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Fe-based nanocrystalline alloy powder prepared by ball-milling is a potential candidate as a soft magnetic composite (SMC). Since the magnetic properties of particles having a random geometry arisi...

This article is the first work to carefully investigate the characteristics of iron loss per weight and relative permeability between the flake and spherical powders with a sinusoidal excitation up to a high frequency of 3.5 MHz in experiments using three separate measurement systems. The composition of the considered powder samples contains 0.001 wt% C, 0.012 wt% Si, 0.09 wt% Mn, 0.0004 wt% P, 0.008 wt% S, and 0.06 wt% O. The flake particle has the preferred orientation that the easy axes are normal to the platelet face, and the water atomized iron powder was processed with ball milling with the lubrication. Key objectives of the utilization of the three independent measurement systems with different specialized equipment and probes are to cross-check and overcome unexpected measurement errors of the related devices in use for validating measured results thoroughly. Experimental results demonstrate the much better performances on the iron loss per weight and relative permeability of the flake powder than that of the spherical powder at high frequencies. Physics-based explanations for the measured results are also presented. Furthermore, two estimation functions based on a six-parameter Steinmetz equation for the measured iron loss of the powders are developed by using MATLAB.

In this study, Eu3+-containing amorphous silica nanoparticles and Eu compounds were successfully synthesized via a mechanochemical solid-state reaction between silica nanoparticles and EuCl3·6H2O. This reaction was induced by a grinding process, and the states of Eu3+ in the silica/europium composites were investigated. The silica/europium composites exhibited orange–red color luminescence owing to the 5D0–7F0, 5D0–7F1, and 5D0–7F2 transitions, which indicated the presence of Eu3+ in the silica framework and the newly formed Eu compounds such as EuOCl and Eu(OH)2Cl. The mechanochemical reaction because of the grinding process effectively induced an interaction between the silica surface and europium chloride; subsequently, Eu(OH)2Cl was formed in the silica/europium composites. Additionally, the Eu(OH)2Cl in the silica/europium composite exhibited a higher thermal stability than that of simple Eu(OH)2Cl, indicating that the mechanochemical reaction mediated the formation of Eu(OH)2Cl and new chemical bonding between the newly formed Eu(OH)2Cl and the silica surface, providing improved thermal stability to Eu(OH)2Cl. Thus, we successfully prepared silica nanoparticles containing not only Eu(III) in the silica framework but also Eu compounds that exhibit unique chemical bonding during a mechanochemical reaction.

This study aims to reveal the effects of pressure during cold isostatic pressing (CIP) on the microstructure and optical properties of fluorescent HAp complexes. Although the microsturucture-dependent properties of fluorescent HAp complexes have been reported to improve the antibacterial properties of photocatalyst coating layers, the mechanism behind the changes in the fluorescence properties of highly compressed HAp complexes has not yet been unveiled. CIP was successfully used to fabricate fluorescent HAp – amino acid complexes, and their fluorescence intensities increased with increasing fabrication pressure. Peak wavelength of fluorescence emitted by the HAp – amino acid complexes exhibited yellow to red shift. Although the thickness of the amino acid layer was saturated in higher pressure cases, the concentration of amino acids increased proportionally with pressure, which suggests changes in the packing structures of the ligands in the HAp– amino acid complexes. Polarized Raman spectroscopy measurements clearly detected ligands normally arranged to the HAp layer under high pressure fabrication conditions, which can provide the tightly packed ligand structure in the HAp– amino acid complexes. These tightly packed ligand structure in the HAp– amino acid complexes could emit stronger fluorescence owing to the increased density of complexations. This newly found pressure dependency in the optical properties of HAp–amino acid complexes is beneficial for developing biocompatible fluorescence materials or enhancement agents for antibacterial coating layers.

We synthesized nanostructured mesoporous silica (MS)/hydroxyapatite (HA) hybrid particles in the presence of amphiphilic poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (PEO20PPO70PEO20) triblock copolymer (P123). The particles exhibited slit-shaped mesostructures and underwent hybridization reaction between the MS and HA phases containing P123. Furthermore, the aggregated form of the particles exhibited dispersion stability in water in the monodispersed state (average particle size: 145 nm and coefficient of variation: 4.3% in the case of the maximum added amount of P123). Then, the structures of the hydration layer and the adsorbed protein on the particles were investigated to understand the effect of the hydration layer structures on the protein secondary structures. The ratio of the bonding water (intermediate and nonfreezing water) to free water increased upon hybridization, and it decreased with increasing P123 concentration. Upon hybridization, the component ratio of the asymmetric O–H stretching vibration between free water molecules decreased, and that of the symmetric O–H stretching vibration of intermediate water molecules increased. With increasing P123 concentration, the asymmetric O–H stretching vibration between free water molecules increased and the symmetric O–H stretching vibration of intermediate water molecules decreased. It was found that the protein native state component ratios of α-helix and β-sheet increased with increasing symmetric O–H stretching vibration between intermediate water molecules, and they decreased with decreasing asymmetric O–H stretching vibration between free water molecules. Moreover, the cytotoxicity against osteoblasts (MC3T3-E1) was evaluated and the hybrid particles exhibited a high cell density, indicating their bioactivity. On the hybrid particles interacting with P123, the cells were three-dimensionally assembled and uniaxially grown with the culture. Therefore, this is the first successful report of the synthesis of nanostructured MS/HA hybrid particles interacting with P123, and the controlled hydration layer structures on the particle surfaces were found to contribute to the protein secondary structures, promoting cytocompatibility.

The aim of this study is to observe visible light-induced antibacterial effects of the luminescent complex of hydroxyapatite and 8-hydroxyquinoline with gray titania coating. Plasma-sprayed Hydroxyapatite (HAp) coating has been widely used as bonding between alveolar bones with dental implants. However, bacterial infection on the surfaces of dental implants has recently been reported and conventional antibacterial technologies cannot last long-term use. Therefore a novel technology using the complex of hydroxyapatite and 8-hydroxyquinoline (8-Hq) with gray titania was proposed, which can be activated by visible light. Ti2O3 powder was used in a plasma-spraying process to fabricate visible-light-sensitive titania coating. The plasma-sprayed HAp/Ti2O3 was characterized by Raman Spectroscopy, FTIR and XRD. Its photo catalytic activity was evaluated using chemiluminescence observation and antibacterial property was evaluated by optical density measurement (OD), colony forming unit (CFUs) and fluorescent microscope observation. The plasma-sprayed Ti2O3 powder revealed that its phase changed to TiO2(Rutile) though the color of the plasma-sprayed Ti2O3 powder kept dark gray, which possessed its absorbency in visible-light region. The plasma-sprayed Ti2O3 powder was then called gray titania and 1 O 2 was generated from the gray titania by irradiating three types of laser (blue, green and red). Antibacterial evaluation revealed that both the existence of the complex and the irradiation of LEDs could significantly decrease the numbers of colony forming unit (CFUs). Furthermore, HAp-8Hq complex decreased adhesion of E. coli even without light irradiation. An enhancement in the antibacterial property of HAp complexes with gray titania coating can be attributed to an increased power density of light on the surface of gray titania by fluorescence.

The process of texture formation on iron particles was investigated via simple ball milling using graphite particles as milling aid. During milling, the shape of the iron particles changed from granular to platelets owing to repetitive compression and balls rolling in a direction perpendicular to the platelet faces. Simultaneously, a {001} + {111} double-fiber texture was formed, which is characteristic of a metal with a bcc structure deformed under uniaxial compression and multidirectional rolling. Based on these observations, it is concluded that the texture obtained through simple ball milling was induced by uniaxial compression and a multidirectional-rolling-like deformation. Since the main component of the double-fiber texture is {001} and the easy magnetization axes 〈001〉 are oriented toward the in-plane directions with the platelet face in the texture, the iron particles are ideal candidates for use as magnetic cores in motors, inductors, and other electromagnetic parts.

Organic/inorganic hybrids of 8-hydroxyquinoline (8Hq) molecule and hydroxyapatite nanocrystal (HAp) were mechanochemically prepared. In the hybrids, a green photoluminescence peak at 500 nm newly appeared, suggesting the chemical bonding of the 8Hq molecule with the Ca 2+ ions of HAp. Then, the organic/inorganic interfacial photofunction was clarified by a molecular orbital calculation. The interfacial chemical bonding between the O and N atoms of 8Hq and the Ca 2+ ions of HAp was attributed to both covalent O Ca and ionic N Ca. The resultant wave functions revealed that the green luminescence was attributed to metal-to-ligand charge transfer (MLCT) from the O atoms of phosphate group (HAp) to the π-cloud (8Hq) in the HOMO of the hybrids. Therefore, the photofunctional interfaces of the hybrids were successfully demonstrated.

A simple rubbing treatment was used to mechanochemically modify the surface of polyacrylonitrile-based carbon fibers and its effect on their surface structure and functional groups was studied using several surface characterization techniques. To control the mechanochemical effect, the shear forces accompanying rubbing were kept constant. Scanning electron microscopy tests and the peak positions and widths of the main Raman spectroscopy bands indicated that there were no morphological changes to the carbon fibers following rubbing. In contrast, X-ray photoelectron spectroscopy showed an increase in oxygen-containing functional groups; in addition to hydroxyl species, the main groups introduced were alkoxide, carbonyl, and carboxyl groups. The ratio of carboxyl groups on the carbon fiber surface increased with the shear force magnitude, indicating carbon surface oxidation. The difference between the Raman and X-ray photoelectron spectroscopy results indicates that the modification was confined to the first few atomic layers; therefore, this rubbing method is capable of producing efficient mechanochemical surface modification of carbon fibers. This technique is simple, is relatively inexpensive, and is applicable to carbon fiber-reinforced plastic processing techniques.

In ball-milled iron particles for soft magnetic composites (SMCs), milling aids with lubricity can induce a (0 0 1) fiber texture with superior magnetic properties. Effects of lubricants on the recrystallization behavior of ball-milled iron particles with fiber texture and their magnetic properties of SMCs using the iron particles were investigated. During ball milling, lubricant oil and boron nitride (a solid lubrication particle) were used as lubricants. Both as-milled iron particles have a (0 0 1) fiber texture. However, when these iron particles are recrystallized using heat treatment, the iron particles milled using the lubricant oil almost disappeared while the fiber texture in the particles milled using the boron nitride was strongly retained. Therefore, it is concluded that ball milling for iron particles using boron nitride lubricant can retain (0 0 1) fiber texture in heat-treated iron particles, and SMC using these iron particles have higher permeability and lower coercive force.

To clarify hydroxyapatite (HAp) nanocrystal formation based on the interfacial interactions with organic molecules is important for controlling the dispersion states/shapes of HAp and understanding the biomineralization mechanism. In this study, the effects of cetyltrimethylammonium bromide (CTAB) micelles on the HAp nanocrystal formation process were investigated through both the morphosynthesis technique and the molecular orbital calculations. The HAp nanocrystals synthesized in the presence of CTAB exhibited a controlled rod-like shape and subsequently grew up by a thermal treatment to be larger-sized nanocrystals at a well-dispersed state. It was also found that the CTAB micelles strained and disordered at the higher temperature effectively induced heterogeneous nucleation to initiate the nucleation/growth processes. In contrast, HAp nanocrystals synthesized without CTAB exhibited irregular-shaped and aggregated nanocrystals, which are due to dominantly occurring homogeneous nucleation. According to t...

Cold isostatic pressing successfully formed a chelate complex of 8-hydroxyquinoline (8 Hq) molecules on plasma-sprayed hydroxyapatite (HAp) coating by solid-state reaction. The complex emits a fluorescence peak at approximately 500 nm by UV irradiation. The red shift of the fluorescence was newly observed in the cases of highly compressed complex due to π - π stacking of aromatic ring in the molecular structure of 8 Hq. The immersed complex coating in Simulated Body Fluid (SBF) demonstrated amorphous apatite precipitation and kept its fluorescence property.

The role of graphite/substrate interface in low-friction behavior of graphite was investigated. Iron and graphite powder mixtures were plastically deformed in either Ar–H2 or air atmospheres to obtain bare iron or iron oxide surface. Then, graphite particles adhered to and formed interfaces with surfaces. Friction force microscopy revealed that friction on particle surface milled in Ar–H2 atmosphere was obviously higher. X-ray absorption near-edge structure and transmission electron microscopy revealed that although the basal plane of graphite oriented along the oxidized surface, it did not occur along the bare iron surface, which explains the difference in lubricity on each surface.

Mechanochemically activated graphite (Gp) and iron particle surfaces were prepared, and the Gp/iron composite interfaces were elucidated to utilize new functions. Activated iron particles with the oxygen atoms prepared by a milling under oxygen atmosphere were shown. Alternately, the Gp particles activated by the milling under argon atmosphere easily agglomerated because of the dangling bonds on the edge surfaces. In the composites, the interfacial bonds (e.g., Fe–O–C) between the Gp and iron oxides on the iron were clearly induced while preserving the carbon atom six-ring structures. Furthermore, the molecular orbital calculations suggested that the activated oxygen atoms in the iron oxides effectively abstract hydrogen atoms from the C–H groups of the Gp edge, resulting in the active bare carbon atoms which can form the interfacial bonds; therefore, the interfacial Fe–O–C bonds for a higher adhesive strength were successfully prepared.

The mechanochemical milling was utilized to control the nanostructures of plate-like graphite (Gp) microparticles in an argon atmosphere and at room temperature. The aggregated Gp nanoparticles were prepared by the simple solid-state process without organic solvent. Electron microscope observations, X-ray diffraction patterns and Raman spectra revealed the fractured plate-like Gp microparticles as well as the Gp microparticles agglomerated to each other through the dissociative edge surfaces by the milling process to finally generate the Gp nanoparticle aggregates. In the process, the ratio of the edge plane surfaces with the dangling bondings to layered internal surfaces clearly increased with the milling. Therefore, the low environmental burden process for preparing the Gp nanoparticle aggregation was achieved.

Composites between carbon fibers (CFs) and heterogeneous materials have been widely studied and their fabrication techniques have been developed. However, their hydrophobic surfaces make it difficult to disperse CFs into hydrophilic resins, which results in weak junctions with ceramics. To develop high-strength composite fibers, it is important to design interfacial chemical bonds. Thus, surface-modification techniques of CFs have recently become the main focus and their interfaces have been characterized by various analytical methods. In this Minireview, various techniques that modify the CF surface by coating with inorganic polymers (metal oxide compounds) are highlighted, and the applications of novel nanocomposite fibers are also described. Furthermore, interfacial bonds between CFs and polymer resins are reviewed and discussed in terms of CF-reinforced plastics and their future prospects.

Mechanochemically activated iron oxide formation on α-iron (Fe) microparticles for the efficient reaction with methane (CH4) was investigated using a simple milling process to successfully clarify ...

The mechanochemical surface functionalization of iron oxides with disordered lattices on bare iron (Fe) particles was investigated using simple milling processes to clarify the formation mechanism of the oxide layer and investigate the near-surface models with different states. The homogeneous α-Fe particles at the milling equilibrium were first prepared under an argon atmosphere. After the subsequent milling reaction of the particles with oxygen molecules, the surface analyses by X-ray diffraction and Raman and X-ray photoelectron spectroscopies revealed that the near-surface layers consisted of two iron oxide phases (α-Fe2O3 and Fe3O4) through oxygen atom diffusion, and the α-Fe2O3 was dominantly grown on the near surface. During the initial reaction, the signals from an electron spin resonance suggested the dangling bond formation on α-Fe2O3. The oxygen atoms effectively induce disordered lattices in the local area to form oxidized Fe3+ clusters, and the geometric distortion formed the dangling bonds, ...

The mechanochemical fabrication of the composites between carbon fibers (CFs) and nylon-6 (N6) was investigated using a milling process. By the milling, defected surfaces were generated on CFs to obtain the homogeneous length with preserving the cylindrical shape of CF. Fourier transform infrared spectra revealed that the band intensities due to C═O, C–N and O–H bondings increased with the milling. The band position of C–N was shifted to a higher wavenumber, while that of C═O did not change, implying that the main chain of N6 was dissociated at the C–N neighboring the C═O bonds by the force, and subsequently, new bonds between the N atoms of the activated N6 and the C atoms on CFs would be formed. Therefore, the efficient fabrication of the CF/N6 composite fibers with the interfacial bondings was achieved using the mechanochemical reaction.

Collagen fibril membranes (CFMs) with a high mechanical property were fabricated with a lateral face evaporation method, in which type I atelocollagen extracted from tilapia scales was used. The density and thickness of the CFM obtained were 0.51 ± 0.04 mg/cm 3 and 50 ± 5 μm. The collagen fibrils in the CFM had a similar periodic stripped pattern of 67 nm with native collagen fibrils. The CFM was crosslinked in gaseous glutaraldehyde for different duration in order to increase the mechanical property. The crosslinking degrees of the CFMs analyzed by free amino groups gradually increased to 70.3 % against the exposure duration until 6 hours, and reached a plateau. The denaturation temperatures of the CFMs with the crosslinking degrees at 20.4 % to 43% were linearly increased from 49°C to 75°C. The tensile strength of the CFMs was slightly improved until the crosslinking degree at 33.3 % and then the tensile strength rapidly increased to be 68 MPa. It was suggested that a percolation phenomenon took place in the CFMs by crosslinking of collagen fibrils with polymerized GA molecules.

The fabrication of copper–graphite composites by a milling process was investigated using a centrifugal ball mill. The copper particles were homogeneously milled in a graphite vessel, and the reaction time was varied. Scanning electron microscopy images clearly revealed that a fragment of graphite ground by the copper particle adheres to the copper particle surface, indicating the formation of a copper–graphite composite. The composite graphite amount per 1 g of copper particles increased to 0.46 mg at the milling time 5 min, and subsequently decreased to 0.25 mg at 60 min, indicating the suitable milling-time for the interfacial adhesion. When using only the copper particles, the naturally oxidized layer on the surface decreased with milling. On the other hand, when using only the graphite, the characteristic graphite structure is disrupted and the defect structure increased with milling. Thus, the new copper surface generated by milling strongly reacts with the defect structure of the graphite. It is suggested that the interfacial bonding between the copper and graphite was attributed to a Van der Waals attraction and/or binding force due to oxygen atoms located at the interface.

Hybrid nanocrystals of 8-hydroxyquinoline (8Hq) molecules and hydroxyapatite nanocrystals (HAp) were successfully prepared by a mechanochemical solid-state reaction. The hybrid nanocrystals exhibit a significant thermal stability and efficient photoluminescence peak at 500 nm, which were attributed to metal–ligand charge transfer at the interface between the oxygen atoms of 8Hq and the calcium ions of HAp, and the interfacial photofunctions were mechanochemically controlled. The interfacial bonding structures were also supported by a DV-Xα molecular orbital calculation.

The fabrication of iron–graphite composites was investigated using a milling process. Based on the milling time of the process, the average particle size of the host iron particles decreased to 10 µm. The size of the graphite particles decreased to a nanometer scale, resulting in the graphite strongly adhering to the iron surfaces. Raman spectra revealed that the graphite aromatic ring structure disappeared and the iron near-surface layer was changed to iron oxide phases. The dangling bond of the fragmented graphite combined with the oxidized iron surface by interfacial binding to efficiently form the interfacial composites.

Europium (III) (Eu(3+))-doped nanoporous silica spheres were synthesized, and the states of Eu(3+) ions in the silica framework structure were investigated. The ordered nanopores were preserved with the doping at the Eu(3+) molar concentration to Si up to 10 mol%, and the O-Si-O and Si-OH groups in the structures were clearly rearranged with the doping, indicating the interaction of Eu(3+) with the O atoms. The significant morphological changes in the spheres were observed with the doping. The photoluminescence spectral shapes due to the transitions of (5)D(0)-(7)F(1) and (5)D(0)-(7)F(2) were indicative of the presence of the Eu(3+) in an environment of a low symmetry. It was found that the Eu(3+) was located inside the silica framework to electrostatically interact with the environmental O atoms, which would prevent the aggregation among Eu(3+) ions to show the efficient luminescence. Therefore, the interactions between the Eu(3+) ions and silica framework structures in the spheres were successfully clarified.

Europium (III) (Eu 3+ )-containing nanoporous silicas were successfully synthesized by two different loading methods (adsorption or doping), and the states of the Eu 3+ in the structure were investigated. The Eu 3+ -adsorption indicated that the Eu 3+ interacts with hydroxyl groups on the pore surface and H 2 O molecules to enhance the quenching, whereas the Eu 3+ -doping indicated that the Eu 3+ was located inside the structure framework that produced the efficient luminescence. The interaction between the Eu 3+ and silica structure depended on the loading method.

Composites between carbon fibers (CFs) and heterogeneous materials have been widely studied and their fabrication techniques have been developed. However, their hydrophobic surfaces make it difficult to disperse CFs into hydrophilic resins, which results in weak junctions with ceramics. To develop high-strength composite fibers, it is important to design interfacial chemical bonds. Thus, surface-modification techniques of CFs have recently become the main focus and their interfaces have been characterized by various analytical methods. In this Minireview, various techniques that modify the CF surface by coating with inorganic polymers (metal oxide compounds) are highlighted, and the applications of novel nanocomposite fibers are also described. Furthermore, interfacial bonds between CFs and polymer resins are reviewed and discussed in terms of CF-reinforced plastics and their future prospects.

Crystallographically anisotropic platelet iron particles were successfully prepared using a conventional ball mill with addition of graphite (Gp) particles. The morphological and structural changes resulting from the milling were investigated using scanning electron microscopy and X-ray diffraction. The spherical iron particles were plastically deformed into platelet shapes during the milling. Simultaneously, it is suggested that the size of the Gp particles decreased and adhered as nanoparticles on the surface of the iron particles. The adhered Gp particles affected the plastic deformation behavior of the iron particles: the {001} planes of α-iron were oriented parallel to the particle face, and no preferred in-plane orientation was observed. This study not only details the preparation of soft magnetic metal particles that crystallographically oriented to enhance their magnetic properties but also provides new insight into the activities of the well-established and extensively studied mechanical milling method.

The incorporation of anthracene (Ant) into nanoporous silica/surfactant nanocomposite spheres was successfully achieved using a mechanochemical solid state reaction. The Ant molecules were incorporated into the nanopores while preserving the silica nanostructures, indicating the effective hydrophobic interactions with the alkyl chains of the surfactant. The blue photoluminescence intensity due to the monomer state was enhanced by increasing the mechanochemical milling force, suggesting this is an efficient preparation method for a luminescent medium by monomeric assembly of the Ant molecules.