Facile preparation of core@shell and concentration-gradient spinel particles for Li-ion battery cathode materials.

Core@shell and concentration-gradient particles have attracted much attention as improved cathodes for Li-ion batteries (LIBs). However, most of their preparation routes have employed a precisely-controlled co-precipitation method. Here, we report a facile preparation route of core@shell and concentration-gradient spinel particles by dry powder processing. The core@shell particles composed of the MnO2 core and the Li(Ni,Mn)2O4 spinel shell are prepared by mechanical treatment using an attrition-type mill, whereas the concentration-gradient spinel particles with an average composition of LiNi0.32Mn1.68O4 are produced by calcination of their core@shell particles as a precursor. The concentration-gradient LiNi0.32Mn1.68O4 spinel cathode exhibits the high discharge capacity of 135.3 mA h g-1, the wide-range plateau at a high voltage of 4.7 V and the cyclability with a capacity retention of 99.4% after 20 cycles. Thus, the facile preparation route of the core@shell and concentration-gradient particles may provide a new opportunity for the discovery and investigation of functional materials as well as for the cathode materials for LIBs.

Evaluation of particles released from single-wall carbon nanotube/polymer composites with or without thermal aging by an accelerated abrasion test.

To provide data required for assessing the environmental health and safety risks of nanocomposites, abrasion-induced particle release from single-wall carbon nanotube (SWCNT)/polymer composites with or without thermal aging were evaluated by a shot blast system. First, overall composite weight loss (i.e., overall particle release) as a result of shot blasting was measured. Incorporating 5 wt% SWCNTs in polystyrene (PS) matrix was observed to reduce overall particle release by approximately 30% compared with pure PS. Heat treatment of the 5 wt% SWCNT/PS composites at 100°C for 10 days induced very slight change in overall particle release due to shot blasting. However, heat treatment at 350°C for 1 hr greatly deteriorated the abrasion resistance of the composites, enhancing overall particle release. Second, to verify the existence and form of SWCNTs released from the composites, released particles were observed by electron microscopy. Micron-sized particles with protruding SWCNTs and submicron-sized SWCNT clusters were observed in the particles released from the composites. Heat treatment of the composites at 350°C for 1 hr enhanced SWCNT release, which mainly formed clusters or rope-like bundles.

Non-Prestonian behavior of rectangular shaped ceria slurry in shallow trench isolation chemical mechanical planarization.

Rectangular ceria particles were synthesized using the flash creation method. The influence of the morphology of ceria particles and the surfactant concentration on the removal rate was systematically investigated. These ceria slurries with polymeric surfactant molecules as the passivation agents of Si3N4 film, shows an exceptional non-Prestonian behaviors. The non-Prestonian behavior can be attributed to the increase in the contact area of the ceria particles with the SiO2 film, which is dominated by the morphology of the ceria particles. Force measurements using an atomic force microscope (AFM) at different concentrations of polymeric surfactant molecules was used to identify the interactions between the polymeric molecules and the oxide film and analyze the non-Prestonian behavior of ceria slurry having rectangular abrasives.

Carbon nanoparticle-entrapped macroporous Mn3O4 microsphere anodes with improved cycling stability for Li-ion batteries.

Manganese oxide (Mn3O4) has garnered substantial attention as a low-cost, environment-friendly anode material. It undergoes a conversion reaction involving the formation of Li2O and metallic Mn to provide high-energy Li-ion batteries. However, its low electrical conductivity and significant volume change reduce its capacity during the initial lithiation/delithiation, hindering its practical application. To improve the cycle performance, we propose a new composite structure wherein we entrap carbon nanoparticles in macroporous Mn3O4 microspheres with a unique maze-like porous interior. We fabricate the Mn3O4/C composites using a scalable two-step process involving the thermal decomposition of MnCO3 in water vapor and mixing in a carbon-dispersed solution. The fabricated Mn3O4/C composites with varying carbon contents exhibit a high maximum discharge capacity retention of 86% after 50 cycles, compared to the 18% given by bare Mn3O4. The entrapped carbon nanoparticles improve the cycle performance both electrochemically and physically. The microstructure of the composite particles and the fabrication process developed in this study will help improve the performance of other conversion-type anode materials that suffer from cycle degradation, including inexpensive transition metal oxides and sulfides.

Effect of ball collision direction on a wet mechanochemical reaction.

Mechanochemical reactions can be induced in a solution by the collision of balls to produce high-temperature and high-pressure zones, with the reactions occurring through a dissolution-precipitation mechanism due to a change in solubility. However, only a fraction of the impact energy contributes to the mechanochemical reactions, while the rest is mainly consumed by the wear of balls and the heat generation. To clarify whether the normal or tangential component of collisions makes a larger contribution on the reaction, herein we studied the effect of collision direction on a wet mechanochemical reaction through combined analysis of the experimental reaction rates and simulated ball motion. Collisions of balls in the normal direction were found to contribute strongly to the wet mechanochemical reaction. These results could be used to improve the synthesis efficiency, predict the reaction, and lower the wear in the wet mechanochemical reactions.

Magnetorheological Fluids with Surface-Modified Iron Oxide Magnetic Particles with Controlled Size and Shape.

This study is focused on surface-modified Fe3O4@SiO2 particles with precisely controlled sizes and shapes applied in magnetorheological (MR) fluids. After the preparation of the monodisperse spindle-shaped and cubic Fe3O4@SiO2 particles, surface modification with dodecyltrimethoxysilane (DTM) was carried out via a silane coupling reaction to increase the dispersion stability of the particles. Afterward, MR fluids were prepared by mixing the DTM-modified Fe3O4@SiO2 particles with silicon oil. Transmission electron microscopy observations demonstrated that spindle-shaped Fe3O4@SiO2 particles could form a more stable chain-like structure than cubic Fe3O4@SiO2 particles upon application of an external magnetic field. The rheological measurements of MR fluids also indicated that the surface modification with DTM, the introduction of anisotropic shapes, and the increase in the particle size all played positive roles in the improvement in MR properties.

Anisotropic polyhedral self-assembly of Ag-CNT nanocomposites.

We report the unique assembling behavior of Ag NP supported CNT nanocomposites. Initially Ag NPs were precipitated homogeneously on the walls of SDS-coated CNTs by a NaBH4 chemical reduction and/or photoreduction directly in an aqueous solution. An additional Ag source was subsequently added into the Ag-CNT dispersion and Ag was further reduced using hydroxylamine in a weakly alkaline condition. The morphology of the resulting Ag-CNT nanocomposites strongly depended on the Ag+ ion concentration. Interestingly, an anisotropic polyhedral self-assembly of Ag-CNT nanocomposites was observed when the Ag concentration was increased to 0.1 M (real concentration).

Wet Mechanical Route To Synthesize Morphology-Controlled NH4MnPO4·H2O and Its Conversion Reaction into LiMnPO4.

A mechanical route using a grinding apparatus such as a planetary ball mill is a simple and scalable method to produce powder materials. However, the control of the particle shapes is difficult. In this paper, we report a wet mechanical process in water to synthesize NH4MnPO4·H2O (AmMnP) with various shapes (plates, flakes, rods, and nanoparticles). This process involves planetary ball milling of inexpensive raw materials (NH4H2PO4 and MnCO3) at room temperature. Morphology-controlled AmMnP particles can be obtained by only adjusting the milling conditions such as milling time, ball size, and centrifugal acceleration. Furthermore, the conversion of AmMnP into LiMnPO4 with two different approaches (solid-state and hydrothermal reactions) has been investigated to evaluate its future applicability as a cathode for lithium-ion batteries. As a particle synthesis with a unique morphology can be attained based on a dissolution-precipitation mechanism in a solution via a suitable combination of raw materials, the study results will promote wet mechanical processes to be widely used as classic but advanced particle synthesis method.

Manipulation of the degradation behavior of calcium sulfate by the addition of bioglass.

A bioactive calcium sulfate/glass composite was prepared using a sintering technique, and Ca-P-Si glass particles were prepared by spray pyrolysis. The glass exhibited bioactivity in terms of its ability to form apatite in a simulated body fluid. The glass was transformed into two crystallized phases, i.e., calcium phosphate and calcium silicate, respectively, during the heating stage. The presence of the crystallized phases retarded the densification of calcium sulfate. A high sintering temperature of 1200 °C was needed to prepare the composite. The increased addition of glass enhanced the strength and decreases the degradation rate of calcium sulfate. The new composite is not only degradable but also bioactive.

Grafting of material-binding function into antibodies Functionalization by peptide grafting.

Quite recently, a few antibodies against bulk material surface have been selected from a human repertoire antibody library, and they are attracting immense interest in the bottom-up integration of nanomaterials. Here, we constructed antibody fragments with binding affinity and specificity for nonbiological inorganic material surfaces by grafting material-binding peptides into loops of the complementarity determining region (CDR) of antibodies. Loops were replaced by peptides with affinity for zinc oxide and silver material surfaces. Selection of CDR loop for replacement was critical to the functionalization of the grafted fragments; the grafting of material-binding peptide into the CDR2 loop functionalized the antibody fragments with the same affinity and selectivity as the peptides used. Structural insight on the scaffold fragment used implies that material-binding peptide should be grafted onto the most exposed CDR loop on scaffold fragment. We show that the CDR-grafting technique leads to a build-up creation of the antibody with affinity for nonbiological materials.

Thermoresponsive gelling behavior of concentrated alumina suspensions containing poly(acrylic acid) and PEO-PPO-PEO copolymer.

Thermoresponsive gelling behavior of concentrated alumina suspensions with poly(acrylic acid) (PAA) and triblock copolymer (PEO(101)-PPO(56)-PEO(101), Pluronic F127) was investigated as a function of PAA concentration (0.4-1.2 mass%) for ceramic solid free forming. The copolymer species assemble into micelles at temperatures above 15°C, yielding aqueous physical gel. In this study, the concentrated alumina aqueous suspensions (φ=35 vol%) were first prepared using the anionic dispersant of PAA, and then the copolymer species (10 mass%) were dissolved at a cooled temperature at 10°C. The addition of the copolymer species had a negligible influence on the adsorption state of PAA onto the alumina surfaces. The PAA concentration needed for the saturation adsorption on the alumina surfaces was ~0.6 mass%. When the PAA concentration was this value or slightly less, the suspension became gel state at 30°C from low viscous state at 10°C. The thermally induced alumina gel had excellent viscoelastic properties, and thereby the three dimensional periodic ceramic structures were successfully fabricated by a direct colloidal printing method that using the gels as "solid" inks at the room temperature. On the other hand, when it exceeded the saturation adsorption limit, the gelling behavior was not observed, indicating that the non-adsorbing PAA species may partly suppress the micellization of the copolymer on the heating.

Arrangement of palladium nanoparticles templated by supramolecular self-assembly of SDS wrapped on single-walled carbon nanotubes.

We report a facile route to selectively deposit and arrange palladium (Pd) nanoparticles on single-walled carbon nanotubes (SWCNTs) having sub 10 nm diameter by using supramolecular self-assembly of sodium dodecyl sulfate (SDS) as a soft template.

Oriented growth behavior of Ag nanoparticles using SDS as a shape director.

We report a chemical approach for synthesizing shape-controlled Ag nanoparticles by using the surfactant SDS as a soft template. The experimental approach includes a two-step reaction: the first step is quickly generating Ag seed clusters by a chemical reaction using sodium borohydride as a reducing reagent; the second is the slow growth of controllable Ag nanoparticles by a mild chemical reaction using hydroxylamine hydrochloride as a reducing reagent. Spherical, polyhedral, and fibrous Ag nanoparticles are synthesized successfully in aqueous solution having SDS concentrations of 0.01, 0.02, and 0.2 wt.%, respectively. Size, morphology, and dispersion stability of these Ag nanoparticles depend on the concentrations of both SDS and AgNO(3).