Fabrication and magnetic properties of FePt nanoparticle assemblies embedded in MgO-matrix systems

Hydrophilic FePt nanoparticles (NPs) have been embedded into the MgO-matrix systems via a sol–gel process to prevent FePt NPs from aggregating and sintering during the heat-treatment process required for the L1₀ ordering. The chemically ordered L1₀-phase FePt can be obtained after annealing at 700 °C for 60 min in atmosphere containing H₂. The effect of the pH value of MgO collosol and FePt nanocrystal loading amount on the structure, morphology, and magnetic properties of FePt/MgO nanocomposites has been investigated. The neutral pH value of 7 in MgO sol is beneficial to stabilize FePt NPs and obtain higher chemical ordering parameter S for the face-centered tetragonal -FePt/MgO nanocomposites with larger coercivity. The FePt NPs loading amount also plays a key role in tuning the microstructure and magnetic properties of the nanocomposites. The relatively higher FePt NPs loading with FePt/MgO molar ratio (R_FM) of 1:2 leads to relatively perfect hexagonal assembly and pure L1₀ phase. When the R_FM is 1:5 and 1:10, the MgO-matrix in nanocomposites causes the Fe element loss in FePt NPs along with formation of secondary phases such as magnesioferrite or Pt₃Fe during the annealing process. Under optimal processing of neutral pH value of 7 and R_FM of 1:2, the presence of MgO matrix produces more homogeneous microstructures and better magnetic properties with higher room-temperature coercivity (H _C = 4.65 kOe).     

Size Control of FePt Nanoparticles Produced by Seed Mediated Growth Process

Monodisperse FePt nanoparticles with average size of 2.4?nm were successfully synthesized via chemical co-reduction of iron acetylacetonate, Fe(acac)₃, and platinum acetylacetonate, Pt(acac)₂, by 1,2-hexadecanediol as a reducing agent and oleic acid and oleyl amine as surfactant. Then using the seed mediated growth process smaller sized FePt nanoparticles are used as seeds for the growth of larger sized FePt particles and there is no specific limitation to achieve upper size range by this method. In this work, we could synthesize FePt nanoparticles up to 4.0?nm. Monodispersity with relatively narrow size distribution and having the same elemental composition with the atomic percentage of Fe _x Pt_100?x (x?=?63) are the main advantages of this method. As-made FePt nanoparticles have the chemical disordered face centered cubic structure with superparamagnetic behavior at room temperature. After annealing these particles become ferromagnetic with high magnetocrystalline anisotropy and their coercivity increases with increasing particle sizes and reaches a maximum value of 5,200?Oe for size of 46.5?nm     

Synthesis of face-centered tetragonal FePt nanoparticles and granular films from Pt@Fe2O3 core-shell nanoparticles

This paper describes a new approach for making face-centered tetragonal (fct) FePt nanoparticles with a diameter of 17 nm and granular films from Pt@Fe2O3 core-shell nanoparticle precursors. The core-shell nanoparticles were converted to fct FePt through a reduction and alloy formation process at enhanced temperatures. The Fe and Pt elemental analysis was conducted on both individual nanoparticles and granular films using energy-dispersive X-ray (EDX) spectroscopy. Our convergent evidence from selected area electron diffraction (SAED), powder X-ray diffraction (PXRD), and EDX analysis indicates that the final products are fct FePt alloys. The fct FePt films have coercivities of 8.0-9.1 kOe at 5 K and 7.0 kOe at 300 K measured by a SQUID magnetometer. These values depend on the conversion temperatures of Pt@Fe2O3 nanoparticles. Unlike the previously synthesized disordered face-centered cubic (fcc) FePt nanoparticles with diameters of 4-6 nm (Sun, S. H.; Murray, C. B.; Weller, D.; Folks, L.; Moser, A. Science 2000, 287, 1989), the FePt nanoparticles presented in this work not only possess the preferred fct phase but also are in a size range that is expected to be ferromagnetic and have high coercivity, which is important to the practical applications in ultrahigh density data storage media and magnetic nano devices.     

Direct synthesis of fct-structured FePt nanoparticles at low temperature with assistance of poly(N-vinyl-2-pyrrolidone)

Direct synthesis of fct-structured FePt nanoparticles was successfully achieved by using poly(N-vinyl-2-pyrrolidone) as a protective reagent at lower temperature than the case using low molecular weight ligands as a protective reagent. Experimental data suggest that a transformation of FePt nanoparticles from face-centered cubic to face-centered tetragonal (fct) structure takes place at reaction temperature of 261 degrees C. The results of XRD and the magnetic properties exhibit that the FePt nanoparticles synthesized at 261 degrees C have partially ordered fct-structure and a ferromagnetic behavior at room temperature.     

The two-phase region in 2(ZnSe)x(CuInSe2)1−x alloys and structural relation between the tetragonal and cubic phases

The two-phase region in the system 2(ZnSe)_x(CuInSe₂)_1−x covers the chemical composition range 0.10<x?0.36, in which a tetragonal and a cubic phase are coexisting. The structural relation between both phases was determined by selected area diffraction (SAD) and transmission electron microscopy (TEM). Both crystal structures are very similar and the extremely small mismatch of the lattice constants of the tetragonal phase and the embedding cubic matrix phase allows for the grain boundaries to be virtually strain-free and, therefore, without notable dislocations. The tetragonal phase forms grains of flat discus-like shape in the ambient cubic matrix, with the short discus axis parallel to the tetragonal c-axis. TEM experiments proved that the discus-shaped tetragonal particles are collinear with the (100)_cub, (010)_cub and (001)_cub planes of the cubic phase. Cooling and annealing experiments revealed a near-equilibrium state only to be realized for small cooling rates less than 2 K/h and/or for a long-time annealing with subsequent rapid quenching. Only then there will be no cation ordering in both, the tetragonal domains and the parental cubic matrix phase. If, however, the samples are kept in a state far away from the equilibrium condition both phases reveal Stannite-type cation ordering. Within the composition range of 0?x?0.10 only tetragonal 2(ZnSe)_x(CuInSe₂)_1−x-alloys exist. At concentration rates above 36 mol% 2(ZnSe) only cubic structured solid solutions of ZnSe and CuInSe₂ are found to be stable. However, in the range 36 mol% to about 60 mol% 2(ZnSe) tiny precipitates with Stannite-like structure exist, too.     

Phase transfer catalysis: Synthesis of monodispersed FePt nanoparticles and its electrocatalytic activity

Using dibenzo-24-crown-8-ether (DB24C8) as phase transfer catalyst, the monodispersed iron–platinum (FePt) alloy nanoparticles with size of ∼17 nm were synthesized by reduction of H₂PtCl₆·6H₂O and FeCl₂·4H₂O in the solvothermal system. The structure, magnetic property and electrocatalytic activity of FePt nanoparticles were characterized by transmission electron microscopy (TEM), X-ray diffraction system (XRD), vibration sample magnetometer (VSM) and CHI 820 electrochemical analyser (three electrodes system, the reference electrode is saturated calomel electrode (SCE), the counter electrode is platinum electrode and the glassy carbon electrode is used as working electrode (GCE)), respectively. The results show that the as-synthesized FePt nanoparticles have a chemically disordered fcc structure and can be transformed into chemically ordered fct structure after annealing treatment above 400 °C, simultaneously accompanying with the coercivity changed from 5 to 2400 Oe. CVs of 0.5 M H₂SO₄/0.5 M CH₃OH on GCE modified with FePt nanoparticles monolayer illustrate that the as-synthesized FePt nanoparticles have strong electrocatalytic activity toward the oxidation of CH₃OH in aqueous solution.     

Hexagonal-to-cubic phase transformation in composite thin films induced by FePt nanoparticles located at PS/PEO interfaces

The organization process of asymmetric poly(styrene-block-ethylene oxide) (PS-b-PEO) copolymer thin films blended with FePt nanoparticles is studied. In a first step, it is shown that FePt nanoparticles stabilized by oleic acid ligands are distributed within the PS matrix phase, whereas the same particles partially covered with short dopamine-terminated-methoxy poly(ethylene oxide) (mPEO-Dopa) are located at PS/PEO interfaces. The swelling of PS domains, induced by FePt_oleic acid nanoparticles during the solvent annealing process, results in formation of a disordered microstructure in comparison to the well-organized hexagonally close-packed (HCP) cylinder phase formed in the neat PS-b-PEO copolymer. The evolution of the microstructure of PS-b-PEO/FePt_mPEO-Dopa composite has been investigated for different solvent annealing treatments. Under high-humidity conditions during the vapor annealing process, the addition of FePt nanoparticles results in formation of spheres in the film split into terraces. The upper and lower terraces are occupied by spheres organized in an unusual square and HCP phases, respectively. Under low-humidity conditions, undulated PEO cylinders oriented parallel to substrate are formed in the presence of FePt nanoparticles. In this case, we observe that most of the nanoparticles accumulate within the core of topological defects, which induces a low nanoparticle concentration at the PS/PEO interfaces and so stabilizes an intermediate undulated cylinder phase.     

Effects of Cu addition on the structure and magnetic properties of L10-FePt nanoparticles prepared by sol–gel method

(FePt)₁₀₀Cu₀, (FePt)₉₅Cu₅ and (FePt)₉₀Cu₁₀ nanoparticles (NPs) were successfully synthesized by the sol–gel method. The relationship between Cu doping and structure and magnetic properties of L1₀-FePt NPs was studied. The results indicated that all three samples originated a L1₀-FePt structure and Cu doping did not destroy the ordered structure of L1₀-FePt. By increasing the Cu content, c/a ratio of the FePtCu NPs linearly decreased. Pawley refinement showed symmetry of (FePt)₉₅Cu₅ NPs was still tetragonal. When the Cu concentration increased from 0 to 10 %, coercivity increased from 7,050 to 11,250 Oe. This result confirms that the prepared alloys can be promising candidates for magnetic storage applications.     

Growth of FePt nanocrystals by a single bimetallic precursor [(CO)3Fe(mu-dppm)(mu-CO)PtCl2

A new single source approach was developed to synthesize face-centered tetragonal (fct) FePt nanoparticles using bimetallic compound (CO)3Fe(mu-dppm)(mu-CO)PtCl2, which has been characterized by single crystal X-ray diffraction and was used as the precursor to ensure the accurate stoichiometry of the final FePt product; the ability of the molecular complex to act as a single source precursor for the formation of fct FePt nanocrystals with an average diameter of 3.2 nm has been demonstrated.     

Synthesis and magnetic properties of silica-coated FePt nanocrystals

Colloidal FePt nanocrystals, 6 nm in diameter, were synthesized and then coated with silica (SiO2) shells. The silica shell thickness could be varied from 10 to 25 nm. As-made FePt@SiO2 nanocrystals have low magnetocrystalline anisotropy due to a compositionally disordered FePt core. When films of FePt@SiO2 particles are annealed under hydrogen at 650 degrees C or above, the FePt core transforms to the compositionally ordered L1(0) phase, and superparamagnetic blocking temperatures exceeding room temperature are obtained. The SiO2 shell prevents FePt coalescence at annealing temperatures up to approximately 850 degrees C. Annealing under air or nitrogen does not induce the FePt phase transition. The silica shell limits magnetic dipole coupling between the FePt nanocrystals; however, low temperature (5 K) and room temperature magnetization scans show slightly constricted hysteresis loops with coercivities that decrease systematically with decreased shell thickness, possibly resulting from differences in magnetic dipole coupling between particles.     

Self-assembled FePt nanocrystals with large coercivity: reduction of the fcc-to-L1(0) ordering temperature

Herein we report the synthesis and properties of Fe(55)Pt(45) nanoparticles, both monodisperse and self-assembled into hexagonal close-packed and cubic arrays of 4.0 +/- 0.2 nm size in an L1(0) structure, obtained by a modified polyol process. The new synthetic route improved the control over the particle composition, thereby reducing the temperature required to convert from face-centered cubic (fcc) to face-centered tetragonal (fct) phase by some 30-50 degrees C without additives. Annealing at 550 degrees C for 30 min converts the self-assembled nanoparticles into ferromagnetic nanocrystals with large coercivity, H(C) = 11.1 kOe. Reducing the fcc-to-fct (L1(0)) ordering temperature avoided particle coalescence and decreased the loss in particle positional order without compromising the magnetic properties, as is generally observed when additives are used.     

Fabrication and characterization of TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> composite nanoparticles and polyurethane/(TiO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript>) nanocomposite films

TiO₂–SiO₂ composite nanoparticles were prepared by a sol–gel process. To obtain the assembly of TiO₂–SiO₂ composite nanoparticles, different molar ratios of Ti/Si were investigated. Polyurethane (PU)/(TiO₂–SiO₂) hybrid films were synthesized using the “grafting from” technique by incorporation of modified TiO₂–SiO₂ composite nanoparticles building blocks into PU matrix. Firstly, 3-aminopropyltriethysilane was employed to encapsulate TiO₂–SiO₂ composite nanoparticles’ surface. Secondly, the PU shell was tethered to the TiO₂–SiO₂ core surface via surface functionalized reaction. The particle size of TiO₂–SiO₂ composite sol was performed on dynamic light scattering, and the microstructure was characterized by X-ray diffraction and Fourier transform infrared. Thermogravimetric analysis and transmission electron microscopy (TEM) employed to study the hybrid films. The average particle size of the TiO₂–SiO₂ composite particles is about 38 nm when the molar ratio of Ti/Si reaches to1:1. The TEM image indicates that TiO₂–SiO₂ composite nanoparticles are well dispersed in the PU matrix.     

The phase diagram of fullerene C60 at high temperatures and pressures

Experimental and literature data were used to calculate the Gibbs energies of polymerized C₆₀ phases and construct the equilibrium T-p phase diagram of fullerene C₆₀ at temperatures from 0 to 1000 K and pressures from 0 to 8 GPa. The diagram contains stability regions of the orthorhombic, tetragonal, and rhombohedral polymerized C₆₀ phases and primitive cubic (PC) and face-centered cubic (FCC) nonpolymerized C₆₀ phases. The orthorhombic phase (linear polymer) is an equilibrium phase at 298 K and 1 bar and in the adjacent region. The equilibrium line observed experimentally (FCC C₆₀—orthorhombic phase) is well described by the phase diagram. The optimum temperatures and pressures of the synthesis of polymerized phases are determined by kinetic rather than thermodynamic parameters.     

Structure and voltage tunable dielectric properties of sol–gel derived Bi1.5MgNb1.5O7 thin films

Bi_1.5MgNb_1.5O₇ (BMN) thin films were fabricated on Au/Ti/SiO₂/Si(100) substrates using a sol?Cgel spin coating process. Thermo decomposition of the BMN precursor gel was discussed. The structures, morphologies, dielectric properties and voltage tunable dielectric properties were investigated. The deposited films showed a cubic pyrochlore structure after annealing at 550?°C or higher temperatures. With the annealing temperature increased from 500 to 800?°C, the root-mean-square surface roughness of the films increased from 0.6 to 6.8?nm. Additional phase, MgNb₂O₆, emerged after annealing at 800?°C due to the volatilization of Bi element. The dielectric properties and tunability of the films were annealing temperature dependent. BMN thin films annealed at 750?°C had a high dielectric constant of 135 and low dielectric loss of 0.002 at 1?MHz. The high tunability of 31.3?% and figure of merit of 156.5 were obtained under an applied electric field of 1?MV/cm at room temperature.     

A fluorescent magnetic nanoalloy--Lanthanon-doped FePt:RE

Employing dibenzo-24-crown-8-ether (DB24C8) as a phase-transfer catalyst, monodispersed fluorescent lanthanon-doped magnetic FePt:RE (RE=Eu, Dy, and Ce) nanoparticles about 3 nm in size were synthesized through the reduction of H2PtCl6.6H2O, Fe2(C2O4)3.5H2O, and RE(NO3)3 (RE=Eu, Dy, and Ce) by propylene glycol using oleic acid as the stabilizer in the solvent-thermal system. The conversion of the as-synthesized chemically disordered fcc FePt:RE nanoparticles to a chemically ordered L1 0 structure occurred after annealing treatment at 873 K, and was simultaneously accompanied by a coercivity increase. It is interesting that the amorphous formation trend is strengthened in an europium-doped FePt:Eu alloy accompanied by enhancement of the coercive force. Its thermal stability indicated that the addition of europium can inhibit the phase transformation. Moreover, the optical measurement results proved that FePt:Dy alloy nanoparticles have fluorescent properties.     

One-step synthesis of FePt nanoparticles with tunable size

A one-step synthesis of FePt nanoparticles is reported. The size, composition, and shape of the particles are controlled by varying the synthetic parameters such as molar ratio of stabilizers to metal precursor, addition sequence of the stabilizers and metal precursors, heating rate, heating temperature, and heating duration. An assembly of large (6 nm or greater) FePt nanoparticles, especially oxide-coated FePt nanoparticles, can sustain higher temperature (up to 650 degrees C) annealing without noticeable particle sintering. Room temperature coercivity of an assembly containing discrete FePt dots can reach as high as 1.3 T, a value that is suitable for hard magnetic applications.     

Transformation of three-dimensional three-connected silicon nets in SrSi2

Dimorphic SrSi₂ is the first compound for which the two simplest three-dimensional three-connected nets are found in its polymorphs. The cubic net of three-connected silicon atoms (SrSi₂ type of structure) can be transformed into the tetragonal one (α-ThSi₂ type of structure) by a high-pressure-high-temperature treatment. The tetragonal phase is quenchable. Heating of this phase to 600–700°C at ambient pressure results in transformation into the cubic one. At a heating rate of 20°C/min complete transformation can be achieved within 5 min in a DTA apparatus. The energy of transformation has been obtained from the peak areas of the DTA curves to ?1.6 ± 0.3 kcal/mole. Although the transformation between the three-dimensional three-connected sets in SrSi₂ must be formally classified as a reconstructive one, a relatively small entropy change (ΔS = 1 ·₁ cal/deg · mole) has been calculated from the change in molar volume and p-T equilibrium conditions. Therefore, structural relations between the cubic and the tetragonal nets are discussed.     

Polyol Process Synthesis of Monodispersed FePt Nanoparticles

Monodispersed FePt nanoparticles are synthesized by reduction of iron(II) acetylacetonate and platinum(II) acetylacetonate with 1,2-hexadecanediol as the reducing reagent in the polyol process. As-prepared FePt nanoparticles are chemically disordered with fcc phase. Transmission electron microscopy (TEM) images show a self-assembled particle array with an average particle size of 3 nm and a standard deviation about 10%. The transformation from chemically disordered fcc to chemically ordered L10 phase is achieved by annealing at 650 degrees C for 30 min in Ar atmosphere where the oxygen level is less than 1 ppm. Magnetic hysteresis measurements show a coercivity of 9.0 kOe at 293K, and 16.7 kOe at 5 K for the annealed FePt nanoparticles.     

Prevention of nanoparticle coalescence under high-temperature annealing

An effective method of employing 3-aminopropyldimethylethoxysilane linker molecules to stabilize 4.4 nm FePt nanoparticle monolayer films on a SiO2 substrate as well as to prevent coalescence of the particles under 800 degrees C annealing is reported. As-deposited FePt nanoparticle films in chemically disordered face-centered-cubic phase transform to mostly chemically ordered L1 0 structure after annealing, while the nanoparticles are free from serious coalescence. The method may fulfill the pressing need to prevent nanoparticle coalescence under high-temperature annealing for the development of FePt nanoparticle based products, such as ultrahigh-density magnetic recording media and novel memory devices.     

Structural stability and electrochemical properties of Gd-doped ZrO2 nanoparticles prepared by sol–gel

Cubic, tetragonal and monoclinic Gd-doped zirconia nanoparticles with nominal composition Gd_xZr_1?xO₂ in the range 0 ≤ x ≤ 0.2, were prepared by annealing dried gels of Gd-containing zirconia at temperatures over the range between 450 and 1,300 °C. The synthesized zirconia-based nanoparticles with increased gadolinium load were characterized by X-ray powder diffraction, infrared and Raman spectroscopies, and transmission electron microscopy. The stabilization of the crystalline forms of Gd-doped ZrO₂ solid solutions depends on the amount of Gd dopant and the annealing temperature. For low Gd loads in Gd_xZr_1?xO₂ being x < 0.05, the tetragonal form is the single phase up to 1,100 °C, whereas the monoclinic is the crystalline form detected up to 1,300 °C. Within the range of compositions 0.05 ≤ x < 0.1, is the tetragonal the only stabilized zirconia crystalline structure over the whole range of temperature up to 1,300 °C. For higher Gd-contents, in the range 0.1 ≤ x ≤ 0.2, is the cubic zirconia form the only stable phase for the whole range of annealing temperatures. Solid-state electrochemistry of the gadolinium-doped zirconia performed by the voltammetry of microparticles approach allowed distinguishing different electrochemical answers of Gd cation associated with slightly different local coordination surrounding of cations. Enantioselective electrocatalytic effect of monoclinic Gd-doped ZrO₂ on the oxidation of l-(+)-tartaric acid and d-(?)-tartaric was also studied.