Classification Performance of a Low Pressure Differential Mobility Analyzer for Nanometer-sized Particles

Size distribution measurements and classification tests by a low pressure differential mobility analyzer (LPDMA) for nanometer-sized silver particles and cesium iodide particles under low pressure conditions (123–300 Torr) were performed using a transmission electron microscope (TEM) and the tandem DMA technique. When the ratio of the sheath gas flow rate and the aerosol gas flow rate was set at 5 : 1, the targeted sizes calculated from the classification voltage applied to the LPDMA at 160 Torr are found to be in good correlation with the count mean Feret diameter obtained from the TEM observation of the particles collected after a classification ranging from 6 to 25 nm, although the targeted sizes set by the LPDMA were approximately 15% greater than the count mean Feret diameter measured by the TEM after classification. The geometric standard deviations of DMA-classified particles measured by TEM and those obtained from the tandem DMA method ranged from 1.08 to 1.17 and from 1.05 to 1.13, respectively. They were slightly greater than the ideal geometric standard deviations (1.05) of the particles classified with the LPDMA, which was calculated by neglecting the broadening effects due to Brownian diffusion. We experimentally demonstrated the validity of our LPDMA system for size measurements and classification of the nanometer-sized particles under low pressure conditions.     

Hydrogen reduction of fine iron-oxide particles

Crystallographic, magnetic, and morphological changes induced by heating highly acicular -Fe₂O₃ particles (40 nm in diameter and an axial ratio of 8) under hydrogen have been observed. Reduction proceeds via a multi-phase process, and is not complete until 600°C. The -Fe particles produced are cylindrical in shape, 100 nm in diameter, and have an axial ratio of 1.7(3). Fourier analysis of x-ray profiles yielded a mean column length of 105(6) nm perpendicular to (110). Mössbauer spectra show two distinct hyperfine fields; at room temperature the values are 33.1(1) and 30.2(1)T. Evidence for diffusive particle motion is not present in 4.2–300 K spectra.     

Time-dependent non-linear size change of C<Subscript>60</Subscript>-ethylenediamine adduct particles in formation process

Addition reaction between C₆₀ and ethylenediamine occurred at room temperature in an ambient condition. C₆₀-ethylenediamine adduct particles were prepared by mixing toluene solutions of C₆₀ and ethyelenediamine. Average diameter of the C₆₀-ethylenediamine adduct particles was changed non-linearly according to the reaction time, which were observed using transmission electron microscopy. Early stage of the reaction, the diameter of the adduct particles was changed from about 250 to about 430 nm. Then, the size of the adduct particles was converged to about 300 nm. During this addition reaction, the crystalline sizes of adduct particles were constant about 2–3 nm, regardless of the sizes of the adduct particles, which were determined by X-ray diffraction measurement.

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In situ observation of UF5 nanoparticle growth in a low-pressure mixed-flow reactor

5 nanoparticles equipped with an in situ size-monitoring system, a LPDMA (low-pressure differential mobility analyzer), was developed to experimentally investigate the nanoparticle growth mechanism. The concentration of photoproduced UF₅ molecules was controlled by changing three factors: (I) the concentration of the feed UF₆ gas, (II) the laser pulse energy of the irradiation, and (III) the repetition rate of the laser pulses. The dependence of the volumetric average diameter of the photoproduced particles on the UF₅ nascent concentration in all three cases was found to be very similar. The result strongly suggests that the reactor functions as a mixed-flow reactor under a complete mixing condition. The particle size measured by the LPDMA was found to be in the range of 6 to 11 nm, and it was approximately proportional to the power 0.3 of the initial concentration of photoproduced UF₅ molecules. Received: 11 May 1998/Accepted: 15 September 1998     

Synthesis of copper-nickel nanoparticles prepared by mechanical milling for use in magnetic hyperthermia

Mechanical alloying of a mixture of copper and nickel powders has been applied for the preparation of copper-nickel alloy particles in the nanometer range. The particles were designed to be used for controlled magnetic hyperthermia applications. The milling conditions were optimized using the desired alloy composition. Utilizing a ball-to-powder mass ratio of 20, we could obtain a nanocrystalline Cu_27.5Ni_72.5 (at%) alloy with a crystallite size of around 10 nm and a Curie temperature of 45 °C.Thermal demagnetization in the vicinity of the Curie temperature of the nanoparticles was determined by thermomagnetic measurements using an adapted TGA-SDTA apparatus. The size and morphology of the particles were determined by XRD measurements and TEM analyses. The magnetic properties were also examined with a VSM. The magnetic heating effects were measured for the powdered material.     

Mössbauer spectra of iron (III) sulfide particles

Trivalent iron sulfide (Fe₂ S ₃) particles were synthesized using a modified polyol method. These particles exhibited a needle-like shape (diameter =?10-50 nm, length =?350-1000 nm) and generated a clear XRD pattern. Mössbauer spectra of the product showed a paramagnetic doublet at room temperature and distributed hyperfine magnetic splitting at low temperature. The Curie temperature of this material was determined to be approximately 60 K. The data suggest that the Fe₂ S ₃ had a structure similar to that of maghemite (γ-Fe₂ O ₃) with a lattice constant of a =?10.6 Å. The XRD pattern calculated from this structure was in agreement with the experimental pattern and the calculated hyperfine magnetic field was also equivalent to that observed in the experimental Mössbauer spectrum.     

有机盐制备的Fe3O4-葡聚糖纳米粒子的磁性能及表征

利用葡糖酸铁(C12H22FeO14·2H2O)和柠檬酸铁(C6H5O7Fe·5H2O)参与的化学共沉积法制备出单分散核心氧化铁的平均粒径为4.1nm,葡聚糖厚度约为11nm,总体平均粒径为26nm的Fe3O4葡聚糖复合纳米粒子.研究结果表明,复合粒子Fe3O4葡聚糖具有超顺磁性.制备过程中没有N2保护,得到的Fe3O4无机粒子的晶体结构几乎没有发生变化,证明了有机盐的抗氧化性,合成的Fe3O4葡聚糖复合纳米粒子具有较好的磁性能.其在室温下(300K)的饱和磁化强度为52emu/g,低温下(5K)的饱和磁化强度为63emu/g.并利用TEM、XRD、DLS和VSM(振动样品磁强计)等手段对其粒结构、形态、粒径和磁性能进行了表征.     

A remark on nano-particle stability of cement C-S-H gel

Hydrated pastes of ordinary Portland cement prepared with different water-to-cement ratios were investigated by using the small-angle neutron scattering technique in the region of Q ∈ (0.0045, 0.11) Å^?1. Samples of cement pastes were subjected to non-standard hydration conditions using a mix with D₂O, low RH, and water-to-cement ratios spread over a very wide interval (0.4; 1.4). The investigation was focused on testing the structural stability of nano-metric particles in the cement C-S-H gel. Owing to the high structural stability of these nano-particles, their average diameter might be used as a microscopic parameter characterizing the nano-metric structure of C-S-H gels. The average diameter of the nano-particles of the studied ordinary Portland cement CEMI 42.5 R-SC was found to be close to the value of 4.2 nm and independent of the water-to-cement ratios.     

Order-disorder transformation in FePt nanoparticles studied by ferromagnetic resonance

We have investigated the ferromagnetic resonance (FMR) response of as-made and temperature annealed FePt magnetic nanoparticles. The as-made nanoparticles, which have been fabricated by a chemical route, crystallize in the low magnetic anisotropy fcc phase and have a diameter in the range of 2-4 nm. The annealing of the particles at high temperatures (T_A=550, 650 and C) in an inert Ar atmosphere produces a partial transformation to the high magnetocrystalline anisotropy L1₀ phase, with a significant increase in particle size and size distribution. FMR measurements at X-band (9.5 GHz) and Q-band (34 GHz) show a single relatively narrow line for the as-synthesized particles and a structure of two superimposed lines for the three annealed samples. The origin of this line shape has been attributed to the presence of the disordered fcc phase. Assuming that the system consists of a collection of identical particles with a random distribution of easy axes, we have been able to estimate a mean value for the magnetic anisotropy constant of the particles in the fcc phase, K∼2×10⁶ erg/cm³. The measured line shape in the annealed samples can be explained if we consider that the magnetic anisotropy of the particles has a gaussian distribution with a relatively broad width.     

Demonstration of ultra-high-resolution MFM images using Co90Fe10-coated CNT probes

We demonstrate ultra-high-resolution magnetic force microscopy images of perpendicular magnetic storage media using carbon nanotube probes coated by ferromagnetic Co₉₀Fe₁₀ films (20, 30, 40, and 50 nm). By optimizing ferromagnetic film thickness (effective tip diameter), we obtained best magnetic domain image with an 40 nm-Co₉₀Fe₁₀-coated tip (50 nm tip diameter) about a lateral detect density of 1200 k flux per inch on perpendicular magnetic storage medium, one of the highest resolutions in MFM imaging reported for this material system and structure. The observed dependence of tip dimension on signal contrast and image resolution was successfully explained by a theoretical analysis indicating that the signal contrast, along with the physical probe-tip dimension, should be taken into account to design magnetic probes tips for high-resolution magnetic force microscopy.     

Individual-collective crossover driven by particle size in dense assemblies of superparamagnetic nanoparticles

Prussian blue analogues (PBA) ferromagnetic nanoparticles Cs ^I _x Ni ^II [Cr ^III (CN)₆ ] _z ·3(H₂O) embedded in CTA⁺ (cetyltrimethylammonium) matrix have been investigated by magnetometry and magnetic small-angle neutron scattering (SANS). Choosing particle sizes (diameter D = 4.8 and 8.6 nm) well below the single-domain radius and comparable volume fraction of particle, we show that the expected superparamagnetic regime for weakly anisotropic isolated magnetic particles is drastically affected due to the interplay of surface/volume anisotropies and dipolar interactions. For the smallest particles (D = 4.8 nm), magnetocrystalline anisotropy is enhanced by surface spins and drives the system into a regime of ferromagnetically correlated clusters characterized by a temperature-dependent magnetic correlation length L _mag which is experimentally accessible using magnetic SANS. For D = 8.6 nm particles, a superparamagnetic regime is recovered in a wide temperature range. We propose a model of interacting single-domain particles with axial anisotropy that accounts quantitatively for the observed behaviors in both magnetic regimes.     

H2O2氧化法制备Fe3O4纳米颗粒及与共沉淀法制备该样品的比较

在近中性条件下，利用H₂Ｏ₂氧化Fe(OH)2胶体成功制备了Fe₃ Ｏ₄纳米颗粒.分别利用透射电镜(TEM)，x射线衍射仪(XRD)，振动样品磁强计(VSM)和超导量子干涉仪（SQUI D）对样品的形貌，结构，宏观磁性进行了表征和测量.TEM图像表明样品为球形颗粒，直径 大小约18nm，且分布较均匀.XRD结果表明样品为立方尖晶石结构.穆斯堡尔谱测量表明样品 室温下对应两套六线谱，样品的晶体结构存在缺陷，内磁场略小于块体Fe₃Ｏ4的值. 宏观磁测量表明样品的饱和磁化强度可达67×10^-3A·m²/g，在20 K出现了Verw ey转变.选择该法制备的Fe₃Ｏ₄纳米颗粒与共沉淀法得到的样品作 了磁性比较.宏观磁 测量表明共沉淀法制备的样品在外磁场为1T时仍未饱和，磁化强度仅为46×10^-3A·m²/g，在178K出现了超顺磁转变温度，且在测量温度范围内没有发现Verwe y转变. 关键词： 亚铁磁 超顺磁 穆斯堡尔谱     

Magnetism of gadolinium nanoparticles near <Emphasis Type="Italic">T</Emphasis><Subscript><Emphasis Type="Italic">c</Emphasis></Subscript>

Influence of temperature and magnetic field H on magnetism of spherical Gd nanoparticles of different sizes (89, 63, 47, 28, and 18 nm) was studied in the temperature range 250 K < T < 325 K. The particles were obtained by metal vapor condensation in the flow of helium. The particles with d = 18 nm did not show a magnetic transition; their structure is a combination of two cubic phases (FCC1 and FCC2). Large particles remained in the HCP phase and had an admixture of the FCC1 phase, the amount of which decreased as the particle sizes increased; magnetic transition took place at T _c = 293 K. The admixture of O₂ did not alter the structure but decreased the magnetization σ and magnetic permeability μ. An orientation transition in polycrystalline gadolinium initiated by the magnetic field H was proved in an experiment. The orientation transition in Gd particles smaller than 63 nm, the magnetic structure of which is close to the single-domain structure, occurred near T _c without the influence of H.     

Evolution of structural properties of iron oxide nano particles during temperature treatment from 250 °C-900 °C: X-ray diffraction and Fe K-shell pre-edge X-ray absorption study

Iron oxide nano particles with nominal Fe₂O₃ stoichiometry were synthesized by a wet, soft chemical method with heat treatment temperatures from 250 °C to 900 °C in air. The variation in the structural properties of the nano particles with the heat treatment temperature was studied by X-ray diffraction and Fe K-shell X -ray absorption spectroscopy. X-ray diffractograms show that at lower annealing temperatures the nano particle comprise both maghemite and hematite phases. With increasing temperature, the remainder of the maghemite phase transforms completely to hematite. Profile analysis of the leading Bragg reflections reveals that the average crystallite size increases from 50 nm to 150 nm with increasing temperature. The mean primary particle size decreases from 105 nm to 90 nm with increasing heat treatment temperature. The X-ray diffraction results are paralleled by systematic changes in the pre-edge structure of the Fe K-edge X-ray absorption spectra, in particular by a gradual decrease of the t_2g/e_g peak height ratio of the two leading pre-edge resonances, confirming oxidation of the Fe from Fe²⁺ towards Fe³⁺. Transmission electron microscopy (TEM) on the samples treated at temperatures as high as 900 °C showed particles with prismatic morphology along with the formation of stacking fault like defects. High resolution TEM with selected area electron diffraction (SAED) of samples heat treated above 350 °C showed that the nano particles have well developed lattice fringes corresponding to that of (110) plane of hematite.     

Size-induced effect on nano-crystalline CoFe2O4

Cobalt ferrite (CoFe₂O₄) nano-particles have been synthesized successfully and we studied the effect of temperature on them. The particles have been annealed at different temperatures ranging from 373 to 1173 K. Significant effect on the physical parameters like crystalline phase, crystallite size, particle size, lattice strain and magnetic properties of the nano-particles has been investigated. The studies have been carried out using a powder X-ray diffractometer (XRD), a transmission electron microscope (TEM) and a vibrating sample magnetometer (VSM). A thorough study of the variation of specific surface area and particle size with annealing is presented here, with their effects on saturation magnetization.     

Effect of temperature on rotational viscosity in magnetic nano fluids

Flow behavior of magnetic nano fluids with simultaneous effect of magnetic field and temperature is important for its application for cooling devices such as transformer, loud speakers, electronic cooling and for its efficiency in targeted drug delivery and hyperthermia treatment. Using a specially designed horizontal capillary viscometer, temperature-sensitive and non-temperature-sensitive magnetic nano fluids are studied. In both these case the temperature-dependent rotational viscosity decreases, but follows a quite different mechanism. For temperature-sensitive magnetic nano fluids, the reduction in rotational viscosity is due to the temperature dependence of magnetization. Curie temperature (^T _c ) and pyromagnetic coefficient are extracted from the study. A fluid with low T _c and high pyromagnetic coefficient is useful for thermo-sensitive cooling devices and magnetic hyperthermia. For non-temperature-sensitive magnetic nano fluids, reduction in rotational viscosity is due to removal of physisorbed secondary surfactant on the particle because of thermal and frictional effects. This can be a good analogy for removal of drug from the magnetic particles in the case of targeted drug delivery.      

Hydrothermal synthesis of MnO2 nanowires: structural characterizations,optical and magnetic properties

In this paper, 1D single-crystalline MnO₂ nanowires have been successfully synthesized by hydrothermal method using KMnO₄ and (NH₄)₂S₂O₈ as raw materials. X-ray diffraction patterns and high-resolution TEM images reveal pure tetragonal MnO₂ phase with diameters of 15–20 nm. Photoluminescence studies exhibited a strong ultraviolet (UV) emission band at 380 nm, blue emission at 452 nm and an extra weak defect-related green emission at 542 nm. UV–visible spectrophotometery was used to determine the absorption behavior of nanostructured MnO₂ and a direct optical band gap of 2.5 eV was acquired by Davis–Mott model. The magnetic properties of the products have been evaluated using vibrating sample magnetometer, which showed that MnO₂ nanowires exhibited a superparamagnetic behavior at room temperature. The magnetization versus temperature curve of the as-obtained MnO₂ nanowires shows that antiferromagnetic transition temperature is 99 K.     

Impact of silica environment on hyperfine interactions in &#x01d716;-Fe2O3 nanoparticles

Magnetic nanoparticles have found broad applications in medicine, especially for cell targeting and transport, and as contrast agents in MRI. Our samples of ??-Fe₂O₃ nanoparticles were prepared by annealing in silica matrix, which was leached off and the bare particles were then coated with amorphous silica layers of various thicknesses. The distribution of particle sizes was determined from the TEM pictures giving the average size ～20 nm and the thickness of silica coating ～5; 8; 12; 19 nm. The particles were further characterized by the XRPD and DC magnetic measurements. The nanoparticles consisted mainly of ??-Fe₂O₃ with admixtures of ～1 % of the α phase and less than 1 % of the γ phase. The hysteresis loops displayed coercivities of ～2 T at room temperature. The parameters of hyperfine interactions were derived from transmission Mössbauer spectra. Observed differences of hyperfine fields for nanoparticles in the matrix and the bare ones are ascribed to strains produced during cooling of the composite. This interpretation is supported by slight changes of their lattice parameters and increase of the elementary cell volume deduced from XRD. The temperature dependence of the magnetization indicated a two-step magnetic transition of the ??-Fe₂O₃ nanoparticles spread between ～85 K and ～150 K, which is slightly modified by remanent tensile stresses in the case of nanoparticles in the matrix. The subsequent coating of the bare particles by silica produced no further change in hyperfine parameters, which indicates that this procedure does not modify magnetic properties of nanoparticles.     

Polyol synthesis and magnetic study of Mn3O4 nanocrystals of tunable size

Nanosized manganese oxide particles were prepared by the so-called polyol process. The average diameter of the particles was controlled by the growth time. X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photon spectroscopy (XPS) show that the particles are well crystallized, pure, stoichiometric Mn₃O₄ single crystals of uniform size ranging from about 5 to 12 nm. The variation of their dc-magnetization, M, as a function of the magnetic field, H, and temperature, T, clearly corresponds to ferromagnetic ordering at low temperature, with a Curie temperature slightly higher than 40 K. The evidence for superparamagnetism in these particles, due to their very small size, has been discussed in the light of their M(H) and M(T) for zero-field-cooled (ZFC) and field-cooled (FC) plots.     

Mössbauer study of Cu1−xZnxFe2O4 catalytic materials

In the present work, we have synthesized and characterized magnetic nanoparticles of maghemite γ-Fe₂O₃ to study their structural and magnetic properties. For the preparation, magnetite precursor, were oxidized by adjusting the pH = 3.5 at about 80 °C in an acid medium, The mean size of the maghemite particles calculated from the X-ray diffractogram was around 5.7 nm. Mössbauer spectroscopy measurements at room temperature show their superparamagnetic behavior. Furhermore, Mössbauer measurements were carried out at 77 K and 4.2 K in order to find the typical hyperfine fields of the maghemite. Magnetite phase was not found. FC and ZFC magnetization curves measured at 500 Oe indicate a blocking temperature of 105.3 K. The magnetization measurements also show almost zero coercivity at RT. TEM images show nanoparticles with diameter smaller than 10 nm, which are in good agreement with the X-ray pattern and the fitting of the magnetization data.