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At least 55 records · Page 3

Pulsed laser deposition and structural evolution of BaF 2 nanolayers in Eu-doped BaF 2 /Al 2 O 3 layered optical nanocomposite thin films

Here, we have developed a pulsed laser deposition (PLD) geometry for the growth of uniform BaF 2 nanoscale thin films, through control of the deposition conditions. Our goal is to use the BaF 2 layers with controllable structure as component layers in layered optical nanocomposites. The structure of the BaF 2 nanolayer evolves as a function of the layer thickness: BaF 2 grows via a layer-by-layer growth mode on Al 2 O 3 ; the layers are amorphous for a thickness < 3 nm, and then become nanocrystalline as the layer thickness increases. The BaF 2 nanocrystals have an FCC crystal structure with a weak < 111 > texture that becomes stronger for thicker films. We then demonstrate that our BaF2 films can be introduced into layered Al 2 O 3 /BaF 2 /EuO x nanocomposite films, which allows for control of the relative position of the Eu ions and the BaF 2 layer. Cross-section samples of the multilayered films show interfacial intermixing between the layers, which is related to implantation during the PLD process. This intermixing enables the incorporation of Eu ions into BaF 2 layers and form a thin Eu-doped BaF 2 nanolayer at the interface. The layered nanocomposite films show photoluminescence (PL) emission from Eu 3+ ions, and the PL intensity changes can be correlated with the crystallinity and crystal size changes in the BaF 2 layer. Our results provide guidance for achieving thin film nanocomposite materials with controllable structure and photoluminescence behavior for light emitting diodes, photovoltaics and other optical applications.

36 MATERIALS SCIENCE↗

Mechanically and Thermally Enhanced 3D-Printed Photocurable Polymer Nanocomposites Containing Functionalized Chitin Nanowhiskers by Stereolithography

Additive manufacturing, or simply 3D printing (3DP), where objects are built through layer-wise material deposition, has gained significant academic and industrial attention as a result of the development of advanced and functional materials requiring rapid, customized, and flexible solutions. In the context of green manufacturing, diversifying environmentally and economically sustainable material portfolios is an essential endeavor for the success of 3DP technology that uses widely available, highly valuable, and renewable materials. Here, we used stereolithography (SLA) for processing methacrylate-based photocurable resins containing crab shell-derived chitin nanowhiskers (CNWs), which are surface-functionalized by reactive acrylate groups. Results from full spectral, thermal, structural, and topological analyses corroborate not only the surface functionalization of CNWs but also indicate the presence of these photocurable CNW (pCNW) fillers in the 3D-printed nanocomposites. Owing to the strong interfacial bond induced by the physical and chemical crosslinking between the pCNW and methacrylate (MA) polymer matrix, the internally formulated nanocomposites displayed enhanced thermomechanical properties (e.g., storage modulus and glass transition temperature) compared to those of commercially available pure SLA resins. For instance, the inclusion of 0.5 wt % pCNW improved the tensile strength and stiffness to up to 78 and 71%, respectively, without compromising the toughness and ductility of the printed material. Accordingly, this result also evidences the compatibility between the filler and resin materials. Consequently, the formation of a crosslinked network in the nanocomposite structure results in a higher thermal stability and activation energy (i.e., up to ~79%) for all the hybrid materials than the pristine MA. Finally, the high-resolution SLA print features, dimensional accuracy, and enhanced mechanical performance of our microstructure-forming functionalized chitin-based nanocomposites make them promising materials for a wide range of robust and high-performance industrial applications.

36 MATERIALS SCIENCE↗

Development of Fe 3 O 4 core–TiO 2 shell nanocomposites and nanoconjugates as a foundation for neuroblastoma radiosensitization

Neuroblastoma is the most common extracranial solid malignancy in childhood which, despite the current progress in radiotherapy and chemotherapy protocols, still has a high mortality rate in high risk tumors. Nanomedicine offers exciting and unexploited opportunities to overcome the shortcomings of conventional medicine. The photocatalytic properties of Fe 3 O 4 core-TiO 2 shell nanocomposites and their potential for cell specific targeting suggest that nanoconstructs produced using Fe 3 O 4 core-TiO 2 shell nanocomposites could be used to enhance radiation effects in neuroblastoma. In this study, we evaluated bare, metaiodobenzylguanidine (MIBG) and 3,4-Dihydroxyphenylacetic acid (DOPAC) coated Fe 3 O4@TiO 2 as potential radiosensitizers for neuroblastoma in vitro. The uptake of bare and MIBG coated nanocomposites modestly sensitized neuroblastoma cells to ionizing radiation. Conversely, cells exposed to DOPAC coated nanocomposites exhibited a five-fold enhanced sensitivity to radiation, increased numbers of radiation induced DNA double-strand breaks, and apoptotic cell death. The addition of a peptide mimic of the epidermal growth factor (EGF) to nanoconjugates coated with MIBG altered their intracellular distribution. Cryo X-ray fluorescence microscopy tomography of frozen hydrated cells treated with these nanoconjugates revealed cytoplasmic as well as nuclear distribution of the nanoconstructs. The intracellular distribution pattern of different nanoconjugates used in this study was different for different nanoconjugate surface molecules. Cells exposed to DOPAC covered nanoconjugates showed the smallest nanoconjugate uptake, with the most prominent pattern of large intracellular aggregates. Interestingly, cells treated with this nanoconjugate also showed the most pronounced radiosensitization effect in combination with the external beam x-ray irradiation. Further studies are necessary to evaluate mechanistic basis for this increased radiosensitization effect. Preliminary studies with the nanoparticles carrying an EGF mimicking peptide showed that this approach to targeting could perhaps be combined with a different approach to radiosensitization – use of nanoconjugates in combination with the radioactive iodine. Much additional work will be necessary in order to evaluate possible benefits of targeted nanoconjugates carrying radionuclides.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Multilaminate Energy Storage Films from Entropy‐Driven Self‐Assembled Supramolecular Nanocomposites

Abstract Composite materials comprising polymers and inorganic nanoparticles (NPs) are promising for energy storage applications, though challenges in controlling NP dispersion often result in performance bottlenecks. Realizing nanocomposites with controlled NP locations and distributions within polymer microdomains is highly desirable for improving energy storage capabilities but is a persistent challenge, impeding the in‐depth understanding of the structure–performance relationship. In this study, a facile entropy‐driven self‐assembly approach is employed to fabricate block copolymer‐based supramolecular nanocomposite films with highly ordered lamellar structures, which are then used in electrostatic film capacitors. The oriented interfacial barriers and well‐distributed inorganic NPs within the self‐assembled multilaminate nanocomposites effectively suppress leakage current and mitigate the risk of breakdown, showing superior dielectric strength compared to their disordered counterparts. Consequently, the lamellar nanocomposite films with optimized composition exhibit high energy efficiency (>90% at 650 MV m −1 ), along with remarkable energy density and power density. Moreover, finite element simulations and statistical modeling have provided theoretical insights into the impact of the lamellar structure on electrical conduction, electric field distribution, and electrical tree propagation. This work marks a significant advancement in the design of organic–inorganic hybrids for energy storage, establishing a well‐defined correlation between microstructure and performance.

Li, He↗

Optimizing Piezoelectric Nanocomposites by High‐Throughput Phase‐Field Simulation and Machine Learning

Abstract Piezoelectric nanocomposites with oxide fillers in a polymer matrix combine the merit of high piezoelectric response of the oxides and flexibility as well as biocompatibility of the polymers. Understanding the role of the choice of materials and the filler‐matrix architecture is critical to achieving desired functionality of a composite towards applications in flexible electronics and energy harvest devices. Herein, a high‐throughput phase‐field simulation is conducted to systematically reveal the influence of morphology and spatial orientation of an oxide filler on the piezoelectric, mechanical, and dielectric properties of the piezoelectric nanocomposites. It is discovered that with a constant filler volume fraction, a composite composed of vertical pillars exhibits superior piezoelectric response and electromechanical coupling coefficient as compared to the other geometric configurations. An analytical regression is established from a linear regression‐based machine learning model, which can be employed to predict the performance of nanocomposites filled with oxides with a given set of piezoelectric coefficient, dielectric permittivity, and stiffness. This work not only sheds light on the fundamental mechanism of piezoelectric nanocomposites, but also offers a promising material design strategy for developing high‐performance polymer/inorganic oxide composite‐based wearable electronics.

42 ENGINEERING↗

Preparation and Photocatalytic Hydrogen Production of TiO 2 /(AlMnCoNiZn) 3 O 4 Nanocomposites

Photocatalytic water splitting is a promising strategy for addressing the global energy crisis and environmental pollution. In this study, spinel-type high-entropy oxide (HEO) nanoparticles, (AlMnCoNiZn) 3 O 4 , were successfully synthesized via a solution combustion method. TiO 2 /(AlMnCoNiZn) 3 O 4 nanocomposites with varying molar ratios were subsequently fabricated through solid-state sintering, and their photocatalytic water-splitting performance was systematically investigated. The hydrogen production rate initially increased and then decreased with increasing TiO 2 content. The optimal nanocomposite achieved a hydrogen evolution rate of 1450 μmol·h −1 ·g −1 under simulated sunlight irradiation, which is 2.2 times higher than that of pure TiO 2 nanoparticles. In addition, the TiO 2 /(AlMnCoNiZn) 3 O 4 nanocomposites exhibited significantly improved photocorrosion resistance compared with TiO 2 nanoparticles. After 12 h irradiation under a 500-W high-pressure mercury lamp, the hydrogen production rates of the nanocomposites and pure TiO 2 retained 79.3% and 5.47% of their initial values, respectively. These results demonstrate the important role of (AlMnCoNiZn) 3 O 4 and other HEOs in enhancing the photocatalytic performance of nanoheterojunction catalysts. Lastly, this work broadens the potential applications of (AlMnCoNiZn) 3 O 4 and related HEO materials in the field of photocatalysis.

Heterojunction↗

Block copolymer-mediated synthesis of TiO2/RuO2 nanocomposite for efficient oxygen evolution reaction

Abstract An amphiphilic block copolymer, poly (styrene-2-polyvinyl pyridine-ethylene oxide), was used as a structure-directing and stabilizing agent to synthesize TiO 2 /RuO 2 nanocomposite. The strong interaction of polymers with metal precursors led to formation of a porous heterointerface of TiO 2 /RuO 2 . It acted as a bridge for electron transport, which can accelerate the water splitting reaction. Scanning electron microscopy, energy-dispersive X -ray spectroscopy, transmission electron microscopy, and X -ray diffraction analysis of TiO 2 /RuO 2 samples revealed successful fabrication of TiO 2 /RuO 2 nanocomposites. The TiO 2 /RuO 2 nanocomposites were used to measure electrochemical water splitting in three-electrode systems in 0.1-M KOH. Electrochemical activities unveil that TiO 2 /RuO 2 -150 nanocomposites displayed superior oxygen evolution reaction activity, having a low overpotential of 260 mV with a Tafel slope of 80 mVdec −1 . Graphical abstract

36 MATERIALS SCIENCE↗

Impact of cobalt doping on structural and magnetic properties of zinc oxide nanocomposites synthesized by mechanical ball-milling method

A series of zinc oxide (ZnO) semiconductor nanocomposite samples doped with different concentrations of cobalt (Co) were successfully synthesized via simple and highly effective mechanical ball-milling method using suitable precursors. All doped nanocomposites crystallized in hexagonal wurtzite formation of ZnO. No alteration in the wurtzite structure, with no evidence of any segregated secondary phase(s) was detected with increasing doping concentrations. This result unambiguously verified the substitution of Zn 2+ sites by Co 2+ ions in the ZnO host lattice for different doping concentrations. Moreover, room temperature ferromagnetic behavior was observed in all doped nanocomposite samples in the reported work. Present study clearly shows that mechanical ball-milling is a facile, inexpensive, eco-friendly method to synthesize crystalline and magnetic Co doped ZnO nanocomposites for next generation spin-based devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Strong graphene oxide nanocomposites from aqueous hybrid liquid crystals

Combining polymers with small amounts of stiff carbon-based nanofillers such as graphene or graphene oxide is expected to yield low-density nanocomposites with exceptional mechanical properties. However, such nanocomposites have remained elusive because of incompatibilities between fillers and polymers that are further compounded by processing difficulties. Here we report a water-based process to obtain highly reinforced nanocomposite films by simple mixing of two liquid crystalline solutions: a colloidal nematic phase comprised of graphene oxide platelets and a nematic phase formed by a rod-like high-performance aramid. Upon drying the resulting hybrid biaxial nematic phase, we obtain robust, structural nanocomposites reinforced with graphene oxide.

36 MATERIALS SCIENCE↗

Zinc Oxide–Graphene Nanocomposite-Based Sensor for the Electrochemical Determination of Cetirizine

A nanocomposite electrode of graphene (Gr) and zinc oxide (ZnO) nanoparticles was fabricated to study the electrochemical oxidation behavior of an anti-inflammatory drug, i.e., cetirizine (CET). The voltametric response of CET for bare CPE, Gr/CPE, ZnO/CPE, and the ZnO-Gr nanocomposite electrode was studied. The modifier materials were characterized using scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray powder diffraction (XRD) to comprehend the surface morphology of the utilized modifiers. The influence of pH, scan rate, and accumulation time on the electrooxidation of CET was examined. It was found that the electrochemical oxidation of CET was diffusion-controlled, in which two protons and two electrons participated. The detection limit was found to be 2.8 × 10 -8 M in a linearity range of 0.05–4.0 µM. Study of excipients was also performed, and it was found that they had negligible interference with the peak potential of CET. The validation and utility of the fabricated nanocomposite sensor material were examined by analyzing clinical and biological samples. Stability testing of the nanocomposite electrode was conducted to assess the reproducibility, determining that the developed biosensor has good stability and high efficiency in producing reproducible results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bismuth Subcarbonate Decorated Reduced Graphene Oxide Nanocomposite for the Sensitive Stripping Voltammetry Analysis of Pb(II) and Cd(II) in Water

In this paper, bismuth subcarbonate (BiO)2CO3-reduced graphene oxide nanocomposite incorporated in Nafion matrix ((BiO)2CO3-rGO-Nafion) was synthesized and further applied, for the first time, in the sensitive detection of Pb(II) and Cd(II) by square-wave anodic stripping voltammetry (SWASV). The as-synthesized nanocomposites were characterized by energy-dispersive spectroscopy (EDS), Raman spectroscopy, scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). (BiO)2CO3 composite plays a key role in the improvement of the detection sensitivity, which can form multicomponent alloy with cadmium and lead. Additionally, the unique structure of rGO can enlarge the surface area and provide abundant active sites. Moreover, Nafion incorporation in the nanocomposite can effectively increase the adhesion and mechanical strength of the film, and further improve the preconcetration ability due to the cation-exchange capacity of its abundant sulfonate groups. As expected, the (BiO)2CO3-rGO/Nafion nanocomposite-modified glassy carbon electrode ((BiO)2CO3-rGO-Nafion/GCE) achieved low detection limits of 0.24 μg/L for Pb(II) and 0.16 μg/L for Cd(II), in the linear range of 1.0–60 μg/L, and showed some excellent performance, such as high stability, good selectivity, and sensitivity. Finally, synthetic water samples were prepared and further used to verify the practicability of the (BiO)2CO3-rGO-Nafion/GCE with satisfactory results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Hybrid materials and nanocomposite materials, methods of making same, and uses thereof

Hybrid materials and nanocomposite materials, methods of making and using such materials. The nanoparticles of the nanocomposite are formed in situ during pyrolysis of a hybrid material comprising metal precursor compounds. The nanoparticles are uniformly distributed in the carbon matrix of the nanocomposite. The nanocomposite materials can be used in devices such as, for example, electrodes and on-chip inductors.

Archer, Lynden A.↗

Tunable anisotropy of co-based nanocomposites for magnetic field sensing and inductor applications

A method includes producing an amorphous precursor to a nanocomposite, the amorphous precursor comprising a material that is substantially without crystals not exceeding 20% volume fraction; performing devitrification of the amorphous precursor, wherein the devitrification comprises a process of crystallization; forming, based on the devitrification, the nanocomposite with nano-crystals that contains an induced magnetic anisotropy; tuning, based on one or more of composition, temperature, configuration, and magnitude of stress applied during annealing and modification, the magnetic anisotropy of the nanocomposite; and adjusting, based on the tuned magnetic anisotropy, a magnetic permeability of the nanocomposite.

Leary, Alex M.↗

Comparative study of helium bubbles in a Ti-Ta alloy and a Ti/Ta nanocomposite

Here, we investigated the size, density, and distribution of helium (He) bubbles in a Ti-Ta single-phase alloy and a Ti/Ta dual-phase nanocomposite using transmission electron microscopy. The Ti/Ta nanocomposite was fabricated via phase separation during high-temperature annealing of the single-phase Ti-Ta alloy. He ion implantation in the Ti-Ta single-phase alloy leads to the formation of nano-scale He bubbles (~1.7 nm in size, ~2.6×10 5 /μm 3 in volumetric density). He bubbles were found to segregate to grain boundaries. Under identical implantation conditions, numerous He bubbles also formed in the Ti/Ta nanocomposite. Closer inspection revealed that He bubbles in the Ti-rich phase are smaller and of higher volumetric density (~1.2 nm, ~8.4×10 5 /μm 3 ) than those in the Tarich phase (~3 nm, ~1.8×10 5 /μm 3 ) and the single-phase alloy. He bubbles were also observed to decorate phase boundaries, but they were generally smaller than those on grain boundaries. These results suggest that Ti/Ta phase boundaries are less conducive to the growth of large He bubbles than grain boundaries in the Ti-Ta single phase alloy.

36 MATERIALS SCIENCE↗

Target Configuration Effect on Microstructures and Properties of Vertically Aligned Nanocomposites

Vertically aligned nanocomposites (VANs) are unique thin films with vertical nanostructures embedded in a matrix material, allowing for the integration of two distinct materials. These nanocomposites offer novel combined physical properties, such as nanocomposite-based multiferroics and strongly coupled physical properties, such as magneto-optic coupling. Much work has been conducted in exploring different two-phase combinations and various processing conditions to achieve novel tunable properties that cannot be obtained by any single-phase material alone. Here, in this work, the target configuration effects are explored for the growth of LaFeO 3 –CoNi 2 O 4 VANs. Both mixed and pie-shaped targets are utilized to compare the target configuration effects on the phase separation, morphology tuning, and their resulting physical properties, including optical and magnetic properties. This work suggests that the target configuration is another important parameter for achieving the desired VAN morphology and can be used to design different two-phase VANs with tailorable properties.

36 MATERIALS SCIENCE↗

Exploiting Saturation Regimes and Surface Effects to Tune Composite Design: Single Platelet Nanocomposites of Peptoid Nanosheets and CaCO 3

Mineral-polymer composites found in nature exhibit exceptional structural properties essential to their function, and transferring these attributes to the synthetic design of functional materials holds promise across various sectors. Biomimetic fabrication of nanocomposites introduces new pathways for advanced material design and explores biomineralization strategies. This study presents a novel approach for producing single platelet nanocomposites composed of CaCO 3 and biomimetic peptoid (N-substituted glycines) polymers, akin to the bricks found in the brick-and-mortar structure of nacre, the inner layer of certain mollusc shells. The significant aspect of the proposed strategy is the use of organic peptoid nanosheets as the scaffolds for brick formation, along with their controlled mineralization in solution. Here, we employ the B28 peptoid nanosheet as a scaffold, which readily forms free-floating zwitterionic bilayers in aqueous solution. The peptoid nanosheets were mineralized under consistent initial conditions (σ calcite = 1.2, pH 9.00), with variations in mixing conditions and supersaturation profiles over time aimed at controlling the final product. Nanosheets were mineralized in both feedback control experiments, where supersaturation was continuously replenished by titrant addition and in batch experiments without a feedback loop. Complete coverage of the nanosheet surface by amorphous calcium carbonate was achieved under specific conditions with feedback control mineralization, whereas vaterite was the primary CaCO 3 phase observed after batch experiments. Thermodynamic calculations suggest that time-dependent supersaturation profiles as well as the spatial distribution of supersaturation are effective controls for tuning the mineralization extent and product. We anticipate that the control strategies outlined in this work can serve as a foundation for the advanced and scalable fabrication of nanocomposites as building blocks for nacre-mimetic and functional materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Stable and Recyclable Photocatalysts of CsPbBr 3 @MSNs Nanocomposites for Photoinduced Electron Transfer RAFT Polymerization

All-inorganic metal halide perovskite CsPbX 3 (X = Cl, Br, I) nanocrystals (NCs) have demonstrated attractive optoelectronic characteristics. However, their photocatalytic properties are limited by their poor stability and easy recombination of photogenerated carriers. Herein, we introduced a CsPbBr 3 @MSNs nanocomposite (CsPbBr 3 NCs embedded in dendritic mesoporous silica nanospheres (MSNs)) as photocatalysts for photoinduced electron transfer reversible addition–fragmentation chain transfer (PET-RAFT) polymerization. In this study, the CsPbBr 3 nanocrystals (~8.1 nm; PLQY of 62 ± 2.1%) were embedded in dendritic MSNs using a nanoconfinement strategy. PET-RAFT polymerization was successfully initiated using the CsPbBr 3 @MSNs nanocomposite as the photocatalyst. Reaction variables, such as catalyst loading, monomer composition, and excitation light wavelengths, were varied to yield polymers with the desired control of molecular weight and dispersity as well as block copolymers with high chain-end fidelity. In addition, the perovskite-based photocatalysts could be readily separated and purified, which allowed effective and rapid recycling of the nanocomposites for multiple polymerization cycles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reducing leakage current and enhancing polarization in multiferroic 3D super-nanocomposites by microstructure engineering

Abstract Multiferroic materials have generated great interest due to their potential as functional device materials. Nanocomposites have been increasingly used to design and generate new functionalities by pairing dissimilar ferroic materials, though the combination often introduces new complexity and challenges unforeseeable in single-phase counterparts. The recently developed approaches to fabricate 3D super-nanocomposites (3D‐sNC) open new avenues to control and enhance functional properties. In this work, we develop a new 3D‐sNC with CoFe 2 O 4 (CFO) short nanopillar arrays embedded in BaTiO 3 (BTO) film matrix via microstructure engineering by alternatively depositing BTO:CFO vertically-aligned nanocomposite layers and single-phase BTO layers. This microstructure engineering method allows encapsulating the relative conducting CFO phase by the insulating BTO phase, which suppress the leakage current and enhance the polarization. Our results demonstrate that microstructure engineering in 3D‐sNC offers a new bottom–up method of fabricating advanced nanostructures with a wide range of possible configurations for applications where the functional properties need to be systematically modified.

36 MATERIALS SCIENCE↗