Size effect on the conduction electron spin resonance of small sodium particles in sodium azide NaN3

The conduction electron spin resonance from small (10 to 1000 Å sodium metal particles has been measured as a function of the particle size. The particles were formed inside single crystals of sodium azide by X-irradiating and annealing them at 280°C. The particle sizes were deduced from the optical absorption measurements reported in the previous article. According to the theory of the quantum size effect in small metal particles, very narrow resonances should have been observed. No such resonances were seen. The measured widths were between 7.5 and 20 G and could be analysed in terms of the bulk width plus a temperature independent but size dependent surface term. The reason why no quantum size effect was observed is not understood.     

A Monte Carlo study of surface segregation in alloys

The Monte Carlo method has been applied to the study of surface segregation in a multi-layer, regular solution model of alloy surfaces. Three different alloy configurations have been investigated: semi-infinite slabs, thin films and small particles. The results show that the alloy component with the lowest surface energy tends to segregate to the first three or four surface atom layers and that segregation is greater in clustering alloys than in ordering alloys. Furthermore, segregation is more pronounced in low coordination surfaces, as evidenced by a comparison of {110} and {100}-oriented surfaces of fcc alloys. The degree of surface segregation in thin films and small particles (in the particle size range studied) tends to be smaller than in semi-infinite slabs, because of mass conservation constraints, and decreases with decreasing film thickness and particle size. The results obtained are contrasted with previous calculations and possible avenues for improving surface segregation models are discussed.     

Size effect on the optical and paramagnetic absorption of silver particles in a glass matrix

A study has been made of the optical absorption produced by small (10–100 Å) silver particles in a glass matrix. Measurements of the width of the absorption agree quite well with those calculated theoretically using the particle sizes estimated from electron microscopy, whilst the peak position of the absorption calculated for the smallest size particles does not seem to be so reliable. Contrary to the theoretical predictions of the quantum size effect in small metal particles and to experimental results obtained by other workers, no conduction electron spin resonance was observed from the silver particles at room temperature or at 7.5°K.     

X-ray photoemission spectroscopy (XPS) analysis of Fe82B18-Al2O3 granular systems

X-ray photoemission spectroscopy (XPS) has been used to investigate the surface composition (down to some hundreds of Å) of granulars consisting of Fe₈₂B₁₈ small particles (?～40–70 Å) dispersed in an alumina insulating matrix.Fully oxidized iron and boron are found in the outermost region of samples while in depth analysis, achieved by Ar⁺ ion etching, provides evidence of both metallic and oxidized states for the two elements.Aluminate forms, suggestive of an interaction at the surface of the alloy particle and alumina, are also present in the sub-surface region and the interaction extent is quantitatively evaluated as a function of the particle size.     

Thickness dependence of magnetization in FeNi invar alloy film

The thickness dependence of magnetization of FeNi Invar alloy films was observed by means of small angle Lorentz electron diffraction. A remarkable reduction of magnetization at room temperature was observed for films with thickness below 400 Å. This may be ascribable to the instability of the ferromagnetic state in Fe-Ni Invar alloys.     

Differential sputtering of MgO/Au cermet films and its application to high-yield secondary-electron emitters

Very large differential-sputtering effects in fine-grained (particle size < 50 Å) MgO/Au cermet films have been observed by Auger electron spectroscopy. Under Ar-ion bombardment, the surface Au content was found to decrease exponentially with time by up to a factor of 20. A theoretical model for differential sputtering of granular systems is presented that gives good agreement with the experimental data. The differential sputtering produces a MgO-rich surface layer and therefore results in excellent secondary-electron-emission properties for low-energy incident electrons.     

Effect of crystallite size on coercive force of thin electrodeposited Ni-Fe films

Thin Ni-Fe films were electrodeposited onto Cu-substrates which had been evaporated onto glass microscope slides. The coercive force of the as-plated films increased with increasing crystallite size. The coercive force of films stripped from their substrates was determined after increasingly severe anneals. The results obtained suggest that for crystallite sizes in the approximate range 300 to 800 Å the coercive force does not depend appreciably on crystallite size as such. The observed increase of coercive force with annealing may be explained in terms of surface roughness.     

Effect of Al particle size on the reaction kinetics and densification of TiAl intermetallics

The present investigation deals with response of the particle size of aluminum on the reactive sintering of Ti–Al intermetallics and subsequently on their reaction kinetics and densification behavior. Aluminum powders of initial average particle size of 44 μm were milled for various durations in a planetary ball mill to produce average particles sizes of 100, 28 and 7 μm. These aluminum powders of various particle sizes i.e. 100, 28 and 7 μm were mixed with titanium powder of average particles size of 44 μm in the ratio of 1:1 corresponding to the Ti–Al intermetallic composition. The reactive sintering temperatures of the mixtures were determined by DTA and the effect of change in particle Al particle size has been determined for the activation energy ofthe self-propagating reaction. The effect of Al particle size on the sintering was determined by studying density and microstructure.     

Curietemperatur und Kollektivmagnetisierung bei ein- und vielkristallinen dünnen Nickelschichten

With a method of observing the temperature dependence of therf-permeability the Curie temperatureΘ of evaporated thin films (thicknessD from 30 to 300 Å) of nickel with various structures was investigated. Monocrystalline samples withD about 50 Å showedΘ-values comparable to the bulk material. The behaviour of some polycrystalline and several granulated films depends to a large extent on the structure (varied by conditions of deposition). It may be explained with a model that treats aggregates of small ferromagnetic particles with a high spontaneous magnetization but an interaction that may be considerably weaker than the full ferromagnetic exchange coupling. There appears a transition (to superparamagnetism) temperatureT _A which can be much lower than the Curie temperature. The expected dependence of T_A on particle size fits approximately with the experimental results from therf-method and electron diffraction data at samples of various structures.     

Electrodeposition of nanocrystalline Zn-Ni alloy from alkaline glycinate bath containing saccharin as additive

Nanocrystalline Zn-Ni (crystallite sizes 13-68 nm) alloy coatings were produced from an alkaline glycinate bath containing saccharin as additive. X-ray diffraction (XRD) was used to determine the phase composition and average crystallite size of nanocrystalline Zn-Ni alloy coatings. The average grain size of a deposit was also studied by transmission electron microscopy (TEM). The effects of saccharin concentration and current density on the crystallite size and surface roughness of the coatings were studied. Crystallite size and average surface roughness were diminished as a result of increasing saccharin concentration. Scanning electron microscopy (SEM) examination showed that coatings had a colony-like morphology and the colony size was increased with increasing current density. Microhardness testing was carried out in order to determine the degree of dependence of this mechanical property on the crystallite size. It was found that microhardness did not depend on crystallite size (Hall-Petch).     

Particle size effect on thermal conductivity of AlN films with embedded diamond particles

Fabricating composite thin films is an effective and economic solution to improve the thermal performance of the films. The diamond particles of different sizes were successfully embedded in AlN thin films by a chemical solution approach, which was confirmed by scanning electron microscope, x-ray diffraction analysis and x-ray photoelectron spectroscopy. The thermal properties of the films embedded with different diamond particles were studied by using a 3-omega method, which was observed to be strongly dependent on the particle size. A 19 % enhancement in thermal conductivity can be achieved by embedding diamond particles of 1-μm radius in AlN thin films. However, the thermal conductivity decreases after embedding with 10-nm radius diamond particles. The results are discussed with high volume model, which confirms that the interface thermal resistance between the embedded materials and the films plays an important role in determining the thermal conductivity of the as-grown carbon material embedded AlN films.     

Catalytic soot oxidation in microscale experiments: Simulation of interactions between co-deposited graphitic nanoparticle agglomerates and platinum nanoparticles

Continuously regenerating catalytic soot traps are under development to reduce particulate emissions from diesel exhaust. A good understanding of the processes that take place during soot oxidation is needed to optimize diesel soot trap performance. To gain insight into these processes from the perspective of nanoparticle technology, the effects of catalyst particle size and the interparticle distance between soot and catalyst particles were measured. A model catalyst was prepared by depositing Pt nanoparticles on a SiO/SiO₂-coated transmission electron microscope (TEM) grid. A soot surrogate composed of graphitic nanoparticle agglomerates generated by laser ablation was deposited on the same surface. This system simulates, morphologically, catalytic soot traps used in practice. The reaction was carried out in a tubular flow reactor in which the gas phase simulated diesel exhaust gas, composed of a mixture of 10% O₂ and 1000 ppm NO with the remainder N₂. The progress of the carbon nanoparticle oxidation was monitored off-line by analysis of electron microscopy images of the agglomerates before and after reaction. This experimental method permitted the correlation of reaction rate with particle sizes and separation distances as well as catalyst surface area in the direct environs of the soot particles. The experimental results revealed no effect of Pt catalyst particle size in the range 7–31 nm on the rate of reaction. Also observed were a decrease in the rate of reaction with increasing distance between carbon agglomerates and catalyst particles and a linear dependence of the reaction rate on the fractional catalyst surface area coverage.     

Controlled synthesis of photoluminescent Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> nanoparticles from metal-organic polymeric precursor

Bi₄Ti₃O₁₂ (BIT) nanoparticles with a narrow average particle size distribution in the range of 11–46 nm was synthesized via a metal-organic polymeric precursor process. The crystallite size and lattice parameter of BIT were determined by XRD analysis. At annealing temperatures >550 °C, the orthorhombic BIT compound with lattice parameters a = 5.4489 Å, b = 5.4147 Å, and c = 32.8362 Å was formed while at lower annealing temperatures orthorhombicity was absent. Reaction proceeded via the formation of an intermediate phase at 500 °C with a stoichiometry close to Bi₂Ti₂O₇. The particle size and the agglomerates of the primary particles have been confirmed by FESEM and TEM. The decomposition of the polymeric gel was ascertained in order to evaluate the crystallization process from TG-DSC analysis. Raman spectroscopy was used to investigate the lattice dynamics in BIT nanoparticles. In addition, investigation of the dependence of the visible emission band around the blue–green color emission on annealing temperatures and grain sizes showed that the effect of grain size plays important roles, and that oxygen vacancies may act as the radiative centers responsible for the observed visible emission band.     

Kramers Kronig analysis of the optical properties of small silver particles

In order to complete a preceding paper the dielectric constant? of the particle material of small silver particles with diameters between 210 and 25 Å is computed in the wavelength region 365≦λ≦455 nm from the measured spectra of thesmall particle plasma reasonance absorption. For this purpose a properKramers Kronig relation is derived, and is checked by applying to particles with Drude free electron gas. The results, concerning the silver particles, are that the real part of? changes slightly, whereas the imaginary part is markedly enhanced (up to the ten-fold of the bulk values) if the particle size decreases. This size dependence of? can quantitatively be described with thefree path effect within the accuracy of the measured values. Conversely, thebulk dielectric constant of silver is obtained by applying the free path effect to the measured dielectric constant of the small particles.     

Auger study of preferred sputtering on binary alloy surfaces

Auger Electron Spectroscopy has been used to investigate the preferred sputtering behavior on homogeneous Cu/Ni alloy surfaces. Measurements were made on a range of alloy compositions with Ar⁺ sputter ions of 0.5 to 2 keV energy. A kinetic model has been formulated to describe the time variation of the surface composition during sputtering. Based on this model, we were able to determine the individual sputter yields for Cu and Ni atoms in the alloy and the depth of the surface layer where the composition is altered by sputtering. The sputter yields were found to be relatively independent of the alloy composition but increased almost linearly with energy. The depth of the altered layer was comparable to the Auger sampling depth with its value increasing from 10 Å to more than 20 Å when ion energy increased from 0.5 to 2 keV.     

Tensile properties and interfacial interactions of bimodal hard/soft latex blends

In this work, the effect of composition, particle size and particle size ratio on the tensile properties of well-characterized hard/soft latex blends was investigated. Four blends of hard/soft latices, with varying particle sizes (either small or large), and volume fractions of 100/0, 80/20, 60/40, 50/50, 40/60, 20/80 and 0/100 were studied. The stress at break increased and the strain at break decreased as the amount of hard particles in the blend increased. A simple model, introduced by Pukanszky for filled polymers and polymer blends, proved to be a very useful tool for evaluating the tensile properties of the latex blends. Parameter B of the model could be related to the specific surface of the dispersed hard particles and the particle size ratio. Increasing the specific surface of the dispersed hard particles resulted in an increase in parameter B. The influence of particle size ratio on parameter B was shown to depend on the formation of aggregates.     

Taylor dispersion of nanoparticles

The ability to detect and accurately characterize particles is required by many fields of nanotechnology, including materials science, nanotoxicology, and nanomedicine. Among the most relevant physicochemical properties of nanoparticles, size and the related surface-to-volume ratio are fundamental ones. Taylor dispersion combines three independent phenomena to determine particle size: optical extinction, translational diffusion, and sheer-enhanced dispersion of nanoparticles subjected to a steady laminar flow. The interplay of these defines the apparent size. Considering that particles in fact are never truly uniform nor monodisperse, we rigorously address particle polydispersity and calculate the apparent particle size measured by Taylor dispersion analysis. We conducted case studies addressing aqueous suspensions of model particles and large-scale-produced “industrial” particles of both academic and commercial interest of various core materials and sizes, ranging from 15 to 100 nm. A comparison with particle sizes determined by transmission electron microscopy confirms that our approach is model-independent, non-parametric, and of general validity that provides an accurate account of size polydispersity—independently on the shape of the size distribution and without any assumption required a priori.     

Fractional Penetrations for Electrostatically Charged Fibrous Filters in the Submicron Particle Size Range

Particle penetrations through commercially available, electrically charged fibrous filters have been measured. The particles were monodisperse and in charge equilibrium. Tests were conducted for several particle sizes in the range 0.02 μm ≤ x ≤ 1 μm. The face velocity was varied in the range of 2 cm/s to 30 cm/s. The penetration has a bimodal dependence on particle size. This behaviour is not found for uncharged filters. The reduction in penetration and bimodal dependence is attributed to electrical collection effects. As the face velocity is increased, the electrostatic collection effects are significantly reduced. The results agree quantitatively with a model for particle penetration through charged fibrous filters recently presented in the literature by the authors.     

An empirical relationship between atoms and ions sputtered from single crystal surfaces

The temperature dependence of long range order at a (100) surface of Cu₃Au has been determined by low energy electron diffraction. Auger electron spectroscopy revealed that the composition of the alloy near the surface is changed by ion bombardment, but the stoichiometric composition is reconstituted by annealing. The order parameter of the surface, which was obtained from the temperature dependence of a superlattice beam, appears to be a continuous function of temperature, unlike the bulk order parameter. The disordering process at the surface begins about 60°K below a critical temperature which is common to both the surface and the volume. Monte Carlo calculations of the order parameter as a function of temperature for a model incorporating nearest- and next-nearest-neighbor interactions reproduce the experimental results and also provide an evaluation of the change in order parameter as a function of layer number for boundary conditions corresponding to a copper or a copper-gold surface.     

Kinetic stability of hematite nanoparticles: the effect of particle sizes

Nanoparticles are ubiquitous in environment and are potentially important in many environmental processes such as sorption, coprecipitation, redox reactions, and dissolution. To investigate particle size effects on nanoparticle aggregation and stability, this study tested aggregation behavior of 12(±2), 32(±3), and 65(±3) nm (hydrated radius) hematite particles under environmental relevant pH and ionic strength conditions. The results showed that at the same ionic strength and pH conditions, different particle sizes show different tendency to aggregate. At the same ionic strength, aggregation rates are higher for smaller particles. The critical coagulation concentration also depends on particle size, and decreases as particle size decreases. As the particle size decreases, fast aggregation shifted to lower pH. This may be related to a dependence of PZC on particle size originating from change of structure and surface energy characteristics as particle size decreases. Under the same conditions, aggregation occurs faster as particle concentration increases. Even though the nanoparticles of different sizes show different response to the same pH and ionic strength, DLVO theory can be used to qualitatively understand hematite nanoparticle aggregation behavior.