Thermomagnetic determination of Fe3O4 magnetic nanoparticle diameters for biomedical applications

The utility and promise of magnetic nanoparticles (MagNPs) for biomedicine rely heavily on accurate determination of the particle diameter attributes. While the average functional size and size distribution of the magnetic nanoparticles directly impact the implementation and optimization of nanobiotechnology applications in which they are employed, the determination of these attributes using electron microscopy techniques can be time-consuming and misrepresentative of the full nanoparticle population. In this work the average particle diameter and distribution of an ensemble of Fe₃O₄ ferrimagnetic nanoparticles are determined solely from temperature-dependent magnetization measurements; the results compare favorably to those obtained from extensive electron microscopy observations. The attributes of a population of biocompatible Fe₃O₄ nanoparticles synthesized by a thermal decomposition method are obtained from quantitative evaluation of a model that incorporates the distribution of superparamagnetic blocking temperatures represented through thermomagnetization data. The average size and size distributions are determined from magnetization data via temperature-dependent zero-field-cooled magnetization. The current work is unique from existing approaches based on magnetic measurement for the characterization of a nanoparticle ensemble as it provides both the average particle size as well as the particle size distribution.     

Surface effects in maghemite nanoparticles

A consistent model is presented for the variation of saturation magnetization with particle size in maghemite nanoparticles, based on the existence of a magnetically disordered layer with a constant thickness of 1 nm. For particles smaller than 3 nm, layer thickness increases rapidly, and M_S is already zero for 2.5 nm particle size. Magnetization measurements have been performed on maghemite–polymer nanocomposites with low size dispersion and a regular distribution of particles in the matrix. A representative number of samples have been studied with a diameter size in the range from 1.5 to 15 nm and ±10% of size dispersion.     

Effect of particles on the flow structure and dispersion of solid impurities in a two-phase axisymmetric jet

The Euler approach is used for studying the structure of a flow and the propagation of a disperse impurity in a submerged two-phase jet for small values of the mass concentration of particles (M _L1 = 0 to 0.5) upon a variation of the size and material of particles in a wide range. The effect of particles on the propagation of a two-phase jet, gas turbulence, and solid phase dispersion is analyzed. The addition of particles decreases the jet opening angle, increases the jet range, suppresses turbulence, and deteriorates turbulent mixing with the surrounding submerged space. It is shown that at the first stage, particle accumulation effects (pinching) in the axial region of the jet appear upon an increase in the particle size and the density of the particle material. Then, upon an increase in the inertia of particles, pinching changes to intense scattering of the disperse phase in the initial cross sections of the jet. The results are compared with the results of measurements for mono- and polydisperse two-phase jet flows.     

Light Scattering Studies on Phase Behavior of PP/PcBR Blends During Melt‐Mixing

Phase formation, morphology, and their evolution of binary blends of polypropylene with poly(cis‐butadiene) rubber were investigated by a back small angle laser scattering (BSALS) on‐line system and online sampling. The morphology formation process can be divided into three stages: early stage, intermediate stage, and late stage. Phase contrast microscopy (PCM) and small angle laser scattering (SALS) measurements have been introduced to compare with the results of BSALS and the corresponding phase morphology was also observed using scanning electron microscopy (SEM). Structure parameters such as average chord length l¯₁ and integral invariant Q were calculated to describe the relationship between phase evolution and processing conditions. Furthermore the velocity constant of the dispersed phase dimension variation k=dQ/dt was calculated at the early stage to describe the relationship with different volume fractions of dispersed phase. The characteristic wavevector q _m , and its corresponding maximum intensity I _m , increase monotonically with time and vary exponentially with time at the early stage of phase dispersion; the slope yields the change rate constants of domain size for q _m and I _m , α and β, respectively. The rate constants α and β increase with increasing content of dispersed phase, and α/β ≈1.     

On-Line Particle Size Analysis Using Ultrasonic Velocity Spectrometry

A new method is described for the determination of particle size distribution of slurries based on ultrasonic velocity spectrometry combined with gamma-ray transmission. This method shares the advantages of ultrasonic attenuation spectroscopy of being capable of analyzing highly concentrated samples without dilution. However the ultrasonic velocity method is better suited to fine particles of diameter from about 0.1 to 30 μm, a greater volume of slurry is analysed and therefore sampling errors are reduced, and precise theoretical models are readily available to permit the accurate determination of size distribution by inversion of ultrasonic velocity measurements. The method can also be used to accurately determine particle size cut points by linear correlation. Using either inversion or correlation methods, the accuracy of particle size information from ultrasonic velocity spectroscopy is significantly enhanced by the independent measurement of solids loading by gamma-ray transmission. In addition, larger sizes can be measured by combining the ultrasonic velocity method with ultrasonic attenuation measurements. The method has been tested in the laboratory on a wide variety of mineral and paint slurries. The method determined the size distribution of single component silica and alumina samples in water in agreement with laser diffraction measurements and the method successfully distinguished well and poorly dispersed TiO₂ suspensions. For composite samples the method discriminated separate TiO₂ and CaCO₃, components and determined their proportions to within 0.25% volume. In addition the method, in combination with ultrasonic attenuation measurements, determined the size fractions of iron ore slurries below 10 and 30 μm to within 1.3% and 1.0% relative respectively, when compared with laser diffraction measurement of particle size. The CSIRO is presently designing an industrial gauge which will be manufactured and installed in an industrial slurry stream in 1997.     

Global Rainbow Thermometry for Mean Temperature and Size Measurement of Spray Droplets

Global rainbow thermometry is a new technique for measuring the average size and temperature of spray droplets. For data inversion a global rainbow pattern is employed, which is formed by constructive interference of laser light scattered by an ensemble of spherical droplets. The non‐spherical droplets and liquid ligaments provide a uniform background and hence do not influence the interference pattern from which average size and temperature are derived. This is a large improvement with respect to standard rainbow thermometry, investigated since 1988, which is strongly influenced by particle shape. Moreover, the technique is applicable to smaller droplets than the standard technique because the global pattern is not spoiled by a ripple structure. Data inversion schemes based on inflection points, minima and maxima are discussed with respect to spray dispersion and droplet flux. The temperature derivation from inflection points appears to be independent of spray dispersion. Preliminary measurements in a heated water spray are reported. The mean diameter obtained from the rainbow pattern is smaller than the arithmetic mean diameter measured by phase‐Doppler anemometry. The accuracy of the temperature measurement by global rainbow thermometry is shown to be a few degrees Celsius.     

Optical,structural and magnetic properties of Zn0.9Cd0.1S:yCo nanoparticles

Zn_0.9Cd_0.1S:yCo nanoparticles were prepared by a co-precipitation method at low temperature. The obtained products were identified to be of cubic structure without any impurity phase. Cobalt incorporation leads to an increase in the local strain value and a decrease in the lattice constants as measured from XRD. Magnetic measurements showed that cobalt was incorporated in the Zn_0.9Cd_0.1S lattice as Co²⁺ and substituted for the Zn site as there was no evidence of the presence of metallic cobalt. Transmission electron microscopy suggests the crystalline nature of nanoparticles, with average particle size of ∼3.5 nm. UV-Vis measurements showed a red shift with respect to undoped nanoparticles in energy band gap with increasing cobalt concentration. Photoluminescence spectra reveal the defect-related emissions. The decay time constant is found to be in the nanosecond regime and is attributed to the spatial confinement of photo generated electron–hole pairs.     

Nanoparticle Tracking Analysis: Enhanced Detection of Transparent Materials

This study proposes a novel and simple in-house design of a nanoparticle tracking analysis (NTA) device for the online characterization of nanoparticles in an aqueous solution. The particle size distribution of two sets of model nanoparticles, for example, transparent (SiO₂) and opaque (TiO₂) materials with respect to water as a dispersion medium could be successfully analyzed. Experiments are conducted using two different laser wavelengths of 632.8 (red) and 510 nm (green) and a range of concentrations. The accuracy of the green laser is larger compared to the red laser for all particle concentrations used. The measured average diameter using the presented in-house NTA setup is in the acceptable range compared to the electron microscopy data. The average diameter of the transparent (SiO₂) and opaque (TiO₂) samples is calculated as 36.29 and 27.26 nm using NTA, 36.44 and 27.8 nm analyzing field emission scanning electron microscopy images, and 23.97 and 19.7 nm analyzing transmission electron microscopy images. In the new viewing sample holder, nanoparticles undergo mere Brownian motion with no bulk drift velocity. The effect of solid concentration and wavelength of the laser light on the performance of the NTA sensor is investigated, and the optimal concentration range for model particles is reported.     

Glass like magnetic alternating field susceptibility behavior of structurally frozen ferrofluids

Four ferrofluids, distinct in size distribution and aggregate structure, were investigated. The relaxation time ,related to the temperature of susceptibility maximum, was fitted to a Vogel-Fulcher law. A mean ordering temperature, T₀, was calculated using magnetic particle parameters derived from the structure. It is assumed that at T₀ the particle moments of particle clusters correlate, leading to a spin glass-like transition. Hence, then dynamic slows down considerably, as indicated by a strong broadening of relaxation-time distribution. T₀ roughly agrees with the energy of competing interaction between particle moments, as calculated from the structure of particle aggregates. Differences between particle arrangements clearly influence the dispersion and absorption, particularly within the cluster phase. Received 15 July 1998     

Conductivity of a small metallic particle

The size-dependent ac-conductivity of a small metallic particle is studied for electrons enclosed in a box with random impurities. The exact wave functions and energies are calculated numerically up to 500 electrons, then the Kubo-formula is evaluated, and an ensemble average is performed. A strong size- and frequency dependence of the conductivity is found which is in good agreement with random matrix results. The size dependence of the dc-conductivity agrees qualitatively with microwave absorption measurements on submicron particles.     

Two-dimensional site-bond percolation as an example of a self-averaging system

The Harris-Aharony criterion for a static model predicts that if a specific heat exponent α>0, then this model does not exhibit self-averaging. In the two-dimensional percolation model, the index α= ?1/2. This means that, in accordance with the Harris-Aharony criterion, the model can exhibit self-averaging properties. We study numerically the relative variances R _M and R _χ for the probability M of a site belonging to the “infinite” (maximum) cluster and for the mean finite-cluster size χ. It was shown that two-dimensional site-bond percolation on the square lattice, where the bonds play the role of the impurity and the sites play the role of the statistical ensemble over which the averaging is performed, exhibits self-averaging properties.     

Luminescence characteristics of K2Ca2(SO4)3:Eu,Tb micro- and nanocrystalline phosphor

K₂Ca₂(SO₄)₃ microcrystalline pure, doped with Eu, Tb and co-doped with Eu, Tb was prepared by solid-state diffusion method. Nanoparticles of these phosphors were also prepared by the chemical co-precipitation method. The formation of the compounds was confirmed by XRD. The particle size was calculated by broadening of the XRD peaks using Scherrer's formula. The particle size of nanocrystalline powder material was approximately found to be around 20 nm. Thermoluminescence and photoluminescence were studied to see the effect of co-doping and particle size. Tb³⁺ co-doping decreases the intensity in the Eu²⁺ doped phosphor due to the energy transfer and multiple de-excitations through various radiative and non-radiative processes. The sensitivity of K₂Ca₂(SO₄)₃:Eu,Tb microcrystalline phosphor was around 15 times more than LiF-TLD 100 and 7 times more than CaSO₄:Dy. A high temperature peak (615 K) was observed in case of the nanoparticles, which was attributed to a particle size induced phase transition. This was confirmed by differential scanning calormetry measurements. The decrease in the sensitivity in case of nanoparticles is attributed to the particle size effect i.e. volume to surface ratio. Theoretical analysis of the glow curves was done by glow curve convolution deconvolution method to calculate trapping parameters of various peaks.     

Effect of particle size of graphites on electrical conductivity of graphite/polymer composite

The effect of particle size of graphite particles on the dispersion state of graphite particles and electrical conductivity of graphite/low-density polyethylene (LDPE) composites is investigated. Graphite particles which have plate-like and spherical shapes and mean particle sizes of 2.1 to 82.6 μm are used. Scanning electron microscopy observation showed that graphite particles are not aggregated and ordered along the direction of mixing-roll in the polymer matrix. X-ray diffraction measurements show that crystallite size of the (110) plane of polyethylene crystal and the crystallinity are significantly affected by the particle size of graphite particles. These results were interpreted as due to the orientation of PE crystallites. The electrical conductivity of composites changes discontinuously at the critical volume fraction of particles, Ø_c. The Ø_c values given by the percolation equation increase with decreasing of the particle size of graphites. The plate-like graphite particles with a mean particle size of 2.1 μm could induce conductivity at Ø_c of 0.135. The values of Ø_c increased linearly with increasing of the mean particle sizes of the plate-like graphites. The value of Ø_c of spherical graphite particle is the largest value, 0.292, in all specimens.     

Average fluorescence yields of M4,5 subshells for thorium and uranium

M_4,5 subshells average fluorescence yields (ϖ_M4,5) have been determined for thorium and uranium using M_4,5 X-ray production cross-sections at 5.96 keV incident photon energy. The measurements have been performed using a ⁵⁵Fe annular source and an Ultra-LEGe detector. The present values are compared with calculated theoretical values and theoretical average M shell fluorescence yields (ϖ_M). Fair agreement (to within 22–27%) is typically obtained between present average fluorescence yields (ϖ_M4,5) and calculated theoretical values.     

Performance Evaluation of Different Phase-Doppler Systems

The results of comparative measurements of three different phase-Doppler systems applied to a steady-state water spray are discussed. The three receiving systems, i. e. DANTEC 57X receiving optics with covariance processor, an AEROMETRICS fibre-based receiver with DSA processor and standard INVENT phase-Doppler extension, were used with a 2-D fibre-optics-based transmitting system. A constant scattering angle of 70° was chosen, which is near the Brewster angle for water. Measurements were taken in the spray cone of hollow-cone pressure atomizer at two different axial distances from the nozzle. Local size distributions, size/velocity correlations and the mean diameters D₁₀ and D₃₂ were compared. The results indicate very good agreement between the different systems, especially with respect to the mean diameters. Larger scatter of the results occurs for the measured volume flow rates, but the calculated mean volume flow rates coincide fairly well with the nominal flow rate of the atomizer.     

Study on the lattice distortion of the As-prepared nanosized TiO2 particles via detonation method

Quantitative XRD measurements of the nanosized TiO₂ particles obtained from the detonation soot have been carried out. The lattice parameters, such as grain size, cell volume, lattice constants and lattice strain were obtained. The relationships between the change ratio of cell volume (the reciprocal of the particles size, or the mass ratio of explosive and TiO₂ precursor) and the lattice strain of the different TiO₂ phases were also discussed. The relationship between the change ratio of cell volume and the particle size of TiO₂ particles was also studied. The results demonstrated that with the decreasing of the particles size, the lattice strain of anatase phase increased, while the lattice strain of rutile phase increased firstly and then decreased to some extent. It is different from the linear relationship between the lattice distortion and the reciprocal of the particles size reported in other literatures. In the meantime, the lattice strains were different with the different mass contents of RDX in the microstructures of the TiO₂ particles. The direct reflection of microstructure changes is the changes of the particle size of TiO₂ particles. Based on the XRD results, the particular characteristics of the detonation process and interfacial effects of nanocrystalline materials, a crude explanation was also given.     

Roles of oleic acid during micropore dispersing preparation of nano-calcium carbonate particles

In the present work, nano-calcium carbonate powder was prepared by micropore dispersion method with assistance of oleic acid as surfactant. CO₂ gas was dispersed into the Ca(OH)₂/H₂O slurry via a glass micropore-plate with the diameter of micropore about 20 μm. To investigate the effect of oleic acid on the size of CaCO₃ particles, different amount of oleic acid was added in Ca(OH)₂/H₂O slurry at 5 °C and 25 °C, respectively. XRD patterns show that cubic calcite is the only crystalline phase in all cases. ZPA data and TEM photo indicate that the average particle size synthesized at 5 °C without oleic acid is of about 40 nm, slightly smaller than that of prepared at 25 °C, and that the dispersity of sample prepared at 5 °C is better than that of 25 °C. When oleic acid is added in both temperatures, the average particle size decreases a little. FT-IR spectra demonstrate that oleic acid interacts with Ca²⁺ and carbon-carbon double bond existed on the surface of particle. Consequently, two opposite roles of oleic acid during the process of preparation of nano-CaCO₃ were proposed, namely preventing nanoparticles from growing during reaction and making nanoparticles reunite to a certain extent after reaction.     

The Bose-Einstein condensation in a finite one-dimensional homogeneous system of noninteracting bosons

Condensation of the ideal Bose gas in a closed volume having the shape of a rectangular parallel-epiped of length L with a square base of side length l (L ? l) is theoretically studied within the framework of the Bose-Einstein statistics (grand canonical ensemble) and within the statistics of a canonical ensemble of bosons. Under the condition N(l/L)⁴ ? l, where N is the total number of gas particles, dependence of the average number of particles in the condensate on the temperature T in both statistics is expressed as a function of the ratio t=T/T ₁, where T ₁ is a certain characteristic temperature depending only on the longitudinal size L. Therefore, the condensation process exhibits a one-dimensional (1D) character. In the 1D regime, the average numbers of particles in condensates of the grand canonical and canonical ensembles coincide only in the limiting cases of t → 0 and t → ∞. The distribution function of the number of particles in the condensate of a canonical ensemble of bosons at t ≤1 has a resonance shape and qualitatively differs from the Bose-Einstein distribution. The former distribution begins to change in the region of t ～ 1 and acquires the shape of the Bose-Einstein distribution for t ? 1. This transformation proceeds gradually that is, the 1D condensation process exhibits no features characteristic of the phase transition in a 3D system. For N(l/L)⁴ ? 1, the process acquires a 3D character with respect to the average number of particles in the condensate, but the 1D character of the distribution function of the number of particles in the condensate of a canonical ensemble of bosons is retained at all N values.     

An ultrasonic characterization of ferrofluid

Nanoparticles of Cr₂O₃ are prepared through hydrothermal synthesis process using CrO₃/PVA in aqueous solution using sucrose as a reducing agent. The calcination temperature is taken 300 and 350 °C. XRD and SEM of the powdered Cr₂O₃ particles are done for the characterization. The average particle size is found 30–80 nm. It is found that average particle size increases with calcination temperature. The UV–visible absorption spectra are taken for the study of photo-physical properties of ferrofluids. Ultrasonic velocity and absorption measurements are performed in Cr₂O₃ ferrofluid using variable path interferometer and pulse-echo techniques, respectively. The achieved results are discussed in correlation with the magnetic and other physical properties of Cr₂O₃.