NMR relaxivity of coated and non-coated size-sorted maghemite nanoparticles

ABSTRACT

The effect of polymer coating on MNR relaxometry of maghemite nanoparticles has been studied. The samples were carefully sorted by size in order to reach narrow size distribution (<0.2) with size ranging from 4.5 to 12.5?nm. Relaxation dispersion profile as well as studies at a fixed Larmor frequency, were recorded for numerous either uncoated or polymer coated samples. The NMR relaxivities r₁ and r₂ increase with nanoparticle diameter. We have analysed the role of polydispersity for nanoparticles with the same mean size on the dispersion curves. We have compared the role of coating on nanoparticles NMR relaxivity between bare and poly(sodium acrylate-co-maleate) coated nanoparticles. We have investigated the influence of nanoparticle size on the T₁ and T₂ activation energy Ea. While Ea decreases with nanoparticle diameter when determined from T₁, it increases from T₂ determination. The influence is more important for small particles (<9?nm) than for big particles (>9?nm). Moreover, the PAAMA coating changes the energy Ea obtained from T₂: Ea becomes independent of the nanoparticle diameter. These results highlight the need of a complete characterisation of the role of the coating on the relaxation of magnetic particles.     

Influence of impurities on the low-temperature deformation of nanocrystalline copper

The influence of ZrO₂ particles on the low-temperature deformation of nanocrystalline copper produced by strong plastic deformation is investigated using equichannel angular pressing. A comparison is made between the deformation characteristics in tension and compression in the temperature range 4.2–400 K, measured for copper and the composite Cu:0.3 vol. % ZrO₂. It is shown that within 4.2–200 K the yield point σ _sm of the composite is higher than that for copper, attaining 680 MPa at 4.2 K, then the yield points are close in value up to room temperature, and diverge again as the temperature is raised. Possible causes of the dissimilar influence of an impurity on the strength and plasticity characteristics of nanocrystalline copper in various temperature intervals are discussed. Fiz. Tverd. Tela (St. Petersburg) 40, 1639–1641 (September 1998)     

Characterization of ZrO2-promoted Cu/ZnO/nano-Al2O3 methanol steam reforming catalysts

Three Cu/ZnO/ZrO₂/Al₂O₃ methanol reforming catalysts were investigated using X-ray photoelectron spectroscopy (XPS). The catalysts which contained ZrO₂ from a monoclinic nanoparticle ZrO₂ precursor exhibit both a higher activity toward the methanol steam reforming reaction and a lower CO production rate compared to catalysts composed of an XRD-amorphous ZrO₂ produced by impregnation using a Zr(NO₃)₂ precursor. The presence of a monoclinic phase appears to result in an increased charge transfer between the Zr and Cu species, as evidenced by a relatively electron-rich ZrO₂ phase and a partially oxidized Cu species on reduced catalysts. This electron deficient Cu species is more reactive toward the methanol reforming reaction and partially suppresses CO formation through the reverse water gas shift or methanol decomposition reactions.     

The comparison of photocatalytic activity of synthesized TiO2 and ZrO2 nanosize onto wool fibers

TiO₂ and ZrO₂ nanocrystals were successfully synthesized and deposited onto wool fibers using the sol-gel technique at low temperature. The photocatalytic activities of TiO₂-coated and ZrO₂-coated wool fibers were measured by studying photodegradation of methylene blue and eosin yellowish dyes. The initial and the treated samples were characterized by several techniques such as scanning electron microscopy (SEM), transmission electron microscopy (TEM), diffuse reflectance spectroscopy (DRS) and X-ray diffraction. The TEM study shows dispersed particles with 10-30 nm in size for TiO₂-coated and 20-40 nm in size for ZrO₂-coated samples on the fiber surface. Comparison of the photocatalytic activity of the coated samples reveals superiority of TiO₂ modified sample with respect to that of ZrO₂ for degradation of both dyes. Our observations indicate that by applying this technique to the fabrics, self-cleaning materials could be designed for practical application.     

碳纳米管表面金纳米颗粒的形成与结构转变

利用分子动力学模拟研究了室温下金纳米颗粒在碳纳米管表面的结构和作用能.研究结果表明,金纳米颗粒随着尺寸的增大会发生不同于孤立状态下的结构转变.当原子数小于130时,颗粒属于无序结构;当原子数大于140时,呈现面心立方晶体结构.小金纳米颗粒和碳纳米管结合紧密,相互作用能正比于面对碳纳米管的颗粒表面面积. 关键词： 金纳米颗粒 碳纳米管 分子动力学模拟     

Methane-assisted combustion synthesis of nanocomposite tin dioxide materials

Combustion synthesis of tin dioxide (SnO₂) was studied using a new synthesis approach where the combustion environment was augmented to control the temperature and flow conditions using methane as a supplemental fuel. The experiments were carried out at atmospheric pressure using a multi-element diffusion flame burner with a gas-phase precursor for SnO₂ and solid-phase precursor for metal additives. In the methane-assisted (MA) system, the inert carrier gas was replaced with methane as the transport gas for the SnO₂ and metal additive precursors. Two additive precursors were investigated: gold acetate and aluminum acetate. Particle morphology, primary particle size, crystallinity, phase, molecular and elemental composition were studied using transmission electron microscopy, X-ray diffraction, and energy-dispersive spectroscopy. Particle imaging velocimetry and thermocouple measurements provided velocity and temperature data for the synthesis environment experienced by particles. The MA system provided conditions for rapid sintering of particles into large faceted single crystals of SnO₂ (d_p = 46 nm) compared to methane unassisted system (d_p = 19 nm), thus offering a degree of control over grain size. Additionally, large aspect ratio (2.6 ± 0.9) single crystal SnO₂ particles were produced using the MA system. Gold-doped SnO₂ produced using the MA system yielded gold particles encapsulated in a layer of SnO₂. The characteristic reaction-, coagulation- and sintering-times were investigated for nanoparticle formation in the two systems using simplified models. The analysis provided qualitative justification for the trends observed in particle morphology. The modification of characteristic times in this study demonstrates a route for controlling size and morphology of single or multicomponent systems.     

Radiation stability of ZnO pigment modified by ZrO2 · Y2O3 nanopowders

The effect of the zinc oxide’s powder modification by ZrO₂ · Y₂O₃ nanoparticles on the spectra of diffuse reflectance and their changes after irradiation with 100-keV protons was studied at concentrations of 1, 3, 5, 7, 10, 15, and 30 wt % and T = 650 and 800 °C. Induced absorption spectra of irradiated powders were decomposed into bands of elementary defects. The effect of temperature on the band area and a change in the total absorbance of ZnO powders during nanoparticle modification and concentration was demonstrated.     

Simulation of the absorption spectra of nanometallic Al particles with core–shell structure: size-dependent interband transitions

Nanoaluminum combined with an oxidizing polymer binder is representative of a new class of nanotechnology energetic materials termed “structural energetic materials” that can be laser initiated by near-infrared heating of the Al particles. The visible and near-IR absorption spectra of Al nanoparticles passivated by the native oxide Al₂O₃, embedded in nitrocellulose (NC) binder, are simulated numerically using a model for the metallic dielectric function that incorporates the effects of interband transitions. The effects of oxide thickness, nanoparticle size and size distribution, and particle shape on the absorption characteristics are investigated. The nanoparticle spectra evidence an absorption peak and valley in the 550–1,100 nm range that redshift with decreasing nanoparticle size. Calculations indicate that this peak-valley structure results from interband transitions, and the unusual redshift cannot be explained without using an interband transition onset frequency that varies with nanoparticle size.     

Influence of yttrium on EPR characteristics of chromium ions in nanoscale particles of zirconium dioxide

The EPR and proton magnetic resonance methods were applied to study zirconium hydroxide samples which transformed to nanoscale ZrO₂ powders upon annealing. The samples were obtained from solutions with mixture compositions (ZrO₂ + 0.5 mol % Cr₂O₃) and (ZrO₂ + 3 mol % Y₂O₃ + 0.5 mol % Cr₂O₃). The influence of yttrium on the recharging of the chromium ion upon annealing of samples was studied in the temperature range 100–950°C. A significant influence of yttrium on internal stresses caused by heating and cooling in the lattice of nanoscale ZrO₂ particles was detected using the EPR method. It was shown that the typical features of the influence of yttrium on total (over the entire crystallite) and local (near chromium ions) lattice distortions depend on the sample heating temperature and are different for various annealing temperatures.     

Zn-ZrO2 nanocomposite coatings: Elecrodeposition and evaluation of corrosion resistance

The Zn and Zn-ZrO₂ composite coatings were produced by electrodeposition technique using sulphate bath. ZrO₂ particles were characterized using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The ZrO₂ particle size distribution in the plating bath and Zeta potential and the ZrO₂ were measured using dynamic light scattering technique (DLS). The corrosion resistance properties of Zn and Zn-ZrO₂ composite coatings were compared by examining the experimental data acquired through polarization, open circuit potential (OCP) and Tafel measurements. The corrosion environment was 3.5 wt% NaCl solution. The variation of amount of ZrO₂ in the solution on their % wt inclusion in the composite and on composite microhardness was investigated. XRD patterns were recorded for Zn and Zn-ZrO₂ coatings to compare their grain size. The SEM images of coatings before and after corrosion under chemical and electrochemical conditions were presented. The results were analyzed to establish the superiority of Zn-ZrO₂ composite over Zn coating.     

Study on preparation and properties of molybdenum alloys reinforced by nano-sized ZrO<Subscript>2</Subscript> particles

The nano-sized ZrO₂-reinforced Mo alloy was prepared by a hydrothermal method and a subsequent powder metallurgy process. During the hydrothermal process, the nano-sized ZrO₂ particles were added into the Mo powder via the hydrothermal synthesis. The grain size of Mo powder decreases obviously with the addition of ZrO₂ particles, and the fine-grain sintered structure is obtained correspondingly due to hereditation. In addition to a few of nano-sized ZrO₂ particles in grain boundaries or sub-boundaries, most are dispersed in grains. The tensile strength and yield strength have been increased by 32.33 and 53.76 %.     

Effect of boundary scattering on the thermal conductivity of a nanostructured semiconductor material based on the BixSb2 ? xTe3 solid solution

This paper reports on a theoretical and experimental investigation of the behavior of the electrical and thermal conductivities of a nanostructured material based on Bi _x Sb_{2 − x} Te₃ solid solutions. The effect of boundary scattering has been taken into account by introducing the scattering mechanism with a constant mean free path equal to the nanoparticle size. A comparison with the results of the measurements has demonstrated that one can describe satisfactorily the experimental dependences of the electrical and thermal conductivities on the nanoparticle size by using only the parameters of the initial solid solution and its pure constituents. The estimates have revealed that the lattice thermal conductivity of nanostructured materials can be reduced by 20–30% as compared to the initial solid solution with nanoparticle sizes of the order of 20 nm, which should produce a favorable effect on the magnitude of the thermoelectric figure-of-merit.     

Dispersion of zirconium dioxide by pulsed laser radiation

A technique for producing ZrO₂ dioxide nanoparticles under the action of pulsed laser radiation is developed. By the methods of transmission electron microscopy and X-ray phase analysis, it is shown that the high-temperature cubic phase of ZrO₂ is formed during laser ablation. The dependence of the size of ZrO₂ dispersed particles on the laser radiation intensity is determined. A thermodynamic one-dimensional model of laser ablation of zirconium dioxide is analyzed. The results of analytical computations of ablation of ZrO₂ particles are confirmed by experimental data.     

Optical Properties of CdS–PVA Nanocomposites

Semiconductor–polymer nanocomposites, with good control over the nanoparticle size and their dispersion within the polymer matrix, can have applications in many optical and luminescent display devices. Cadmium sulphide (CdS) is the most popular semiconductor nanoparticle exhibiting size dependent properties due to its large exciton binding energy and its suitability for large scale production. The nanoparticles need to be passivated against aggregation with suitable capping agents, without sacrificing the desirable properties like transparency and flexibility of the polymer. Cadmium sulphide nanoparticles capped with polyvinyl pyrrolidone (PVP) are synthesized using cadmium nitrate (Cd(NO₃)₂) and hydrogen sulphide (H₂S) as Cd²⁺ and S^2– sources, respectively. CdS particles with sizes in the range of 5–6 nm are prepared in methanol and the solvent is removed using a rotary evaporator. CdS powder is dispersed in polyvinyl alcohol (PVA) solution with dimethyl formamide (DMF) as solvent to get (PVP–CdS)–PVA nanocomposite film of about 0.2 mm thickness. This has been characterized by powder X-ray diffraction (XRD), optical absorption studies, transmission electron microscopy (TEM), differential scanning calorimetry (DSC) and photoluminescence (PL). Particle size does not change due to incorporation in the polymer matrix and the polymer retains its transparency and flexibility. The nanocomposite shows good photoluminescence property with stronger band edge emission than defect related emission. The latter could be quenched completely by optimizing the PVP content. Irradiation of the nanocomposite with 8 MeV electrons at a dose of 100 kGy could effectively quench the defect related emission.     

Morphology Control of the Electrode for Solid Oxide Fuel Cells by Using Nanoparticles

LSM(La(Sr)MnO₃)/YSZ(Y₂O₃ stabilized ZrO₂) composite cathode for Solid Oxide Fuel Cells (SOFCs) was fabricated by using the composite particle consisting of well-dispersed nano-size grains of LSM and YSZ. The composite cathode had a porous structure as well as uniformly dispersed fine LSM and YSZ grains. Such unique morphology of the composite cathode led high electrochemical activity at 800°C. It suggests that the intermediate temperature (less than 800°C) operation of SOFCs will be achieved by using composite particles.     

Synthesis and CO2 capture property of high aspect-ratio Li2ZrO3 nanotubes arrays

High aspect-ratio Li₂ZrO₃ nanotubes were prepared by hydrothermal method using ZrO₂ nanotubes layers as templates. Characterizations of SEM, XRD, TEM and CO₂ adsorption were performed. The results showed that tetragonal Li₂ZrO₃ nanotubes arrays containing a little monoclinic ZrO₂ can be obtained using this simple method. The mean diameter of the nanotubes is approximately 150 nm and the corresponding specific surface area is 57.9 m² g⁻¹. Moreover, the obtained Li₂ZrO₃ nanotubes were thermally analyzed under a CO₂ flow to evaluate their CO₂ capture property. It was found that the as-prepared Li₂ZrO₃ nanotubes arrays would be an effective acceptor for CO₂ at high temperature.     

纳米颗粒与纳米块材摩尔定压热容的理论计算

探讨了纳米颗粒和纳米块材摩尔定压热容 C_P(T)的理论计算方法,提出了利用纳米颗粒的熔点数据来计算纳米颗粒的德拜(Debye)温度、体膨胀系数和C_P(T)的理论公式,以铜纳米颗粒为例,C_P(T)的理论计算值与实验值符合较好;提出了纳米块材的Debye温度随块材密度变化的关系式,随着块材密度减小,Debye温度降低;铜纳米块材C_P(T)的理论计算值与实验值也符合较好;纳米块材的体 关键词： 纳米颗粒 纳米块材 C_P(T)')" href="#">摩尔定压热容C_P(T) 德拜温度     

Transport properties and magnetoresistance in La0.8Te0.2MnO3/ZrO2 composites

The transport properties and magnetoresistance of electron-doped manganate / insulator composites (La_0.8Te_0.2MnO₃)_{1 - x}/(ZrO₂)_x (x=0, 0.3, and 0.5) are investigated. It is found that the metal-insulator transition temperature of this system shifts to a lower value as the ZrO₂ content increases. The introduction of ZrO₂ enhances both the domain scattering and electron relative scattering in the metal transport region. In the adiabatic small polaron hopping transport region, the thermal activation energy seems invariable regardless of the ZrO₂ content. The application of a magnetic field promotes the charge transportation capabilities of the composites, and the magnetoresistance is enhanced with an increase of the ZrO₂ content. This could be attributed to the more remarkable modification effect of magnetic field on ordering degree in the composites than in pure La_0.8Te_0.2MnO₃.     

Effect of phase transformation on optical and dielectric properties of zirconium oxide nanoparticles

Zirconium oxide nanoparticle (ZrO₂) is synthesized by the hydrothermal method at different calcination temperatures. The structural analysis is carried out by X-ray diffraction and Raman spectra. The sample prepared at 400 °C and 1100 °C showed the cubic and monoclinic phase, respectively, and the sample calcined at 600 °C and 800 °C showed the mixed phase with co-existence of cubic and monoclinic phases. Furthermore, the morphology and particle size of these samples were investigated by scanning electron microscope (SEM) and transmission electron microscope (TEM) analysis. The band gap estimated from UV–Vis spectra of ZrO₂ (zirconia) nanocrystalline materials calcined at different temperatures from 400 °C to 1100 °C was in the range of 2.6–4.2 eV. The frequency dependence of dielectric constant and dielectric loss was investigated at room temperature. The low frequency region of dielectric constant is attributed to space charge effects.     

Characterization of Y<Subscript>2</Subscript>BaCuO<Subscript>5</Subscript> nanoparticles synthesized by nano-emulsion method

Nanoscale yttrium–barium–copper oxide (Y₂BaCuO₅, Y211) particles were synthesized using the emulsion method and the solution method. The basic water-in-oil (w/o) emulsion system consisted of n-octane (continuous oil phase), cetyltrimethylammonium bromide (cationic surfactant), butanol (cosurfactant) and water. The composition of the emulsion system was varied and characterized by measuring the conductivity of the solutions and droplet size. The droplet size of emulsion was determined by using the dynamic light scattering method. The water content, cosurfactant content, and surfactant/n-octane ratio affected the droplet size which was in the range of 3–8 nm, and hence the w/o emulsion system was referred to as a nano-emulsion system. A model was used to verify the droplet size. The influence of salt (Y₂(NO₃)₃) content on the droplet size was investigated and the addition of salt reduced the droplet size. The effects of reaction time and temperature on the Y211 particle sizes were also investigated. The particles were characterized using the TEM, SEM, and XRD. Nanoparticles produced by the nano-emulsion method were calcined at 850°C to form the Y211 phase as compared to solid state processing temperature of 1050°C. Based on the TEM analysis, the average diameter of the Y211 particles produced using the nano-emulsion method was in the range of 30–100 nm. The effect of adding 15% Y211 nanoparticles to the superconductor YBCO-123 as flux pinning centers, was investigated, and the transition temperature was reduced by 3 K.