Realizing reversible phase transformation of shape memory ceramics constrained in aluminum.

Small-scale shape memory ceramics exhibit superior shape memory or superelasticity properties, while their integration into a matrix material and the subsequent attainment of their reversible tetragonal-monoclinic phase transformations remains a challenge. Here, cerium-doped zirconia (CZ) reinforced aluminum (Al) matrix composite is fabricated, and both macroscopic and microscopic mechanical tests reveal more than doubled compressive strength and energy absorbance of the composites as compared with pure Al. Full austenitization in the CZ single-crystal clusters is achieved when they are constrained by the Al matrix, and reversible martensitic transformation triggered by thermal or stress stimuli is observed in the composite micro-pillars without causing fracture in the composite. These results are interpreted by the strong geometric confinement offered by the Al matrix, the robust CZ/Al interface and the local three-dimensional particle network/force-chain configuration that effectively transfer mechanical loads, and the decent flowability of the matrix that accommodates the volume change during phase transformation.

Simultaneous Enhancement of Polymerization Kinetics and Properties of Phthalonitrile Using Alumina Fillers.

Alumina particles are investigated as a potential catalyst for phthalonitrile polymerization and as a property enhancer. In this work, extensive characterizations were conducted on alumina-filled resorcinol-based phthalonitrile to differentiate between the catalytic effect and the filler effect. Thermal gravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy suggest the occurrence of chemical interaction between alumina fillers and phthalonitrile, which provides an insight into the better performance of alumina-filled phthalonitrile resins. This hypothesis is further supported by the additional Al-N peak observed in the X-ray photoelectron spectroscopy (XPS) analysis when alumina is added to phthalonitrile before curing, as well as the presence of an exothermic peak in the differential scanning calorimetry (DSC) analysis that indicates the catalytic polymerization of phthalonitrile. This catalytic phenomenon observed by the addition of alumina fillers is beneficial for the improvement of the conventionally slow curing process of phthalonitrile and, more importantly, is coupled with observable enhancement of thermomechanical properties of the composite.

Bond engineering of molecular ferroelectrics renders soft and high-performance piezoelectric energy harvesting materials.

Piezoelectric materials convert mechanical stress to electrical energy and thus are widely used in energy harvesting and wearable devices. However, in the piezoelectric family, there are two pairs of properties that improving one of them will generally compromises the other, which limits their applications. The first pair is piezoelectric strain and voltage constant, and the second is piezoelectric performance and mechanical softness. Here, we report a molecular bond weakening strategy to mitigate these issues in organic-inorganic hybrid piezoelectrics. By introduction of large-size halide elements, the metal-halide bonds can be effectively weakened, leading to a softening effect on bond strength and reduction in polarization switching barrier. The obtained solid solution C6H5N(CH3)3CdBr2Cl0.75I0.25 exhibits excellent piezoelectric constants (d33 = 367 pm/V, g33 = 3595 × 10-3 Vm/N), energy harvesting property (power density is 11 W/m2), and superior mechanical softness (0.8 GPa), promising this hybrid as high-performance soft piezoelectrics.

3D Printing of Transparent Spinel Ceramics with Transmittance Approaching the Theoretical Limit.

3D printing of transparent ceramics has attracted great attention recently but faces the challenges of low transparency and low printing resolution. Herein, magnesium aluminate spinel transparent ceramics with transmittance reaching 97% of the theoretical limit are successfully fabricated using a stereolithography-based 3D printing method assisted by hot isostatic pressing and the critical factors governing the transparency are revealed. Various transparent spinel lenses and microlattices are printed at a high resolution of ≈100-200 µm. The 3D printed spinel lens demonstrates fairly good optical imaging ability, and the printed spinel diamond microlattices as a transparent photocatalyst support for TiO2 significantly enhance its photocatalytic efficiency compared with its opaque counterparts. Compared with other 3D printed transparent materials such as silica glass or organic polymers, the printed spinel ceramics have the advantages of broad optical window, high hardness, excellent high-temperature stability, and chemical resistance and therefore, have great potential to be used in various optical lenses/windows and photocatalyst supports for application in harsh environments.

Unraveling the Mechanistic Origins of Epoxy Degradation in Acids.

Water diffusion into polymers like thermosetting epoxies is well-studied; however, comparably little has been reported thus far on the related but very different mechanism of acid diffusion and the corresponding influence on material degradation. The diffusion of hydrochloric acid into an amine-cured epoxy system was studied in this work using gravimetric analysis and dielectric monitoring concurrently, and the mass uptake behavior was observed to differ significantly compared with water diffusion, faster by an order of magnitude. A unique 3-stage diffusion of acid into epoxy was observed due to the influence of Coulombic interactions between oppositely charged ionic species diffusing at different rates. Material characterization studies have revealed that the dominant degradation mechanism is physical in nature, with the formation of surface cracks driven by the swelling stresses due to the core-shell swelling behavior in highly concentrated hydrochloric acid, leading to an erosion-type degradation phenomenon. The insights gained from understanding acid electrolyte diffusion could serve to design a more effective and efficient process to enable thermoset recycling by facilitating rapid material breakdown or the design of acid-resistant materials for various applications in chemical storage tanks, batteries, and protective coatings in a corrosive environment.

High-Density 3D-Boron Nitride and 3D-Graphene for High-Performance Nano-Thermal Interface Material.

Compression studies on three-dimensional foam-like graphene and h-BN (3D-C and 3D-BN) revealed their high cross-plane thermal conductivity (62-86 W m-1 K-1) and excellent surface conformity, characteristics essential for thermal management needs. Comparative studies to state-of-the-art materials and other materials currently under research for heat dissipation revealed 3D-foam's improved performance (20-30% improved cooling, temperature decrease by ΔT of 44-24 °C).

High brightness formamidinium lead bromide perovskite nanocrystal light emitting devices.

Formamidinium lead halide (FAPbX3) has attracted greater attention and is more prominent recently in photovoltaic devices due to its broad absorption and higher thermal stability in comparison to more popular methylammonium lead halide MAPbX3. Herein, a simple and highly reproducible room temperature synthesis of device grade high quality formamidinium lead bromide CH(NH2)2PbBr3 (FAPbBr3) colloidal nanocrystals (NC) having high photoluminescence quantum efficiency (PLQE) of 55-65% is reported. In addition, we demonstrate high brightness perovskite light emitting device (Pe-LED) with these FAPbBr3 perovskite NC thin film using 2,2',2″-(1,3,5-Benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) commonly known as TPBi and 4,6-Bis(3,5-di(pyridin-3-yl)phenyl)-2-methylpyrimidine (B3PYMPM) as electron transport layers (ETL). The Pe-LED device with B3PYMPM as ETL has bright electroluminescence of up to 2714 cd/m2, while the Pe-LED device with TPBi as ETL has higher peak luminous efficiency of 6.4 cd/A and peak luminous power efficiency of 5.7 lm/W. To our knowledge this is the first report on high brightness light emitting device based on CH(NH2)2PbBr3 widely known as FAPbBr3 nanocrystals in literature.

Stabilization of 4H hexagonal phase in gold nanoribbons.

Gold, silver, platinum and palladium typically crystallize with the face-centred cubic structure. Here we report the high-yield solution synthesis of gold nanoribbons in the 4H hexagonal polytype, a previously unreported metastable phase of gold. These gold nanoribbons undergo a phase transition from the original 4H hexagonal to face-centred cubic structure on ligand exchange under ambient conditions. Using monochromated electron energy-loss spectroscopy, the strong infrared plasmon absorption of single 4H gold nanoribbons is observed. Furthermore, the 4H hexagonal phases of silver, palladium and platinum can be readily stabilized through direct epitaxial growth of these metals on the 4H gold nanoribbon surface. Our findings may open up new strategies for the crystal phase-controlled synthesis of advanced noble metal nanomaterials.

Synthesis of ultrathin face-centered-cubic au@pt and au@pd core-shell nanoplates from hexagonal-close-packed au square sheets.

The synthesis of ultrathin face-centered-cubic (fcc) Au@Pt rhombic nanoplates is reported through the epitaxial growth of Pt on hexagonal-close-packed (hcp) Au square sheets (AuSSs). The Pt-layer growth results in a hcp-to-fcc phase transformation of the AuSSs under ambient conditions. Interestingly, the obtained fcc Au@Pt rhombic nanoplates demonstrate a unique (101)f orientation with the same atomic arrangement extending from the Au core to the Pt shell. Importantly, this method can be extended to the epitaxial growth of Pd on hcp AuSSs, resulting in the unprecedented formation of fcc Au@Pd rhombic nanoplates with (101)f orientation. Additionally, a small amount of fcc (100)f -oriented Au@Pt and Au@Pd square nanoplates are obtained with the Au@Pt and Au@Pd rhombic nanoplates, respectively. We believe that these findings will shed new light on the synthesis of novel noble bimetallic nanostructures.

Surface modification-induced phase transformation of hexagonal close-packed gold square sheets.

Conventionally, the phase transformation of inorganic nanocrystals is realized under extreme conditions (for example, high temperature or high pressure). Here we report the complete phase transformation of Au square sheets (AuSSs) from hexagonal close-packed (hcp) to face-centered cubic (fcc) structures at ambient conditions via surface ligand exchange, resulting in the formation of (100)f-oriented fcc AuSSs. Importantly, the phase transformation can also be realized through the coating of a thin metal film (for example, Ag) on hcp AuSSs. Depending on the surfactants used during the metal coating process, two transformation pathways are observed, leading to the formation of (100)f-oriented fcc Au@Ag core-shell square sheets and (110)h/(101)f-oriented hcp/fcc mixed Au@Ag nanosheets. Furthermore, monochromated electron energy loss spectroscopy reveals the strong surface plasmon resonance absorption of fcc AuSS and Au@Ag square sheet in the infrared region. Our findings may offer a new route for the crystal-phase and shape-controlled synthesis of inorganic nanocrystals.

The role of metal layers in the formation of metal-silicon hybrid nanoneedle arrays.

We investigated nanoneedle arrays fabricated on a series of metal-silicon substrates using Ga(+) ion beam patterning. It is shown that the low sputtering rate of the metal is preserved on the tip of each nanoneedle in the form of a gallium alloy nanodot. The generated nanodot was found to greatly alleviate the ion sputtering of the underlying materials. These protective metals are promising materials that act as a shelter for the functional layer, which is vulnerable to ion beam irradiation. In the present work, as an example, we report a bundle of GaAs nanowhiskers that were successfully grown on each gold nanodot protected by an iron-gallium alloy.

Towards perfectly ordered novel ZnO/Si nano-heterojunction arrays.

The fabrication of a highly ordered novel ZnO/Si nano-heterojuntion array is introduced. ZnO seed layer is first deposited on the Si (P<111>) surface. The nucleation sites are then defined by patterning the surface through focused ion beam (FIB) system. The ZnO nanorods are grown on the nucleation sites through hydrothermal process. The whole fabrication process is simple, facile and offers direct control of the space, length and aspect ratio of the array. It is found that ZnO/Si nanojunctions show an improved interface when subjected to heat treatment. The recrystallization of ZnO and the tensile lattice strain of Si developed during the heating process contribute the enhancement of their photoresponses to white light. The photoluminescence (PL) measurement result of nano-heterojunction arrays with different parameters is discussed.

Shape memory and superelastic ceramics at small scales.

Shape memory materials are a class of smart materials able to convert heat into mechanical strain (or strain into heat) by virtue of a martensitic phase transformation. Some brittle materials such as intermetallics and ceramics exhibit a martensitic transformation but fail by cracking at low strains and after only a few applied strain cycles. Here we show that such failure can be suppressed in normally brittle martensitic ceramics by providing a fine-scale structure with few crystal grains. Such oligocrystalline structures reduce internal mismatch stresses during the martensitic transformation and lead to robust shape memory ceramics that are capable of many superelastic cycles up to large strains; here we describe samples cycled as many as 50 times and samples that can withstand strains over 7%. Shape memory ceramics with these properties represent a new class of actuators or smart materials with a set of properties that include high energy output, high energy damping, and high-temperature usage.

A hybrid nanostructure array for gas sensing with ultralow field ionization voltage.

We fabricate a unique hybrid nanostructure array for gas sensing based on the polarization mechanism at the nanoscale. It is shown that with platinum nanocrystallites on the top of each nanoneedle, this array can work at ultralow voltages (less than 10 V) as a field ionization gas sensor. We believe that the polarized platinum brings about a local enhanced electrical field, leading to the direct field ionization of gas molecules, which is confirmed by calculations of the charge accumulation and electrical field distribution.

Joining copper oxide nanotube arrays driven by the nanoscale Kirkendall effect.

Various annealing conditions (environment, temperature, and duration) are applied to study the nanoscale Kirkendall effect of copper (Cu) nanowire (NW) arrays on a Si substrate. The results show that an appropriate amount of oxygen supply is crucial for uniform transformation from Cu NWs (average diameter ∼50 nm) into Cu oxide nanotube arrays. An annealing duration of 30 min at 200 °C in a low vacuum environment reveals that the voids are not uniformly distributed at the Cu/Cu oxide interface. This suggests that void growth is due to surface diffusion of Cu along void surfaces. Annealing above 200 °C for 60 min resulted in complete transformation from Cu NWs into Cu oxide nanotubes. X-ray photoelectron spectroscopy characterization indicates that the Cu oxides formed at 200 °C and 300 °C are Cu2O and CuO, respectively. It is demonstrated that the transformation from Cu NW arrays into Cu oxide nanotube arrays can be combined with the joining of stacked Si chips in a single-process step with reasonable joint shear strength. Transmission electron microscopy-electron energy loss spectroscopy elemental mapping analysis reveals that the joint interface is Cu oxide. The outward diffusion of Cu driven by the nanoscale Kirkendall effect is believed to enhance the joining process. By controlling the environment, temperature, and duration, joined Cu2O or CuO nanotube stacked chips can be achieved, which serve as a platform for the further development of nanostructured, stacked devices.

Forest of gold nanowires: a new type of nanocrystal growth.

We report a nanowire growth that is highly unconventional: (1) nanowires can grow from substrate-bound seeds but cannot from colloidal seeds under otherwise the same conditions; (2) the nanowires grow from only one side of the seeds, with their diameter independent of the size of the seeds; and (3) vertically aligned ultrathin nanowires are obtained on substrates, using aqueous solution and ambient conditions. With carefully designed experiments, we propose and test a new mechanism that can explain these unusual phenonmena. It turns out that the strong binding of ligands in this system forces selective deposition of Au at the ligand-deficient interface between Au seeds and oxide substrates. This means of promoting anisotropic growth of nanocrystals into nanowires is previously unknown in the literature. We are able to pinpoint the site of active growth and explain the control of nanowire width. The sustained growth at the active site and the inhibited growth at its parameter push the nanocrystals upward into wires; their diameter is dependent on the dynamic competition of the two processes. The site-specific growth from substrate-anchored seeds provides a rare means to create substrate-nanowire hierarchical structures in aqueous solution under ambient conditions. Rendering a surface conductive, particularly one with complex surface morphology, is now made easy.

Vapor-liquid-solid growth of endotaxial semiconductor nanowires.

Free-standing and in-plane lateral nanowires (NWs) grown by the vapor-liquid-solid (VLS) process have been widely reported. Herein, we demonstrate that the VLS method can be extended to the synthesis of horizontally aligned semiconductor NWs embedded in substrates. Endotaxial SiGe NWs were grown in silicon substrates by tuning the directional movement of the catalyst in the substrates. The location of the SiGe NWs can be controlled by the SiO(2) pattern on the silicon surface. By varying the growth conditions, the proportion of Ge in the obtained NWs can also be tuned. This approach opens up an opportunity for the spatial control of the NW growth in substrates and can potentially broaden the applications of NWs in new advanced fields.

Self-organization of a hybrid nanostructure consisting of a nanoneedle and nanodot.

A special materials system that allows the self-organization of a unique hybrid nanonipple structure is developed. The system consists of a nanoneedle with a small nanodot sitting on top. Such hybrid nanonipples provide building blocks to assemble functional devices with significantly improved performance. The application of the system to high-sensitivity gas sensors is also demonstrated.

Graphene oxide-templated synthesis of ultrathin or tadpole-shaped au nanowires with alternating hcp and fcc domains.

Ultrathin Au nanowires (AuNWs) and tadpole-shaped nanowires are synthesized on graphene oxide (GO) sheet templates. For the first time, 1.6 nm-diameter AuNWs are shown to contain hexagonal close-packed (hcp) crystal domains, and the tadpole-shaped nanowires exhibit alternating sets of hcp and face-centered cubic (fcc) structures, associated with variation in wire thickness.

Synthesis of hexagonal close-packed gold nanostructures.

Solid gold is usually most stable as a face-centred cubic (fcc) structure. To date, no one has synthesized a colloidal form of Au that is exclusively hexagonal close-packed (hcp) and stable under ambient conditions. Here we report the first in situ synthesis of dispersible hcp Au square sheets on graphene oxide sheets, which exhibit an edge length of 200-500 nm and a thickness of ~ 2.4 nm (~ 16 Au atomic layers). Interestingly, the Au square sheet transforms from hcp to a fcc structure on exposure to an electron beam during transmission electron microscopy analysis. In addition, as the square sheet grows thicker (from ~ 2.4 to 6 nm), fcc segments begin to appear. A detailed experimental analysis of these structures shows that for structures with ultrasmall dimensions (for example, <~ 6 nm thickness for the square sheets), the previously unobserved pure hcp structure becomes stable and isolable.