owing to growing environmental concerns, development of lead‐free piezoelectric materials with enhanced properties becomes of great interest. Key to the academic problem is a lack of fundamental understanding on the actual mechanisms involved at the microscopic (unit cell) level. While it is well known that giant responses occur near structural phase boundaries, and it has long been proposed that polarization rotation and nanodomains are major determinants, so far, atomistic understanding of the origin of the response has come mostly from theoretical simulations. Recently, notable breakthroughs have been achieved in improving the properties of piezoceramics and thin films. Precise mapping of atomic displacements by atomically resolved Z‐contrast imaging has demonstrated that gradual polarization rotation bridges the coexisting nanophases. These structural features, which take place on a length scale of just a few nanometers, now visible through aberration‐corrected microscopy, provide a new pivotal understanding on the outstanding piezoelectric behavior that has been obtained in all systems. They also provide key guiding principles for the development of lead‐free piezoelectrics, especially in the form of thin films, which remain far behind bulk ceramics at the time being. Coexistence of nanophases with flexible interconversion, introduced via phase boundary engineering, holds much promise for achieving high performance in other material systems with phase transitions.     

Lead‐Free Polycrystalline Ferroelectric Nanowires with Enhanced Curie Temperature

Ferroelectrics are important technological materials with wide‐ranging applications in electronics, communication, health, and energy. While lead‐based ferroelectrics have remained the predominant mainstay of industry for decades, environmentally friendly lead‐free alternatives are limited due to relatively low Curie temperatures (T _C) and/or high cost in many cases. Efforts have been made to enhance T _C through strain engineering, often involving energy‐intensive and expensive fabrication of thin epitaxial films on lattice‐mismatched substrates. Here, a relatively simple and scalable sol–gel synthesis route to fabricate polycrystalline (Ba_0.85Ca_0.15)(Zr_0.1Ti_0.9)O₃ nanowires within porous templates is presented, with an observed enhancement of T _C up to ≈300 °C as compared to ≈90 °C in the bulk. By combining experiments and theoretical calculations, this effect is attributed to the volume reduction in the template‐grown nanowires that modifies the balance between different structural instabilities. The results offer a cost‐effective solution‐based approach for strain‐tuning in a promising lead‐free ferroelectric system, thus widening their current applicability.     

Self‐Assembled Heteroepitaxial Oxide Nanocomposite Thin Film Structures: Designing Interface‐Induced Functionality in Electronic Materials

Achieving self‐assembling/self‐organizing systems is the holy grail of nanotechnology. Spontaneous organization is not unique to the physical sciences since nature has been producing such systems for millions of years. In biological systems global patterns emerge from numerous interactions among lower‐level components of the system. The same is true for physical systems. In this review, the self‐assembly mechanisms of oxide nanocomposite films, as well as the advantageous functionalities that arise from such ordered structures, are explored.     

High‐Energy Al/CuO Nanocomposites Obtained by DNA‐Directed Assembly

Over the next few years, it is expected that new, energetic, multifunctional materials will be engineered. There is a need for new methods to assemble such materials from manufactured nanopowders. In this article, we demonstrate a DNA‐directed assembly procedure to produce highly energetic nanocomposites by assembling Al and CuO nanoparticles into micrometer‐sized particles of an Al/CuO nanocomposite, which has exquisite energetic performance in comparison with its physically mixed Al/CuO counterparts. Using 80 nm Al nanoparticles, the heat of reaction and the onset temperature are 1.8 kJ g^?1 and 410 °C, respectively. This experimental achievement relies on the development of simple and reliable protocols to disperse and sort metallic and metal oxide nanopowders in aqueous solution and the establishment of specific DNA surface‐modification processes for Al and CuO nanoparticles. Overall, our work, which shows that DNA can be used as a structural material to assemble Al/Al, CuO/CuO and Al/CuO composite materials, opens a route for molecular engineering of the material on the nanoscale.     

Nanoscale Insight Into Lead‐Free BNT‐BT‐xKNN

Piezoresponse force microscopy (PFM) is used to afford insight into the nanoscale electromechanical behavior of lead‐free piezoceramics. Materials based on Bi_1/2Na_1/2TiO₃ exhibit high strains mediated by a field‐induced phase transition. Using the band excitation technique the initial domain morphology, the poling behavior, the switching behavior, and the time‐dependent phase stability in the pseudo‐ternary system (1–x)(0.94Bi_1/2Na_1/2TiO₃‐0.06BaTiO₃)‐xK_0.5Na_0.5NbO₃ (0 <= x <= 18 mol%) are revealed. In the base material (x = 0 mol%), macroscopic domains and ferroelectric switching can be induced from the initial relaxor state with sufficiently high electric field, yielding large macroscopic remanent strain and polarization. The addition of KNN increases the threshold field required to induce long range order and decreases the stability thereof. For x = 3 mol% the field‐induced domains relax completely, which is also reflected in zero macroscopic remanence. Eventually, no long range order can be induced for x >= 3 mol%. This PFM study provides a novel perspective on the interplay between macroscopic and nanoscopic material properties in bulk lead‐free piezoceramics.     

A Water‐Soluble Mechanochromic Luminescent Pyrene Derivative Exhibiting Recovery of the Initial Photoluminescence Color in a High‐Humidity Environment

Switching of the luminescence properties of molecular materials in response to mechanical stimulation is of fundamental interest and also has a range of potential applications. Herein, a water‐soluble mechanochromic luminescent pyrene derivative having two hydrophilic dendrons is reported. This pyrene derivative is the first example of a mechanochromic luminescent organic compound that responds to relative humidity. Mechanical stimulation (grinding) of this pyrene derivative in the solid state results in a change of the photoluminescence from yellow to green. Subsequent exposure to water vapor induces recovery of the initial yellow photoluminescence. The color change is reversible through at least ten cycles. It is also demonstrated that this compound can be applied as a mechano‐sensing material in frictional wear testing for grease, owing to its immiscibility in non‐polar solvents and its non‐crystalline behavior. Transmission electron microscope and atomic force microscope observations of samples prepared from dilute aqueous solutions of the pyrene derivative on suitable substrates, together with dynamic light scattering measurements for the compound in aqueous solution, indicate that this amphiphilic dumbbell‐shaped molecule forms micelles in water.     

Temperature‐Insensitive (K,Na)NbO3‐Based Lead‐Free Piezoactuator Ceramics

The development of lead‐free piezoceramics has attracted great interest because of growing environmental concerns. A polymorphic phase transition (PPT) has been utilized in the past to tailor piezoelectric properties in lead‐free (K,Na)NbO₃ (KNN)‐based materials accepting the drawback of large temperature sensitivity. Here a material concept is reported, which yields an average piezoelectric coefficientd₃₃ of about 300 pC/N and a high level of unipolar strain up to 0.16% at room temperature. Most intriguingly, field‐induced strain varies less than 10% from room temperature to 175 °C. The temperature insensitivity of field‐induced strain is rationalized using an electrostrictive coupling to polarization amplitude while the temperature‐dependent piezoelectric coefficient is discussed using localized piezoresponse probed by piezoforce microscopy. This discovery opens a new development window for temperature‐insensitive piezoelectric actuators despite the presence of a polymorphic phase transition around room temperature.     

Control of the Properties of Micrometer‐Sized Actuators from Liquid Crystalline Elastomers Prepared in a Microfluidic Setup

In this article new results on the preparation of monodisperse particles from a liquid crystalline elastomer in a microfluidic setup are presnted. For this, droplets from a liquid crystalline monomer are prepared in a microfluidic device and polymerized while they are flowing inside a microtube. The parti­cles obtained by this method possess an internal orientation, which gives them actuating properties. When they are heated into the isotropic phase of the liquid crystalline material they show a reversible change in shape whereby they change their length in one direction by almost 100%. It is shown how the variation of experimental parameters during their synthesis impacts the properties of these micro‐actuators. Influence over their primal shape, the strength of their shape changing properties, their size, and their mechanical properties is demontrated. From the systematic variation of experimental parameters a deep understanding of the complex processes taking place in a flowing droplet of a liquid crystalline material is obtainted. Additionally NMR analysis and swelling experiments on these actuating materials are provided.     

Alginate Encapsulation of Bioengineered Protein‐Coated Polyhydroxybutyrate Particles: A New Platform for Multifunctional Composite Materials

Immobilization and display of proteins is extensively used to enhance stability and performance of proteins for technical uses such as in biotechnology. Here, self‐assembled nonporous polyhydroxybutyrate (PHB) particles bioengineered to display proteins of interest are subjected to alginate encapsulation processes. The novel composite spheres are fabricated using ionotropic gelation methods. The immunoglobulin G (IgG) binding domain Z and organophosphate hydrolase (OpdA) are attached to PHB particles, and are examples for bioseparation and bioremediation applications, respectively. Alginate microspheres entrapping Z domain coated PHB particles enable flow‐through purification of IgG. Microsphere porosity is pH tunable and at acidic pH IgG is released from Z domains but retained within microspheres. OpdA‐PHB particles are functionally entrapped in alginate microspheres enabling flow‐through substrate conversion. Attachment of functional proteins to PHB particles enhances retention within the alginate microspheres. The hydrophobic PHB particle core within alginate beads provides payload for lipophilic substances, which adsorption kinetics are aligned with a pseudo‐second‐order kinetic model in agreement with the Freundlich isotherm model. This study describes the development of a multifunctional composite material platform based on alginate spheres encapsulating PHB particles that provide payload for lipophilic substances and can be engineered to display protein functions of interest.     

Programmed High‐Hole‐Mobility Supramolecular Polymers from Disk‐Shaped Molecules

In this paper a simple, casting solution technique for the preparation of two‐dimensional (2D) arrays of very‐high molecular weight (MW) 1D‐Pc supramolecular inorganic polymers is described. The soluble fluoroaluminium tetra‐tert‐butylphthalocyanine (ttbPcAlF) is synthesized and characterized, which can be self‐assembled to form 2D arrays of very‐high‐MW 1D‐Pc supramolecular inorganic polymers. High‐resolution transmission electron microscopy (HRTEM) demonstrates that the 1D‐ttbPcAlF, having a cofacial ring spacing of ～0.36 nm and an interchain distance of ～1.7 nm, self‐assembles into 2D‐nanosheets (～140 nm in length, ～20 nm in width, and equivalent to MW of 3.2 × 10⁵ g mol^?1). The film cast from a 1,2‐dichloroethane (DCE) solution shows a minimum hole‐mobility of ～0.3 cm² V^?1 s^?1 at room temperature by flash‐photolysis time‐resolved microwave conductivity (TRMC) measurements and a fairly high dark dc‐conductivity of ～1 × 10^?3 S cm^?1.     

Auxetic Foam‐Based Contact‐Mode Triboelectric Nanogenerator with Highly Sensitive Self‐Powered Strain Sensing Capabilities to Monitor Human Body Movement

The first contact‐mode triboelectric self‐powered strain sensor using an auxetic polyurethane foam, conductive fabric, and polytetrafluroethylene (PTFE) is fabricated. Utilizing the auxetic properties of the polyurethane foam, the auxetic polyurethane foam would expand into the PTFE when the foam is stretched, causing contact electrification. Due to a larger contact area between the PTFE and the foam as the foam is stretched, this device can serve effectively as a strain sensor. The sensitivity of this method is explored, and this sensor has the highest sensitivity in all triboelectric nanogenerator devices that are used previously as a strain sensor. Different applications of this strain sensor are shown, and this sensor can be used as a human body monitoring system, self‐powered scale to measure weight, and a seat belt to measure body movements inside a car seat.     

Diffused Phase Transition Boosts Thermal Stability of High‐Performance Lead‐Free Piezoelectrics

High piezoelectricity of (K,Na)NbO₃ (KNN) lead‐free materials benefits from a polymorphic phase transition (PPT) around room temperature, but its temperature sensitivity has been a bottleneck impeding their applications. It is found that good thermal stability can be achieved in CaZrO₃‐modified KNN lead‐free piezoceramics, in which the normalized strain d ₃₃* almost keeps constant from room temperature up to 140 °C. In situ synchrotron X‐ray diffraction experiments combined with permitivity measurements disclose the occurrence of a new phase transformation under an electrical field, which extends the transition range between tetragonal and orthorhombic phases. It is revealed that such an electrically enhanced diffused PPT contributed to the boosted thermal stability of KNN‐based lead‐free piezoceramics with high piezoelectricity. The present approach based on phase engineering should also be effective in endowing other lead‐free piezoelectrics with high piezoelectricity and good temperature stability.     

Template‐Free Synthesis of Electroconductive Triphenylamine–Silica Nanotubes Exhibiting a Mixed‐Valence State

The self‐assembly and polycondensation of a triphenylamine‐derived organosilane precursor in an aqueous mixture result in electroactive organosilica nanotubes without the use of template materials. The nanotubes are easily synthesized by the slow addition of water to an acidified organic solution of the precursor, followed by basification with an aqueous NaOH solution. In contrast to conventional sol–gel methods that yield amorphous organosilica materials, the present organosilica nanotubes exhibit birefringence due to the orientation of the triphenylamine moieties within the tube walls. The template‐free formation of nanotubes with optical anisotropy suggests a roll‐up mechanism of 2D nanosheets consisting of hydrolyzed precursors. The organosilica nanotubes contain a high density of oriented triphenylamine moieties, and exhibit a mixed‐valence state with a near‐infrared absorption band due to chemical doping along with high electrical conductivities, on the order of 10⁻³–10⁻² S cm⁻¹. Such nanostructured organosilicas, comprising an electroactive framework, are useful for optoelectronic and photocatalytic applications.     

High‐Temperature BiScO3‐PbTiO3 Piezoelectric Vibration Energy Harvester

Conventionally, effective mechanical vibration energy harvesting is based on (Pb,Zr)TiO₃ (PZT) ceramics, poly(vinylidene fluoride) (PVDF) polymers or PVDF/PZT or other piezoelectric composite materials, and their working temperature is normally limited to room temperature (R‐T) or below 150 °C. Here, bismuth scandium lead titanate (BiScO₃‐PbTiO₃, abbreviated as BSPT) ceramic is reported which has a high Curie temperature point around 450 °C and its application for high‐temperature (H‐T) vibration energy harvesting. Experimental results show that it exhibits an excellent H‐T piezoelectricity, converting mechanical vibration energy into electric power effectively in a wide temperature range from R‐T till 250 °C. This research shows the BSPT piezoelectric energy harvester having the potential application for self‐power source of wireless sensor network system in high temperature circumstance.     

Advanced Materials for High‐Temperature Thermal Transport

High temperature processes are widely used in a variety of existing and emerging industrial and aerospace applications. The thermal properties of high‐temperature materials thus play an important role in controlling the thermal energy, as highlighted by successful applications of thermal barrier coating and aerogels. While thermal transport processes at room and low temperature have witnessed tremendous progress in the past two decades, particularly on the fronts of understanding basic heat transfer properties at the micro‐ and nanoscale, the understanding at high temperature is still at the nascent stage, owing to several unique features at high temperature, such as the dominant Umklapp scattering effect that can render a crystalline material amorphous‐like thermal properties, and the important radiation contribution at high temperature. This lack of systematic understanding, coupled with the challenges in maintaining high‐temperature stability in a large number of materials, has limited the development of materials to meet the thermal transport properties pertaining to several current and emerging high‐temperature applications. This Review is aimed at providing an overview of the basic mechanisms governing thermal transport processes at high temperature, to identify their unique features and challenges, and to explore opportunities in material research for high‐temperature thermal materials.     

Inch‐Size Single Crystal of a Lead‐Free Organic–Inorganic Hybrid Perovskite for High‐Performance Photodetector

Large‐size crystals of organic–inorganic hybrid perovskites (e.g., CH₃NH₃PbX₃, X = Cl, Br, I) have gained wide attention since their spectacular progress on optoelectronic technologies. Although presenting brilliant semiconducting properties, a serious concern of the toxicity in these lead‐based hybrids has become a stumbling block that limits their wide‐scale applications. Exploring lead‐free hybrid perovskite is thus highly urgent for high‐performance optoelectronic devices. Here, a new lead‐free perovskite hybrid (TMHD)BiBr₅ (TMHD = N,N,N,N‐tetramethyl‐1,6‐hexanediammonium) is prepared from facile solution process. Emphatically, inch‐size high‐quality single crystals are successfully grown, the dimensions of which reach up to 32 × 24 × 12 mm³. Furthermore, the planar arrays of photodetectors based on bulk lead‐free (TMHD)BiBr₅ single crystals are first fabricated, which shows sizeable on/off current ratios (≈10³) and rapid response speed (τ_rise = 8.9 ms and τ_decay = 10.2 ms). The prominent device performance of (TMHD)BiBr₅ strongly underscores the lead‐free hybrid perovskite single crystals as promising material candidates for optoelectronic applications.     

Self‐Doping Cathode Interfacial Material Simultaneously Enabling High Electron Mobility and Powerful Work Function Tunability for High‐Efficiency All‐Solution‐Processed Polymer Light‐Emitting Diodes

A variety of N ‐hydrogenated/N ‐methylated pyridinium salts are elaborately designed and synthesized. Thermogravimetric and X‐ray photoelectron spectra analysis indicate the intensities of the N? H covalent bonds are strengthened step‐by‐step from 3,3′‐(5′‐(3‐(pyridin‐3‐yl)phenyl)‐[1,1′:3′,1″‐terphenyl]‐3,3″‐diyl)dipyridine (Tm)‐HCl to Tm‐HBr and then Tm‐TfOH, which results in gradually improved cathode interfacial modification abilities. The larger dipole moments of N⁺? H containing moieties compared to those of the N⁺? CH₃ endow them with more preferable interfacial modification abilities. Electron paramagnetic resonance signals reveal the existence of radical anions in the solid state of Tm‐TfOH, which enables its self‐doping property and high electron mobility up to 1.67 × 10^?3 cm² V^?1 s^?1. Using the Tm‐TfOH as the cathode interfacial layers (CILs), the phenyl‐substituted poly(para ‐phenylene vinylene)‐based all‐solution‐processed polymer light‐emitting diodes (PLEDs) achieve more preferable device performances than the poly[(9,9‐bis(3′‐(N ,N ‐dimethylamino)propyl)‐2,7‐fluorene)‐alt ‐2,7‐(9,9‐dioctylfluorene)]‐based ones, i.e., high current density of nearly 300 mA cm^?2, very high luminance over 15 000 cd m^?2 at a low bias of 5 V. Remarkably, the thickness of the CILs has little impact on the device performance and high efficiencies are maintained even at thicknesses up to 85 nm, which is barely realized in PLEDs with small‐molecule‐based electron transporting layers.     

A Redox‐Triggered Bispecific Supramolecular Nanomedicine Based on Peptide Self‐Assembly for High‐Efficacy and Low‐Toxic Cancer Therapy

Polo‐like kinase 1 (PLK1) and polo‐like kinase 4 (PLK4) are closely associated with the progression of several cancers, and their bispecific inhibitors can kill tumor cells effectively. Herein, a redox‐responsive bispecific supramolecular nanomedicine based on the self‐assembly of a cyclic peptide, termed as C‐1, targeting both PLK1 and PLK4 as a potent anticancer agent is reported. C‐1 is a cyclic peptide in response to reducing agents such as glutathione (GSH), which is constructed by a combined approach of pharmacophore modeling, molecular docking, and reversible cyclization. After entering the cytosol of cancer cell, the disulfide linkage is reduced by intracellular GSH, with the resulting linear conformation self‐assembling into bispecific nanofibers. C‐1 can lead to apoptotic cell death by inducing caspase‐3 activation and PARP cleavage in HeLa cells. Moreover, it suppresses the growth of HeLa cells in cell assays, and inhibits the progression of HeLa cells‐induced xenografts in nude mice without inducing notable side effects. This work provides a successful example of developing the redox‐responsive bispecific nanomedicine for high‐efficacy and low‐toxic cancer therapy.