Dual structural transition in small nanoparticles of Cu-Au alloy

Cu-Au alloy nanoparticles are known to be widely used in the catalysis of various chemical reactions as it was experimentally defined that in many cases the partial substitution of copper with gold increases catalytic activity. However, providing the reaction capacity of alloy nanoparticles the surface electronic structure strongly depends on their atomic ordering. Therefore, to theoretically determine catalytic properties, one needs to use a most real structural model complying with Cu-Au nanoparticles under various external influences. So, thermal stability limits were studied for the initial L1₂ phase in Cu₃Au nanoalloy clusters up to 8.0 nm and Cu-Au clusters up to 3.0 nm at various degrees of Au atom concentration, with molecular dynamics method using a modified tight-binding TB-SMA potential. Dual structural transition L1₂?→?FCC and further FCC?→?Ih is shown to be possible under the thermal factor in Cu₃Au and Cu-Au clusters with the diameter up to 3.0 nm. The temperature of the structural transition FCC?→?Ih is established to decrease for small particles of Cu-Au alloy under the increase of Au atom concentration. For clusters with this structural transition, the melting point is found to be a linear increasing function of concentration, and for clusters without FCC?→?Ih structural transition, the melting point is a linear decreasing function of Au content. Thus, the article shows that doping Cu nanoclusters with Au atoms allows to control the forming structure as well as the melting point.     

Positron annihilation spectroscopy characterization of effect of intermetallic nanoparticles on accumulation and annealing of vacancy defects in electron-irradiated Fe–Ni–Al alloy

The effect of intermetallic nanoparticles like Ni₃Al and nanoparticles of an Fe-rich bcc phase on the evolution of vacancy defects in an fcc Fe–34.2 wt% Ni–5.4 wt% Al model alloy under electron irradiation at elevated temperatures (423 and 573 K) was investigated using positron annihilation spectroscopy. Nanosized (1–8 nm) particles, which are homogeneously distributed in the alloy matrix, cause a several-fold decrease in the accumulation of vacancies as compared to their accumulation in a quenched alloy. This effect depends on the size and the type of nanoparticles. The effect of the nanoparticles increases when the irradiation temperature increases. The irradiation-induced nucleation and the growth of intermetallic nanoparticles were also observed in an alloy pre-aged at 1023 K under irradiation at 573 K. Thus, a quantum-dot-like positron state within ultrafine intermetallic particles, which we revealed earlier, allows control of the evolution of coherent precipitates like Ni₃Al, along with vacancy defects, during irradiation and subsequent annealing. Possible mechanisms of the absorption of point defects by nanoparticles are discussed.     

Nucleation kinetics in a CuCl solid solution in glass: Calculation and comparison with experiment

The kinetics of formation of CuCl nanoparticles in a glass has been studied. The experimental results obtained have been compared with the results of calculations. A method has been developed for calculating the nucleation kinetics, which decreases the time of calculations by a factor of several tens. This has been achieved using the joint kinetic equation for distributions of clusters over the number of particles and over the radius. The distributions over the number of particles and over the radius have been used for small and large clusters, respectively. The concentration of molecules near the surface of clusters has been determined from the asymptotic solution of the diffusion equation. For subcritical clusters, the concentration of molecules near the cluster surface has been taken to be equal to the average concentration in the solid solution. This method has been used to calculate the nucleation kinetics of CuCl nanoparticles in a glass. The results obtained from the calculation of the time dependences of the increase in the concentration and average radius of clusters agree well with experiment.     

Laser ablation synthesis of monodispersed magnetic alloy nanoparticles

Monodispersed CoPt alloy nanoparticles were synthesized by a pulsed laser ablation (PLA) technique coupled with a low-pressure operating differential mobility analyzer (LP-DMA). The CoPt alloy nanoparticles were generated by laser ablating a solid Co–Pt target. In CoPt alloy nanoparticles synthesized from a target with a Co composition of 75 at%, the nanoparticle surfaces were covered by an oxide layer and exhibited a core-shell structure. In contrast, no shell was observed in particles generated from a target with a Co:Pt ratio of 50:50 at%. According to an EDX analysis, the compositions of the individual nanoparticles were almost the same as that of the target material. Finally, the magnetic hysteresis loops of the CoPt alloy nanoparticles exhibited ferromagnetism.     

Semiconductor nanostructures enabled by aerosol technology

Aerosol technology provides efficient methods for producing nanoparticles with well-controlled composition and size distribution. This review provides an overview of methods and results obtained by using aerosol technology for producing nanostruetures for a variety of applications in semiconductor physics and device technology. Examples are given from： production of metal and metal alloy particles： semiconductor nanoparticles; semiconductor nanowires, grown both in the aerosol phase and on substrates; physics studies based on individual aerosol-generated devices; and large area deviees based on aerosol particles.     

Tin/Indium nanobundle formation from aggregation or growth of nanoparticles

Shape and size controlled gram level synthesis of tin/indium (SnIn) alloy nanoparticles and nanobundles is reported. Poly(N-vinylpyrrolidone) (PVP) was employed as a capping agent, which could control the growth and structure of the alloy particles under varying conditions. Transmission electron microscopy showed that unique SnIn alloy nanobundles could be synthesized from the bulk materials above a certain concentration of PVP and below this concentration, discrete spherical nanoparticles of variable size were evolved. The morphology and the composition of the as-synthesized SnIn alloy nanobundles were investigated by high-resolution transmission electron microscopy (TEM). The possible mechanisms on the formation of these structures were discussed.     

Quantum antidot formation and correlation to optical shift of gold nanoparticles embedded in MgO

Quantum antidots are subnanometer scale vacancy clusters, the localized electronic structure of which can significantly alter the properties of a nanomaterial. We use positron spectroscopy to study vacancy clusters generated during the formation of gold nanoparticles via ion implantation in an MgO matrix. We observed that quantum antidots are associated with the nanoparticle surfaces after annealing in an O2 atmosphere, but not after annealing in a H2 atmosphere. In the former case, the presence of quantum antidots bound to the gold nanoparticles correlates with the redshift of the gold surface plasmon resonance, thus allowing an explanation for the redshift based on the transfer of electrons away from the metal particles.     

Oxidation behaviour of Ni nanoparticles and formation process of hollow NiO

The oxidation behaviour of Ni nanoparticles at temperatures from 573 to 673 K and the formation process of hollow oxide particles were studied by transmission electron microscopy. In the course of oxidation, a single large void was observed at one site of the interface between inner Ni and outer NiO layer due to vacancy clustering, which occurs during the oxidation process resulting from the rapid outward diffusion of Ni ions through the NiO layer. This suggests that supersaturated vacancies generated at the interface migrate to the site over a long-range distance and aggregate at the site. Ni nanoparticles were fully oxidized to become hollow NiO, in which nano-holes in the form of vacancy clusters were located at the off-centred positions. The de-centring of the voids in hollow NiO is probably due to the large mobility of vacancies inside Ni during oxidation.     

Health implications of nanoparticles

Nanoparticles are increasingly used in a wide range of applications in science, technology and medicine. Since they are produced for specific purposes which cannot be met by larger particles and bulk material they are likely to be highly reactive, in particular, with biological systems. On the other hand a large body of know-how in environmental sciences is available from toxicological effects of ultrafine particles (smaller than 100 nm in size) after inhalation. Since nanoparticles feature similar reactivity as ultrafine particles a sustainable development of new emerging nanoparticles is required. This paper gives a brief review on the dosimetry of nanoparticles, including deposition in the various regions of the respiratory tract and systemic translocation and uptake in secondary target organs, epidemiologic associations with health effects and toxicology of inhaled nanoparticles. General principles and current paradigms to explain for the specific behaviour of nanoparticles in toxicology are discussed. With that respect we consider nanoparticles to be in the range from 1 to 2 nm (clusters of atoms/molecules) to particles that are smaller than 100 nm at least in one dimension. Since the evidence for health risks of ultrafine and nanoparticles after inhalation has been increasing over the last decade, the paper attempts to extrapolate these findings and principles observed in particle inhalation toxicology into recommendations for an integrated concept of risk assessment of nanoparticles for a broad range of use in science, technology and medicine.Based on this article a book chapter will appear soon (Kreyling et al., 2006).     

T2 relaxation induced by clusters of superparamagnetic nanoparticles: Monte Carlo simulations

Clustering strongly affects the transverse (T2) relaxation induced by superparamagnetic nanoparticles in magnetic resonance experiments. In this study, we used Monte Carlo simulations to investigate systematically the relationship between T2 values and the geometric parameters of nanoparticle clusters. We computed relaxation as a function of particle size, number of particles per cluster, interparticle distance, and cluster shape (compact vs. linear). We found that compact clusters induced relaxation equivalent to similarly sized single particles. For small particles, the shape and density of clusters had a significant effect on T2. In contrast, for larger particles, T2 relaxation was relatively independent of cluster geometry until interparticle distances within a cluster exceeded ten times the particle diameter. Results from our simulations suggest principles for the design of nanoparticle aggregation-based sensors for MRI.     

Surface reconstruction and decahedral structure of bimetallic nanoparticles

We report on energetic surface reconstruction phenomena observed on bimetallic nanoparticle systems of AuPd and AuCu, similar to a resolidification effect observed during the cooling process in lead clusters. These binary alloy nanoparticles show the fivefold edges truncated, resulting in [100] facets on decahedral structures, an effect largely envisioned and reported theoretically, with no experimental evidence so far. We demonstrate experimentally as well as by computational simulations that this new eutectic structure is favored in such nanoalloy systems.     

Dynamic nucleation and growth of Ni nanoparticles on high-surface area titania

Nucleation and growth mechanisms of Ni nanoparticles synthesized via an incipient wetness technique on a high-surface area titania support (i.e., a mixture of anatase and rutile) are studied using environmental transmission electron microscope (ETEM). Most Ni nanoparticles are found to nucleate from the Ni precursor coated on the surface of the titania support. Even though both anatase and rutile supports are the nucleation sites for Ni nanoparticles, it was observed that the particles have different morphologies on the supports, i.e., a non-wetting morphology on the anatase support versus a wetting morphology on the rutile {1 0 1}. This is because the interfacial energy of Ni/rutile is lower than that of Ni/anatase. Titania clusters are found to nucleate on the surface of the Ni particles during in situ ETEM reduction, indicating that the presence of partial titania overlayers is directly related to the synthesis of the Ni/TiO₂ catalysts. The growth mode of the Ni nanoparticles on the titania support is three-dimensional, while that of the rutile cluster on the surface of the Ni is two-dimensional layer-by-layer.     

Formation Mechanism of Laser‐Synthesized Iron–Manganese Alloy Nanoparticles,Manganese Oxide Nanosheets and Nanofibers

Laser ablation in liquids (LAL) has emerged as a versatile approach for the synthesis of alloy particles and oxide nanomaterials. However, complex chemical reactions often take place during synthesis due to inevitable atomization and ionization of the target materials and decomposition/hydrolysis of solvent/solution molecules, making it difficult to understand the particle formation mechanisms. In this paper, a possible route for the formation of FeMn alloy nanoparticles as well as MnO_x nanoparticles, ‐sheets, and ‐fibers by LAL is presented. The observed structural, compositional, and morphological variations are clarified by transmission electron microscopy (TEM). The studies suggest that a reaction between Mn atoms and Fe ions followed by surface oxidation result in nonstoichiometric synthesis of Fe‐rich FeMn@FeMn₂O₄ core–shell alloy particles. Interestingly, a phase transformation from Mn₃O₄ to Mn₂O₃ and finally to Ramsdellite γ‐MnO₂ is accompanied by a morphology change from nanosheets to nanofibers in gradually increasing oxidizing environments. High‐resolution TEM images reveal that the particle‐attachment mechanism dominates the growth of different manganese oxides.     

Size effect on alloying ability and phase stability of immiscible bimetallic nanoparticles

In the present paper, the surface and size effects on the alloying ability and phase stability of immiscible alloy nanoparticles have been studied with calculating the heats of formation of Au-Pt alloy nanoparticles from the single element nanoparticles of their constituents (Au and Pt) with a simple thermodynamic model and an analytic embedded atom method. The results indicated that, besides the similar compositional dependence of heat of formation as in bulk alloys, the heat of formation of alloy nanoparticles exhibits notable size-dependence, and there exists a competition between size effect and compositional effect on the heat of formation of immiscible system. Contrary to the positive heat of formation for bulk-immiscible alloys, a negative heat of formation may be obtained for the alloy nanoparticles with a small size or dilute solute component, which implies a promotion of the alloying ability and phase stability of immiscible system on a nanoscale. The surface segregation results in an extension of the size range of particles with a negative heat of formation. The molecular dynamics simulations have indicated that the structurally and compositionally homogeneous AuPt nanoparticles tend to form a core-shell structure with temperature increasing.     

Cobalt iron-oxide nanoparticle modified poly(methyl methacrylate) nanodielectrics

In this paper, we report the dielectric properties of composite systems (nanodielectrics) made of small amounts of mono dispersed magnetic nanoparticles embedded in a polymer matrix. It is observed from the transmission electron microscope images that the matrix polymeric material is confined in approximately 100 nm size cages between particle clusters. The particle clusters are composed of separated spherical particles which comprise unconnected networks in the matrix. The dielectric relaxation and breakdown characteristics of the matrix polymeric material are altered with the addition of nanometer size cobalt iron-oxide particles. The dielectric breakdown measurements performed at 77 K showed that these nanodielectrics are potentially useful as an electrical insulation material for cryogenic high voltage applications. Finally, structural and dielectric properties of nanocomposite dielectrics are discussed to present plausible reasons for the observed low effective dielectric permittivity values in the present and similar nanodielectric systems. It is concluded that polymeric nanoparticle composites would have low dielectric permittivity regardless of the permittivity of nanoparticles are when the particles are coordinated with a low dielectric permittivity surfactant.     

Synthesis and characterization of polymer encapsulated Cu–Ni magnetic nanoparticles for hyperthermia applications

Copper nickel alloy nanoparticles were synthesized by polyol reduction method and by physical melting process. The particles were further coated with a biodegradable polymer, polyethylene glycol. The particles have a curie temperature in the range of 43–46 °C and are designed to be used for hyperthermia applications. Morphology of these encapsulated particles was determined by electron microscopy. The curie temperature for alloy particles and encapsulated particles was also measured.     

Silver nanoparticles deposited on dielectric surfaces

Surface plasmon polaritons in nanoparticles were used as a sensitive indicator of structural and electronic properties of metallic nanoparticles deposited upon various dielectric substrates. Quantum size and cluster–substrate interactions were separated. The latter were modelled with the dynamic charge transfer effect. For calibration purposes, the free surfaces of the same clusters exposed to a UHV beam were also investigated. The particles were slightly deformed during deposition; their final shapes and, in particular, their contact areas were determined. The width of the plasmon excitation band was roughly doubled compared to that of the free particles, but proved to depend only slightly on the chemical nature of the substrates, in drastic contrast to the case of fully embedded particles. The analogy holds for the dephasing lifetimes. One reason for this is that the contact area varies strongly with the substrate material, while it is constant in systems of matrix-embedded particles. Received: 26 July 2001 / Revised version: 10 September 2001 / Published online: 15 October 2001     

Magnetic properties of self-assembled nanostructure films on the base of amorphous Ni granules

We report on structural and magnetic properties of granular films consisting of 2.5 nm Ni nanoparticles. The films are fabricated by the original laser electrodispersion technique, which allows producing nearly monodisperse and amorphous particles. Atomic force microscopy (AFM) study shows that in 8 nm thickness films the particles are self-assembled in clusters with the lateral size 100-150 nm and the height of about 8 nm. Performed by SQUID, the films magnetization measurements reveal superparamagnetic behaviour, characteristic for an ensemble of non-interacting single domain magnetic particulates. It is found that the magnetic moment of the particulate is equal to that of about 3000 individual Ni nanoparticles and the blocking temperature is close to room temperature. Defined from magnetic measurements, the size of single domain particulates correlates well with the size of the clusters determined from AFM images. We propose that exchange interaction plays an important role in the formation of the particulates by aligning the magnetic moments of the individual Ni nanoparticles inside the clusters. Presence of magnetic clusters with high blocking temperature makes the fabricated films potentially useful for high-density magnetic data storage applications.     

Preparation of magnetic nanoparticles by pulsed plasma chemical vapor synthesis

FePt nanoparticle is expected as a candidate for the magnetic material of the high density recording media. We attempted to synthesize FePt alloy nanoparticles using 13.56 MHz glow discharge plasma with the pulse operation of a square-wave on/off cycle of plasma discharge to control the size of nanoparticles. Vapors of metal organics, Biscyclopentadienyl iron (ferrocene) for Fe and (Methylcyclopentadienyl) trimethyl platinum for Pt, were introduced into the capacitively coupled flow-through plasma chamber, which consisted of shower head RF electrode and grounded mesh electrode. Synthesis experiments were conducted at room temperature under the conditions of pressure 0.27 Pa, source gas concentration 0.005 Pa, gas residence time 0.5 s and plasma powers 60 watts. Pulse width for plasma duration was chosen from 0.5 to 30 s and plasma off period was 4 s to each pulse operation. Visual observations during the particle growth showed plasma emission in the bulk region was increased with the particle growth. These were theoretically explained by using the model for both transient particle charging in the plasma and single particle behavior in the stationary plasma as well as assuming the similarity between the negative charged particle and negative gas containing plasma. Synthesized nanoparticles were directly collected onto TEM grid, which was placed just below the grounded mesh electrode in the plasma reactor downstream. TEM pictures showed two kinds of particles in size, one of which was nanometer size and isolated with crystal structures and the other appeared agglomerate of nanometer size particles. The size of agglomerated particle was controlled in the 10–120 nm range by varying the plasma-on time from 0.5 to 30 s, although the nanometer size particles did not change. The composition of FePt alloy particles could be altered by adjusting the source gas feed ratio. Also magnetization of FePt nanoparticles was measured by use of SQUID (superconducting quantum interference device) magnetometry measurements. As-synthesized FePt nanoparticles did not exhibit loop-shape characteristic, which indicated superpamagnetic property. Annealed nanoparticles with the composition of Fe₅₈Pt₄₂ at 650°C in atmospheric hydrogen showed clear hysterisis loop with the coercivity as large as 10 KOe.     

Cluster structure and corralling effect driven by interaction mismatch in two dimensional mixtures

The formation of clusters with crystal-like order in two dimensions is studied using Monte Carlo simulations. We find that the necessary conditions to induce the formation of clusters of one component is to add a second component that has a larger size and that has a long-range soft repulsive interaction with its own kind but not with the other one. The clusters of the small particles are found to be surrounded by a network of quasi-one-dimensional arrangements of the larger particles. The degree of order of the clusters is found to depend on the concentration of the larger particles. The findings explain recent experimental observations on lipid-poloxamer mixtures and they provide guidelines for how to form ordered clusters of nanoparticles in two dimensions.