Raman spectroscopy investigation of magnetite nanoparticles in ferrofluids

Raman spectroscopy is used to investigate magnetite nanoparticles dispersed in two types of β-cyclodextrin suspensions. An approach is presented for characterization of the magnetic core in liquid surrounding at room temperature and atmospheric pressure. The effect of elevating laser power on the structural stability and chemical composition of magnetite in the ferrofluids is discussed. The data are compared with data from dry by-products from the fluids. Powder samples undergo total phase transition from magnetite to hematite at laser power of 1.95 mW. The same nanoparticles in the fluid undergo transformation at 9 mW, but no hematite positions appear throughout that investigation. The Raman spectra revealed that the main phase of the magnetic core in the fluids is magnetite. That is indicated by a strong and non-diminishing in intensity peak at 670 cm⁻¹. A second phase is present at the nanoparticle’s surface with Raman spectroscopy unveiling maghemite-like and small fractions of goethite-like structures. The Fourier transform infrared spectroscopy investigations confirm deviations in the surface structure and also point to the fact that the oxidation process starts at an early stage after formation of the nanoparticles. The analyses of the infrared data also show that β-cyclodextrin molecules retain their cyclic character and the coating does not affect the oxidation process once the particles are evicted from the fluids. A Mössbauer spectroscopy measurement on a ferrofluidic sample is also presented.     

Cryosynthesis of single-domain magnetite particles

The technique of low temperature synthesis of single-domain magnetite particles at the solid-liquid phase boundary was developed. Spherical magnetite particles 6–50 nm in size were obtained. The phase structure, elemental composition and morphology of the particles were studied using X-ray phase analysis, Auger spectroscopy, and scanning electron and atomic force microscopy.     

Near-edge X-ray absorption fine structure spectroscopy and structural properties of Ni-doped CeO2 nanoparticles

Ni-doped CeO₂ nanoparticles were prepared by using the co-precipitation method. The prepared nanoparticles were characterized using X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, Raman spectroscopy, field emission scanning electron microscopy (FE-SEM) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy. The XRD results infer that Ni-doped CeO₂ nanoparticles have single phase nature similar to that of pure CeO₂ nanoparticles. We have calculated lattice parameters using Powder-X software, particle size using Scherer’s formula and strain using the Williamson-Hall method for all the synthesized samples. We have observed a systematic decrease in the lattice parameters, particle size and strain with an increase in Ni doping in CeO₂. The FE-SEM micrographs also confirm that Ni-doped CeO₂ have nanocrystalline behavior and particles are spherical shaped. From the Raman spectra, it is observed that the intensity of classical CeO₂ vibration modes first increases then decreases with Ni doping. The NEXAFS spectra measured at Ce M_4,5 and Ni L_3,2 edges clearly indicate that Ce ions are in the +4 valence state and Ni ions are in the +2 valence state.     

Mechanochemical and magnetomechanical synthesis of hematite nanoparticles

Samples of hematite were exposed to mechanochemical activation by high energy ball milling for 0–27 h. The milling-induced changes to the structural and magnetic properties of hematite were characterized by X-ray diffraction (XRD) and Mössbauer spectroscopy. The particle size was found to decrease from 80 to 16.5 nm after 8 h of ball milling time, followed by a small increase to 19.8 nm at the end of the milling period. An overall expansion of the crystalline lattice parameters a and c with the milling time was deduced. The magnetic hyperfine field decreased with the ball milling time, from 51.46 down to 50.68 T after 27 h of grinding. Magnetite and traces of iron were observed at the longest milling time employed. The recoilless fraction (f ) was measured simultaneously using a dual Mössbauer absorber consisting of hematite and a stainless steel etalon. The f factor first decreased with the milling time due to occurrence of nanoparticles in the system, had a maximum at 12 h due to agglomerations of nanoparticles and exhibited a second maximum at 27 h, due to the appearance of magnetite in the system. More samples of hematite were subjected to magnetomechanical activation by magnetic ball milling for 52 and 134 h. A phase mixture of hematite and magnetite was observed.     

Synthesis and characterization of magnetite-maghemite nanoparticles obtained by the high-energy ball milling method

We present the process of synthesis and characterization of magnetite-maghemite nanoparticles by the ball milling method. The particles were synthesized in a planetary ball mill equipped with vials and balls of tempered steel, employing dry and wet conditions. For dry milling, we employed microstructured analytical-grade hematite (α-Fe₂O₃), while for wet milling, we mixed hematite and deionized water. Milling products were characterized by X-ray diffraction, transmission electron microscopy, room temperature Mössbauer spectroscopy, vibrating sample magnetometry, and atomic absorption spectroscopy. The Mössbauer spectrum of the dry milling product was well fitted with two sextets of hematite, while the spectrum of the wet milling product was well fitted with three sextets of spinel phase. X-ray measurements confirmed the phases identified by Mössbauer spectroscopy in both milling conditions and a reduction in the crystallinity of the dry milling product. TEM measurements showed that the products of dry milling for 100 h and wet milling for 24 h consist of aggregates of nanoparticles distributed in size, with mean particle size of 10 and 15 nm, respectively. Magnetization measurements of the wet milling product showed little coercivity and a saturation magnetization around 69 emu g^?1, characteristic of a nano-spinel system. Atomic absorption measurements showed that the chromium contamination in the wet milling product is approximately two orders of magnitude greater than that found in the dry milling product for 24 h, indicating that the material of the milling bodies, liberated more widely in wet conditions, plays an important role in the conversion hematite-spinel phase.     

Photothermally enhanced catalytic activity of partially aggregated gold nanoparticles

In the present study, a facile, rapid, and environmentally friendly method was used for the preparation of metal oxide nanoparticles in an ionic liquid medium. This technique involves mixing and heating the corresponding powder material (cadmium oxide, anatase, and hematite) and the selected ionic liquid (trihexyl(tetradecyl)phosphonium chloride, [P_6,6,6,14]Cl), without any other precursors or solvents. The confirmation of the existence of nanoparticles in the ionic liquid was carried out using UV?CVis absorption spectroscopy, and its concentration was determined by X-ray fluorescence. In order to analyze the shape and size distribution, transmission electron microscopy and a ZetaSizer (DLS technique) were used; finding out that the size of the hematite nanoparticles was 10?C55?nm. Nevertheless, for the cadmium oxide and the anatase nanoparticles, the size was between 2 and 15?nm. The composition of the prepared nanoparticles was studied by Raman spectroscopy. The structure of solids did not suffer any modification in their transformation to the nanoscale, as concluded from the X-ray powder diffraction analysis.     

Surfactant assisted surface studies of zinc sulfide nanoparticles

We report a simple soft chemical method for the synthesis of ZnS nanoparticles using varying concentration of cationic surfactant CTAB and examine its surface properties. Powder X-ray diffraction, UV-vis spectroscopy, photoluminescence spectroscopy, selective area electron diffraction, and transmission electron microscopy are used to characterize the as prepared ZnS nanoparticles. XRD and TEM measurements show the size of polydispersed ZnS nanoparticles is in the range of 2-5 nm with cubic phase structure. The photoluminescence spectrum of ZnS nanoparticles exhibits four fluorescence emission peaks centered at 387 nm, 412 nm, 489 nm and 528 nm showing the application potential for the optical devices. In Raman spectra of ZnS nanoparticles, the modes around 320, 615 and 700 cm⁻¹ are observed.     

Mössbauer spectroscopy studies of the magnetic properties of ferrite nanoparticles

Studies of the ferrite nanoparticles prepared by the chemical decomposition of iron chlorides with a various ratio ξ = Fe³⁺/Fe²⁺ are herein presented. The microstructure and the magnetic properties have been studied by transmission electron microscopy (TEM), X-ray diffraction (XRD) and Mössbauer spectroscopy (MS). The TEM studies show that the nanoparticles have almost a spherical shape with the diameter of (12 ± 2) nm for all samples. The measured XRD pattern was mainly composed of lines which were indexed with a cubic spinel structure. The analysis of the Mössbauer data shows that the microstructure of the nanoparticles consists of the core formed by nonstoichiometric magnetite and maghemite shell. A small amount of hematite, probably on the surface of the nanoparticles with ξ = 1.75, 2.0, was detected. At temperatures T ≤ 150 K the spin canting of surface maghemite with ξ = 2.25 was observed while for the samples with ξ = 1.75, 2.0 such effect was suppressed by the presence of hematite on the surface of the nanoparticles. Infield Mössbauer spectra with ξ = 1.75, 2.0 show that magnetic moments of the magnetite/maghemite core are parallel while magnetic moments of the surface hematite are perpendicular to the direction of the external magnetic field.     

Structural, optical and electrical characterization of antimony-substituted tin oxide nanoparticles

Antimony-doped tin oxide (ATO) nanostructures were prepared using chemical precipitation technique starting from SnCl₂, SbCl₃ as precursor compounds. The antimony composition was varied from 5 to 20 wt%. The lower resistance was observed at composition of Sn:95 and Sb:05, when compared with undoped and higher doping concentration of antimony. The average crystalline size of undoped and doped tin oxide was calculated from the X-ray diffraction (XRD) pattern and found to be in the range of 30-11 nm and it was further confirmed from the transmission electron microscopy (TEM) studies. The scanning electron microscopy (SEM) analysis showed that the nanoparticles agglomerates forming spherical-shaped particles of few hundreds nanometers. The samples were further analyzed by energy dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR) and electrical resistance measurements.     

Passivation films on particles of electroexplosion aluminum nanopowders: A review

The physicochemical regularities of the formation of passivating coatings on particles of aluminum electroexplosion nanopowders are examined by means of electron microscopy, X-ray diffraction, differential thermal, chemical analyses and X-ray photoelectron spectroscopy. The thermal characteristics of inorganic passivating coatings for aluminum nanoparticles were demonstrated to be more advantageous compared to organic coatings. The protective action of organic passivating coatings was shown to be independent of their composition—only the particle size was found to be important.     

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.     

Electro-precipitation of Fe3O4 nanoparticles in ethanol

The preparation of superparamagnetic magnetite (Fe₃O₄) nanoparticles by electro-precipitation in ethanol is proposed. Particle average size can be set from 4.4 to 9 nm with a standard deviation around 20%. Combination of wide-angle X-ray scattering (WAXS), Electron energy loss spectroscopy (EELS) and Mössbauer spectroscopy characterizations clearly identifies the particles as magnetite single-crystals (Fe₃O₄).     

Formation and microstructure of carbon encapsulated superparamagnetic Co nanoparticles

Carbon encapsulated magnetic cobalt nanoparticles have been synthesized by the modified arc-discharge method. Both high resolution transmission electron microscopy (HREM) and powder X-ray diffraction (XRD) profiles reveal the presence of 8–15 nm diameter crystallites coated with 1–3 carbon layers. In particular, HREM images indicate that the intimate and contiguous carbon fringe around those Co nanoparticles is good evidence for complete encapsulation by carbon shell layers. The encapsulated phases are identified as hcp α-Co, fcc β-Co and cobalt carbide (Co₃C) nanocrystals using X-ray diffraction (XRD), nano-area electron diffraction (SAED) and energy dispersive X-ray analysis (EDX). However, some fcc β-Co particles with a significant fraction of stacking faults are observed by HREM and confirmed by means of numerical fast Fourier transform (FFT) of HREM lattice images. The carbon encapsulation formation and growth mechanism are also reviewed.     

Phase transfer synthesis of N,N′(1,2-phenylene)bis-hippuricamide tethered metal based functionalized nanoparticles: A study on some novel microbial targeting peptide-mimic nanoparticles

This paper presents the novel synthesis of peptide, N,N′(1,2-phenylene)bis-hippuricamide tethered metal [Cu(II), Zn(II), Ni(II) and Co(II)] based functionalized nanoparticles via modified Brust-Schiffrin methodology. The growth, organic composition and morphology of these functionalized nanoparticles have been evaluated by UV-Vis, FT-IR spectroscopy and scanning electron microscopy. They are structurally and thermally characterized by X-ray diffraction and thermogravimetric analysis. Moreover, the interfacial dealings of these functionalized nanoparticles with Calf-thymus DNA and pUC19 DNA reveal that the functionalized nanoparticles of cobalt is an effective DNA damaging agent under physiological conditions. This has been supported by its efficient antimicrobial character against few fungal and bacterial strains, thereby steering its way towards biomedical applications as a metal based nanocarrier.     

Size-dependent magnetic properties of iron oxide nanoparticles

Uniform iron oxide nanoparticles in the size range from 10 to 24 nm and polydisperse 14 nm iron oxide particles were prepared by thermal decomposition of Fe(III) carboxylates in the presence of oleic acid and co-precipitation of Fe(II) and Fe(III) chlorides by ammonium hydroxide followed by oxidation, respectively. While the first method produced hydrophobic oleic acid coated particles, the second one formed hydrophilic, but uncoated, nanoparticles. To make the iron oxide particles water dispersible and colloidally stable, their surface was modified with poly(ethylene glycol) and sucrose, respectively. Size and size distribution of the nanoparticles was determined by transmission electron microscopy, dynamic light scattering and X-ray diffraction. Surface of the PEG-functionalized and sucrose-modified iron oxide particles was characterized by Fourier transform infrared (FT-IR) and Raman spectroscopy and thermogravimetric analysis (TGA). Magnetic properties were measured by means of vibration sample magnetometry and specific absorption rate in alternating magnetic fields was determined calorimetrically. It was found, that larger ferrimagnetic particles showed higher heating performance than smaller superparamagnetic ones. In the transition range between superparamagnetism and ferrimagnetism, samples with a broader size distribution provided higher heating power than narrow size distributed particles of comparable mean size. Here presented particles showed promising properties for a possible application in magnetic hyperthermia.     

Preparation of improved catalytic materials for water purification

The aim of presented paper was to study preparation of catalytic materials for water purification. Iron oxide (Fe₃O₄) samples supported on activated carbon were prepared by wet impregnation method and low temperature heating in an inert atmosphere. The as-prepared, activated and samples after catalytic test were characterized by Mössbauer spectroscopy and X-ray diffraction. The obtained X-ray diffraction patterns of prepared samples show broad and low-intensity peaks of magnetite phase and the characteristic peaks of the activated carbon. The average crystallite size of magnetite particles was calculated below 20 nm. The registered Mössbauer spectra of prepared materials show a superposition of doublet lines or doublet and sextet components. The calculated hyperfine parameters after spectra evaluation reveal the presence of magnetite phase with nanosize particles. Relaxation phenomena were registered in both cases, i.e. superparamagnetism or collective magnetic excitation behavior, respectively. Low temperature Mössbauer spectra confirm this observation. Application of materials as photo-Fenton catalysts for organic pollutions degradation was studied. It was obtained high adsorption degree of dye, extremely high reaction rate and fast dye degradation. Photocatalytic behaviour of a more active sample was enhanced using mechanochemical activation (MCA). The nanometric size and high dispersion of photocatalyst particles influence both the adsorption and degradation mechanism of reaction. The results showed that all studied photocatalysts effectively decompose the organic pollutants under UV light irradiation. Partial oxidation of samples after catalytic tests was registered. Combination of magnetic particles with high photocatalytic activity meets both the requirements of photocatalytic degradation of water contaminants and that of recovery for cyclic utilization of material.     

Core-shell structure and magnetic properties of magnetite magnetic fluids stabilized with dextran

The adsorption process of different dextran molecules onto the surface of in water dispersed magnetite nanoparticles has been investigated to optimize the preparation of magnetite magnetic fluids (MMFs). An average magnetite core size of 7.1 nm was found by X-ray diffraction and that of 8 nm was found by transmission electron microscopy for the samples prepared at 90 °C. An average hydrodynamic diameter of 25 nm was observed by scanning electron microscopy and that of 25-300 nm was obtained by photon correlation spectroscopy. The dextran was adsorbed by physical adsorption, a molecular weight of 20 kDa gave the best stability of these MMFs. The shell layer of the particles was weakly negatively charged in buffer solutions of pH values between 5.5 and 9.5. The particles seem to be mainly stabilized by sterical repulsion. The maximum available saturation magnetization of the MMFs was 3.5 kA/m.     

Polyol-assisted synthesis of TiO2 nanoparticles in a semi-aqueous solvent

TiO₂ (anatase and rutile) nanoparticles with an average crystallite size of 20-40 nm have been prepared at room temperature by polyol-mediated synthesis technique in a semi-aqueous solvent medium using titanium iso-propoxide as the titanium source, acetone as the oil phase and ethylene glycol as the stabilizer. Phase and microstructure of the resultant materials have been characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy and Raman spectroscopy. Photocatalytic degradation of acetaldehyde using TiO₂ nanoparticles was investigated by gas-chromatography technique.     

Morphology and Phase Composition of Particles Produced by Electro-Discharge-Machining of Iron

Towards producing metallic particles of controlled size and spherical shape, which are of technological importance, we have collected in the filters of an electro-discharge-machine (EDM) the material ejected from the surface of EDM iron pieces. The conditions of machining were varied for kerosene and water as dielectrics, using a discharge current of 25 A and duration times of 16 and 3072 μs for kerosene and of 32, 384 and 768 μs for water, respectively. Scanning electron microscopy was used to assess the effect of the time of discharge on the size of the particles. Mössbauer spectroscopy and X-ray diffraction revealed that for kerosene EDM particles only cementite-like carbides of diverse stoichiometry were formed. While no oxide was found for kerosene spheres, the analyses showed that besides the main fraction of α-Fe, a small percentage of wüstite (and traces of hematite for the 384 μs sample) formed on the water EDM ones.     

New evidences of in situ laser irradiation effects on γ‐Fe2O3 nanoparticles: a Raman spectroscopic study

The nature of the physical mechanisms responsible for the structural modification of the γ‐Fe₂O₃ nanoparticles under laser irradiation has been investigated by Raman spectroscopy. In situ micro‐Raman measurements were carried out on as‐prepared γ‐Fe₂O₃ nanoparticles about 4 nm in size as a function of laser power and on annealed γ‐Fe₂O₃ particles. A baseline profile analysis clearly evidenced that the phase transition from maghemite into hematite is caused by local heating due to laser irradiation with an increase of grain size of nanoparticles. This increasing was clearly determined by X‐ray diffraction from 4 nm in nanoparticles up to more than 177 nm beyond 900 °C in a polycrystalline state. Copyright © 2010 John Wiley & Sons, Ltd.