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At least 109 records · Page 6

Effect of Polymer Removal on the Morphology and Phase of the Nanoparticles in All-Inorganic Heterostructures Synthesized via Two-Step Polymer Infiltration

Polymer templates play an essential role in the robust infiltration-based synthesis of functional multicomponent heterostructures with controlled structure, porosity, and composition. Such heterostructures are be used as hybrid organic–inorganic composites or as all-inorganic systems once the polymer templates are removed. Using iron oxide/alumina heterostructures formed by two-step infiltration of polystyrene-block-polyvinyl pyridine block copolymer with iron and aluminum precursors from the solution and vapor-phases, respectively, we show that the phase and morphology of iron oxide nanoparticles dramatically depend on the approach used to remove the polymer. We demonstrate that thermal and plasma oxidative treatments result in iron oxide nanoparticles with either solid or hollow morphologies, respectively, that lead to different magnetic properties of the resulting materials. Our study extends the boundaries of structure manipulations in multicomponent heterostructures synthesized using polymer infiltration synthesis, and hence their properties.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Electron Radiation-Induced Nickel Nanoparticle Formation in KCl-ZnCl 2 Eutectic Molten Salt Using X-ray Absorption Spectroscopy

Understanding the speciation and local structure of metal solutes in molten salts is essential for predicting thermal properties and the redox and corrosion potentials of molten salts for next-generation nuclear reactors and concentrated solar power plant applications. Here, we employ X-ray absorption spectroscopy combined with electron paramagnetic resonance (EPR) measurements to investigate the effects of electron irradiation on 0.1 wt % NiCl 2 dissolved in molten eutectic KCl-ZnCl 2 salt. Radiation-driven reduction of Ni 2+ leading to nucleation and growth of Ni nanoparticles is studied as a function of electron dose (3–15 MGy) and temperature. Quantitative X-ray absorption near edge structure and linear combination fitting are utilized to investigate the extent of reduction as a function of the electron dose and temperature. A multiple-scattering (MS) approach is used for extended X-ray absorption fine structure analysis to deduce the size of the Ni nanoparticles formed and to understand the effect of the dose on the local structure of the nanoparticles. EPR studies on solidified NiCl 2 dissolved in molten eutectic KCl-ZnCl 2 salt show the formation of magnetic Ni nanoparticles.

36 MATERIALS SCIENCE↗

Confusion-Driven Machine Learning of Structural Phases of a Flexible, Magnetic Stockmayer Polymer

We use a semisupervised, neural-network-based machine learning technique, the confusion method, to investigate structural transitions in magnetic polymers, which we model as chains of magnetic colloidal nanoparticles characterized by dipole–dipole and Lennard-Jones interactions. As input for the neural network, we use the particle positions and magnetic dipole moments of equilibrium polymer configurations, which we generate via replica-exchange Wang–Landau simulations. We demonstrate that by measuring the classification accuracy of neural networks, we can effectively identify transition points between multiple structural phases without any prior knowledge of their existence or location. We corroborate our findings by investigating relevant conventional order parameters. Our study furthermore examines previously unexplored low-temperature regions of the phase diagram, where we find new structural transitions between highly ordered helicoidal polymer configurations.

36 MATERIALS SCIENCE↗

Block copolymer self-assembly derived mesoporous magnetic materials with three-dimensionally (3D) co-continuous gyroid nanostructure

Magnetic nanomaterials are gaining interest for their many applications in technological areas from information science and computing to next-generation quantum energy materials. While magnetic materials have historically been nanostructured through techniques such as lithography and molecular beam epitaxy, there has recently been growing interest in using soft matter self-assembly. In this work, a triblock terpolymer, poly(isoprene-block-styrene-block-ethylene oxide) (ISO), is used as a structure directing agent for aluminosilicate sol nanoparticles and magnetic material precursors to generate organic–inorganic bulk hybrid films with co-continuous morphology. After thermal processing into mesoporous materials, results from a combination of small angle X-ray scattering (SAXS) and scanning electron microscopy (SEM) are consistent with the double gyroid morphology. Nitrogen sorption measurements reveal a type IV isotherm with H1 hysteresis, and yield a specific surface area of around 200 m 2 g −1 and an average pore size of 23 nm. The magnetization of the mesostructured material as a function of applied field shows magnetic hysteresis and coercivity at 300 K and 10 K. Comparison of magnetic measurements between the mesoporous gyroid and an unstructured bulk magnetic material, derived from the identical inorganic precursors, reveals the structured material exhibits a coercivity of 250 Oe, opposed to 148 Oe for the unstructured at 10 K, and presence of remnant magnetic moment not conventionally found in bulk hematite; both of these properties are attributed to the mesostructure. This scalable route to mesoporous magnetic materials with co-continuous morphologies from block copolymer self-assembly may provide a pathway to advanced magnetic nanomaterials with a range of potential applications.

Chemistry↗

Revealing the effect of LiOH on forming a SEI using a Co magnetic “probe”

The solid-electrolyte-interphase (SEI) plays a critical role in lithium-ion batteries (LIBs) because of its important influence on electrochemical performance, such as cycle stability, coulombic efficiency, etc. Although LiOH has been recognized as a key component of the SEI, its influence on the SEI and electrochemical performance has not been well clarified due to the difficulty in precisely controlling the LiOH content and characterize the detailed interface reactions. Here, a gradual change of LiOH content is realized by different reduction schemes among Co(OH) 2 , CoOOH and CoO. With reduced Co nanoparticles as magnetic “probes”, SEI characterization is achieved by operando magnetometry. By combining comprehensive characterization and theoretical calculations, it is verified that LiOH leads to a composition transformation from lithium ethylene di-carbonate (LEDC) to lithium ethylene mono-carbonate (LEMC) in the SEI and ultimately results in capacity decay. This work unfolds the detailed SEI reaction scenario involving LiOH, provides new insights into the influence of SEI composition, and has value for the co-development between the electrode materials and electrolyte.

25 ENERGY STORAGE↗

Linker-Free Magnetite-Decorated Gold Nanoparticles (Fe3O4-Au): Synthesis, Characterization, and Application for Electrochemical Detection of Arsenic (III)

Linker-free magnetite nanoparticles (Fe3O4NPs)-decorated gold nanoparticles (AuNPs) were grown using a new protocol that can be used as a new platform for synthesis of other intact metal–metal oxide nanocomposites without the need for linkers. This minimizes the distance between the metal and metal oxide nanoparticles and ensures the optimum combined effects between the two material interfaces. X-ray diffraction (XRD) and Fourier transform infrared (FTIR) spectroscopy confirmed the successful synthesis of the Fe3O4-Au nanocomposite, without any change in the magnetite phase. Characterization, using transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectroscopy, revealed the composite to consist of AuNPs of 70 ± 10 nm diameter decorated with tiny 10 ± 3 nm diameter Fe3O4NPs in Au:Fe mass ratio of 5:1. The prepared Fe3O4-Au nanocomposite was embedded in ionic liquid (IL) and applied for the modification of glassy carbon electrode (GCE) for the electrochemical detection of As(III) in water. By combining the excellent catalytic properties of the AuNPs with the high adsorption capacity of the tiny Fe3O4NPs towards As(III), as well as the good conductivity of IL, the Fe3O4-Au-IL nanocomposite showed excellent performance in the square wave anodic stripping voltammetry detection of As(III). Under the optimized conditions, a linear range of 1 to 100 μg/L was achieved with a detection limit of 0.22 μg/L (S/N = 3), and no interference from 100-fold higher concentrations of a wide variety of cations and anions found in water. A very low residual standard deviation of 1.16% confirmed the high precision/reproducibility of As(III) analysis and the reliability of the Fe3O4-Au-IL sensing interface. Finally, this proposed sensing interface was successfully applied to analyzing synthetic river and wastewater samples with a 95–101% recovery, demonstrating excellent accuracy, even in complex synthetic river and wastewater samples containing high concentrations of humic acid without any sample pretreatments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

AC Magnetometry Using Nano-ferrofluid Cladded Multimode Interferometric Fiber Optic Sensors for Power Grid Monitoring Applications

The AC magnetic field response of the superparamagnetic nano-ferrofluid is an interplay between the Neel and Brownian relaxation processes and is generally quantified via the susceptibility measurements at high frequencies. The high frequency limit is dictated by these relaxation times which need to be shorter than the time scale of the time varying magnetic field for the nano-ferrofluid to be considered in an equilibrium state at each time instant. Even though the high frequency response of ferrofluid has been extensively investigated for frequencies up to GHz range by non-optical methods, harnessing dynamic response by optical means for AC magnetic field sensing in fiber-optic-based sensors-field remains unexplored. Instead, the incorporation of nano-ferrofluid as sensing materials has been only limited to DC magnetic field sensing, often citing their long response time as a limiting factor to AC field sensing. This work reports the finding of high frequency (up to 15 kHz) AC magnetic field sensing capability of nanomagnetic fluid as the cladding material of a fiber-optic multimode interferometry (MMI) structure optimized for the fourth self-imaging spectral response. The key parameter enabling high frequency response is the short response time (<1 ms) achieved by optimizing both the sensing structure and nano-ferrofluid solution. Focus has been imparted on 60 Hz line-frequency profiles of various current/magnetic fields to test the efficacy of these sensors in metering and monitoring current and current-induced magnetic fields in the electrical power grid systems. The magnetic field sensitivity of 240 mV/Gauss per dBm of transmitted power was achieved for 60 Hz field applied via Helmholtz coil, whereas the 60 Hz AC current sensitivity of 2.83 mV/A was measured due to magnetic field induced by current in a straight conducting wire.

42 ENGINEERING↗

Ferromagnetic Resonance Modes in the Exchange-Dominated Limit in Cylinders of Finite Length

We analyze the magnetic mode structure of axially magnetized finite-length nanoscopic cylinders in a regime where the exchange interaction dominates, along with simulations of the mode frequencies of the ferrimagnet yttrium iron garnet. For the bulk modes, we find that the frequencies can be represented by an expression given by Herring and Kittel by using wavevector components obtained by fitting the mode patterns emerging from these simulations. In addition to the axial, radial, and azimuthal modes that are present in an infinite cylinder, we find localized “cap modes” that are “trapped” at the top and bottom cylinder faces by the inhomogeneous dipole field emerging from the ends. Semiquantitative explanations are given for some of the modes, in terms of a one-dimensional Schrodinger equation, which is valid in the exchange-dominant case. The assignment of the azimuthal-mode number is carefully discussed, and the frequency splitting of a few pairs of nearly degenerate modes is determined through the beat pattern emerging from them.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Energy-relaxation pathways in finite-sized artificial square-ice structures

The energy-relaxation pathway in artificial spin ice structures refers to the series of individual moment reorientations the system undergoes as it relaxes from an initial state to a final low-energy state. The probability of the artificial spin ice structure reaching a ground state depends on the energy of the intermediate states as approximated by an Arrhenius-type relation. In this work, we report that by modifying the geometry of artificial square-ice structures, we can influence the probability of observing the ground state in different configurations. Furthermore, our findings are supported by dipolar energy calculations for various energy-relaxation pathways and the corresponding experimental data obtained by magnetic force microscopy.

Analog computation↗

Solvent Influence on the Magnetization and Phase of Fe-Ni Alloy Nanoparticles Generated by Laser Ablation in Liquids

The synthesis of bimetallic iron-nickel nanoparticles with control over the synthesized phases, particle size, surface chemistry, and oxidation level remains a challenge that limits the application of these nanoparticles. Pulsed laser ablation in liquid allows the properties tuning of the generated nanoparticles by changing the ablation solvent. Organic solvents such as acetone can minimize nanoparticle oxidation. Yet, economical laboratory and technical grade solvents that allow cost-effective production of FeNi nanoparticles contain water impurities, which are a potential source of oxidation. Here, we investigated the influence of water impurities in acetone on the properties of FeNi nanoparticles generated by pulsed laser ablation in liquids. To remove water impurities and produce “dried acetone”, cost-effective and reusable molecular sieves (3 Å) are employed. The results show that the Fe50Ni50 nanoparticles’ properties are influenced by the water content of the solvent. The metastable HCP FeNi phase is found in NPs prepared in acetone, while only the FCC phase is observed in NPs formed in water. Mössbauer spectroscopy revealed that the FeNi nanoparticles oxidation in dried acetone is reduced by 8% compared to acetone. The high-field magnetization of Fe50Ni50 nanoparticles in water is the highest, 68 Am2/kg, followed by the nanoparticles obtained after ablation in acetone without water impurities, 59 Am2/kg, and acetone, 52 Am2/kg. The core-shell structures formed in these three liquids are also distinctive, demonstrating that a core-shell structure with an outer oxide layer is formed in water, while carbon external layers are obtained in acetone without water impurity. The results confirm that the size, structure, phase, and oxidation of FeNi nanoparticles produced by pulsed laser ablation in liquids can be modified by changing the solvent or just reducing the water impurities in the organic solvent.

36 MATERIALS SCIENCE↗

Evidence of a glassy magnetic transition driven by structural disorder in BiFeO 3 nanoparticles

Important effects appear in low and high temperature magnetometry of multiferroic BiFeO 3 (BFO) nanoparticles as sizes are reduced from 105 nm to 18 nm. In these particles, a magnetic transition appears close to 200 K probably associated with a spin reorientation which is absent in bigger particles. At higher temperatures and up to the bulk ferroelectric Curie temperature (1000 K), two additional magnetic transitions can be identified. Around T N 600 K, a size-dependent magnetic transition appears, associated with an antiferromagnetic transition. A model based on atomic vibration instability can describe the variation of T N with nanoparticle size. Furthermore, for certain sizes, the properties are dominated by the glassy state arising from the disorder produced by the formation of a core-shell structure. This implies that the magnetic behavior of nanoparticles is strongly affected by their crystal structure close to the transition temperature. Finally, the structural disorder which couples to the magnetic properties add control to the magnetic and ferroelectric properties of BFO nanoparticles.

36 MATERIALS SCIENCE↗

Hard–Soft Core–Shell Architecture Formation from Cubic Cobalt Ferrite Nanoparticles

Cubic bi-magnetic hard–soft core–shell nanoarchitectures were prepared starting from cobalt ferrite nanoparticles, prevalently with cubic shape, as seeds to grow a manganese ferrite shell. The combined use of direct (nanoscale chemical mapping via STEM-EDX) and indirect (DC magnetometry) tools was adopted to verify the formation of the heterostructures at the nanoscale and bulk level, respectively. The results showed the obtainment of core–shell NPs (CoFe 2 O 4 @MnFe 2 O 4 ) with a thin shell (heterogenous nucleation). In addition, manganese ferrite was found to homogeneously nucleate to form a secondary nanoparticle population (homogenous nucleation). This study shed light on the competitive formation mechanism of homogenous and heterogenous nucleation, suggesting the existence of a critical size, beyond which, phase separation occurs and seeds are no longer available in the reaction medium for heterogenous nucleation. These findings may allow one to tailor the synthesis process in order to achieve better control of the materials’ features affecting the magnetic behaviour, and consequently, the performances as heat mediators or components for data storage devices.

36 MATERIALS SCIENCE↗

Molecular Imaging of Matrix Metalloproteinase-2 in Atherosclerosis Using a Smart Multifunctional PET/MRI Nanoparticle

Matrix metalloproteinases from macrophages are important intraplaque components that play pivotal roles in plaque progression and regression. This study sought to develop a novel multifunctional positron emission tomography (PET) and magnetic resonance imaging (MRI) contrast agents based on MMP-2 cleavable nanoparticles to noninvasive assessment of MMP-2 activity in mouse carotid atherosclerotic plaques. Macrophage-rich vascular lesions were induced by carotid ligation plus high-fat diet and streptozotocin-induced diabetes in CL57/BL6 mice. To render iron oxide nanoparticles (IONP) specific for the extracellular MMP-2, the magnetic nanoparticle base material has been derivatized with 1,4,7-triazacyclononane-1,4,7-triacetic acid (NOTA) for the nuclear tracer 64 Cu labeling and the MMP-2-cleavable peptide modified with polyethylene glycol 2000, yielding a multi-modality reporter ( 64 Cu-NOTA-IONP@MMP2c-PEG2K, MMP2cNPs) for PET/MR imaging. Small animal PET imaging and biodistribution data revealed that MMP2cNPs exhibited remarkable plaque uptake (3.06 ± 0.87% ID/g and 1.83 ± 0.28% ID/g at 4 and 12 h, respectively). And MMP2cNPs were rapidly cleared from the contralateral normal carotid artery, resulting in excellent plaque-to-normal carotid artery contrasts. Furthermore, in vivo MRI showed a preferential accumulation of MMP2cNPs in atherosclerotic lesions compared with the non-cleavable reference compound, MMP2ncNPs. In addition, histological analyses revealed iron accumulations in the carotid atherosclerotic plaque, in colocalization with MMP-2 expression and macrophages. Using a combination of innovative imaging modalities, in this study, we demonstrate the feasibility of applying the novel smart MMP2cNPs as a PET/MR hybrid imaging contrast agent for detection of MMP-2 in atherosclerotic plaque in vivo.

60 APPLIED LIFE SCIENCES↗

Surface Terminations of LaAlO 3 Perovskite Nanoparticles as Viewed by Solid-State Nuclear Magnetic Resonance

Nanocrystal surfaces generally undergo reconstructions that differentiate them from the bulk structures, often in nontrivial ways. Understanding these terminations is critical across diverse fields, from heterogeneous catalysis to the formation of topological states and the synthesis of semiconductor nanomaterials. Determining surface structures is currently an interdisciplinary task, most often involving high-resolution electron microscopy and surface electron diffraction. These methods, however, do not provide a global view of the ensemble of structures present in a sample. Here, we show how surface-sensitive solid-state nuclear magnetic resonance (SSNMR) spectroscopy methods can bridge this gap. In this context, we investigated the surface structure of lanthanum aluminate (LaAlO 3 ) perovskite nanoparticles. Four distinct surface terminations have previously been observed for this material, but their relative abundances were unknown. Using an array of double- and triple-resonance SSNMR methods probing the relative proximities of surface 1 H, 27 Al, 17 O, and 139 La nuclei, we conclude the surface to be majority terminated (80%) by AlO x with substantial (20%) LaO x terminated regions.

Materials↗