Magnetic properties of SiO2-coated iron oxide nanoparticles studied by polarized small angle neutron scattering

The structural and magnetic properties of non-coated and SiO₂-coated iron oxide (Fe₃O₄) nanoparticles (NPs) were investigated by a polarized small-angle neutron scattering (P-SANS) method. Measurement of the P-SANS allowed us to obtain nuclear and magnetic scattering cross sections of the NPs under applied magnetic field. The analysis of the scattering intensity provided the structural parameters and the spatial magnetization distribution of the non-coated and the SiO₂ coated core–shell NPs. The measured radius of both NPs and the shell thickness of the core–shell NPs were in consistent with those measured by the transmission electron microscopy. In comparison, the magnetic core radii of both NPs were 0.12–0.6 nm smaller than the nuclear radii, indicating the magnetization reduction in the surface region of core Fe₃O₄ in both NPs. However, the reduced magnetization region, which is the surface spin canting region, of the SiO₂-coated NPs was relatively narrower than that of the non-coated NPs. We suggest that the SiO₂ coating on the Fe₃O₄ NPs may stabilize the spin order of atoms and prohibit the oxidation or defect formation at the surface region of the Fe₃O₄ NPs, and enhance the corresponding magnetization of the Fe₃O₄ NPs by the reduction of the spin canting layer thickness.     

Oxide nanoparticles in an Al-alloyed oxide dispersion strengthened steel: crystallographic structure and interface with ferrite matrix

Abstract

Oxide nanoparticles are quintessential for ensuring the extraordinary properties of oxide dispersion strengthened (ODS) steels. In this study, the crystallographic structure of oxide nanoparticles, and their interface with the ferritic steel matrix in an Al-alloyed ODS steel, i.e. PM2000, were systematically investigated by high-resolution transmission electron microscopy. The majority of oxide nanoparticles were identified to be orthorhombic YAlO₃. During hot consolidation and extrusion, they develop a coherent interface and a near cuboid-on-cube orientation relationship with the ferrite matrix in the material. After annealing at 1200 °C for 1 h, however, the orientation relationship between the oxide nanoparticles and the matrix becomes arbitrary, and their interface mostly incoherent. Annealing at 1300 °C leads to considerable coarsening of oxide nanoparticles, and a new orientation relationship of pseudo-cube-on-cube between oxide nanoparticles and ferrite matrix develops. The reason for the developing interfaces and orientation relationships between oxide nanoparticles and ferrite matrix under different conditions is discussed.     

Small-angle neutron scattering study of the nano-sized features in an oxide dispersion-strengthened Fe12Cr alloy

Small-angle neutron scattering experiments, along with positron lifetime measurements and transmission electron microscopy observations, were performed on samples of an oxide dispersion-strengthened (ODS) Fe12Cr alloy and its non-ODS counterpart in order to characterize their nano-sized features. The nuclear and magnetic scattering data were analysed using the maximum entropy approach for obtaining the size distribution of the scattering centres in these materials. The positron annihilation results and the TEM information have made possible an interpretation of the volume distribution of the scattering centres having sizes below ~16 nm and their proper quantitative analyses. The smaller scattering centres in the ODS alloy exhibit distributions with modal values at ~6–7 and 12–14 nm. The peak at ~6–7 nm appears to be due to the overlapping of more than one type of scattering centres, while the one at ~12–14 nm can be exclusively attributed to the Y-rich centres. The quantitative analysis of the magnetic scattering data yields a volume fraction and number density of the Y-rich particles estimated in 0.70?±?0.03% and 0.77 × 10²² m^?3, respectively.     

碳化物弥散强化钢力学性能及微观组织研究

用碳化物粒子对低活化钢CLF-1进行弥散强化.结果表明机械合金化的方法可以制备高强度的碳化物弥散强化钢,经过60h球磨可完成合金化过程,同时添加的碳化物粒子很好地提高了低活化钢CLF-1的拉伸性能,得到了比熔炼低活化钢更高的强度和硬度,同时保持了较好的延伸率.     

A small angle neutron scattering study on the mixtures of pluronic L121 and anionic surfactant AOT

Small angle neutron scattering (SANS) experiments have been carried out on the micellar solutions containing mixtures of a hydrophobic triblock copolymer (L121, EO₅PO₆₈EO₅) and a hydrophobic anionic surfactant (AOT, sodium bis(2-ethylhexyl)sulphosuccinate) in water with varying ratio (R) of AOT to L121 for R = 0.15, 0.2, 0.3, 0.5 and 0.6. It is known that either L121 or AOT alone forms vesicles in water, but in the mixture with appropriate ratio of the two components a thermodynamically stable, isotropic solution of apparently small micelle-like aggregates is formed. We find that these micelles are prolate ellipsoidal.      

Effect of heat treatment on pore structure in nanocrystalline NiO: A small angle neutron scattering study

Nanocrystalline nickel oxide powders were calcined at 300, 600 and 900°C and pore structure evolution was followed by small angle neutron scattering (SANS). Pore size distributions at two widely separated size ranges have been revealed. Shrinkage of larger-sized pore with reduction in polydispersity has been observed with increasing heat treatment temperature. The pore structures at various heat treatment temperatures do not scale. This has been attributed to the grain boundary diffusion leading to an asymmetric shrinkage of the pores.      

小角x射线散射结晶聚合物结构的研究

利用结晶聚合物的“三相结构”模型计算了结晶聚合物的一维电子密度相关函数,结论是三相模型的片层厚度和不变量与两相结构的意义不同.利用计算结果分析了一批样品的结构参量,发现用Ruland方法得到的结晶过渡层的厚度与用一维电子密度相关函数的结果是一致的.用Bragg定律求出的结晶聚合物的长周期与相关函数法长周期相差很多.这是因为两种分析结晶过渡层厚度的方法都是以样品电子密度的不均匀区为基础的,本质是一致的.但是Bragg法的长周期与相关函数法的长周期代表的范围不同 关键词： 小角x射线散射 结晶聚合物 三相结构 相关函数     

Small angle neutron scattering study on the aggregation behaviour of PEO-PPO-PEO copolymers in the presence of a hydrophobic diol

Small angle neutron scattering (SANS) measurements on aqueous solutions of four polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymers (commercially known as Pluronic®)F88, P85, F127 and P123 in the presence of hydrophobic C14Diol (also known as Surfynol® 104) reveal information on micellization, micellar size and micellar transitions. While most hydrophilic F88 (with least PPO/PEO ratio) remained unimers in water at 30°C, other copolymers formed micellar solutions. Surfynol® 104 is sparingly soluble in water to only about ～0.1 wt%, but on addition to pluronic solution, it gets incorporated in the micellar region of block copolymer which leads to increase in aggregation number and transformation of spherical to ellipsoidal micelles. The added diol-induced micellization in F88, though hydrophilic copolymers F88 and F127 did not show any appreciable micellar growth or shape changes as observed for P85 and P123 (which are comparatively more hydrophobic). The SANS results on copolymer pairs with same molecular weight PPO but different % PEO (viz. F88 and P85, F127 and P123) and with same molecular weight PEO but different PPO (F88 and F127) reveal that the copolymer with large PPO/PEO ratio facilitate micellar transition in the presence of diol. An increase in temperature and presence of added electrolyte (sodium chloride) in the solution further enhances these effects. The micellar parameters for these systems were found out using available software and are reported.     

Structure Analysis of Solid Lipid Nanoparticles for Drug Delivery: A Combined USANS/SANS Study

Suspensions of solid lipid nanoparticles (SLNs) stabilized with emulsifiers have been extensively investigated (since the 1990s) as drug carriers, although details of their ultrastructure are poorly defined. Previously, a novel microwave‐assisted microemulsion‐based technique to prepare SLNs was reported. To understand the detailed internal structure of these SLNs, ultra‐small angle neutron scattering (USANS) and small angle neutron scattering (SANS) experiments are conducted on suspensions of hydrogenated stearic acid SLNs stabilized with hydrogenated Tween 20 surfactant in D₂O. Together, SANS and USANS gives a combined Q range of 0.000047 to 0.6 Å^?1 (corresponding to a size range of ≈1 nm–15 µm). This extended Q range allows a comprehensive understanding of the hierarchical structure of SLNs. The data are consistent with the multi‐length scale structure of SLNs having polydispersed large particles with roughened surfaces at the microscale level. At the nanoscale level, the results are consistent with the SLNs having an ellipsoidal shape intermediate between spheres and rods, with a crossover from mass fractals to surface fractals. The elucidation of this structure is particularly important given that the structure influences the stability and drug release properties of the nanoparticles. These results assist in the development of systems with desired shape and properties.     

Structure and spectroscopy of the supercapacitor material hydrous ruthenium oxide,RuO2·xH2o,by neutron scattering*

Hydrous ruthenium dioxide, RuO₂·xH₂O, is a material of active investigation as an electrode material for supercapacitors. A combination of elastic and inelastic neutron scattering together with thermal gravimetric studies and DFT calculations have provided new insight into the nature of the surface species present on RuO₂·xH₂O. Our results confirm that hydrous ruthenium oxide is a nanocrystalline material consisting of a core of RuO₂. We show that the surface consists largely of Ru–OH with small amounts of water hydrogen-bonded to the surface. The hydroxyls are stable up to ～200°C, i.e. over the composition range x?=?0.2–2. The optimal supercapacitor material has x?=?0.5–0.7, and in this range, the surface is fully hydroxylated. This provides a route for the proton transport: a proton can attach to a surface hydroxyl to generate coordinated water, proton transport then occurs along the hydrogen-bonded chain by a Grotthuss mechanism.     

Al-Zn-Mg-Cu-Li合金时效过程微结构演化的小角x射线散射研究

应用小角x射线散射技术分析了Al-Zn-Mg-Cu-Li合金在130，150和160℃温度时效24 h析出粒子的微结构参数的变化情况. 粒子的半径随着时效温度的增高而增加，它的比内表面积和体积百分数随着时效温度的增高而减小. 对Porod曲线q³J(q)-q²的分析表明,析出粒子与基体之间有明显的界面. 关键词： 小角x射线散射 Al-Zn-Mg-Cu-Li合金 时效 析出粒子     

Small angle neutron scattering study of U(VI) third phase formation in HNO<Subscript>3</Subscript>/DHDECMP-<Emphasis Type="Italic">n</Emphasis>-dodecane system

Small angle neutron scattering studies (SANS) were carried out to understand the formation of third phase in DHDECMP-dodecane-UO₂(NO₃)₂/HNO₃ system. It was observed that third phase formation takes place due to the formation of UO₂(NO₃)₂.DHDECMP reverse micelles in the dodecane phase. SANS data obtained were interpreted with particle interaction model using Baxter sticky spheres model.      

A comparative study of nanoparticles in premixed flames by scanning mobility particle sizer, small angle neutron scattering, and transmission electron microscopy

Scanning mobility particle sizer (SMPS) and transmission electron microscopy (TEM) studies were conducted for TiO₂ and soot particles. The TiO₂ particles were produced from a premixed stagnation ethylene-oxygen-argon flame (? = 0.36) doped with titanium tetraisopropoxide. Soot was generated from a burner-stabilized premixed ethylene-oxygen-argon flame (? = 2.5). The close agreement among SMPS, TEM, and X-ray diffraction results for TiO₂ nanoparticles demonstrates that the probe sampling/mobility measurement technique is accurate for on-line analysis of the size distribution of particles as small as 3 nm in diameter. In the case of soot, notable disagreement between the SMPS and TEM sizes was found and attributable to the fact that the soot taken from the flame studied herein is liquid-like and that upon deposition on the TEM grid, the primary particles do not retain their sphericity. This interpretation is supported by measurements with photo ionization aerosol mass spectrometry, small angle neutron scattering, and thermocouple particle densitometry.     

High resolution neutron scattering study of low-energy magnetic excitations in Nd2-xCexCuO4

The low-energy magnetic excitations (?ω ≤ 2 meV) of polycrystalline samples of Nd_2-xCe_xCuO₄ with x = 0, 0.1 and 0.15 have been measured with high resolution inelastic neutron scattering using time-of-flight technique at temperatures below 0.3 K. All observed scattering originates from transitions within the ground state doublet of Nd³⁺. For Nd₂CuO₄ the response is inelastic, and shows at least three different modes, of which one is almost dispersionless. For x = 0.1 the excitation spectrum shifts towards lower energies, but the main features of the undoped compound are still visible, whereas for x = 0.15 the response is mainly quasi-elastic but remains localised in Q-space around the first magnetic Bragg point (0.5 0.5 1). A comparison with data obtained on a triple-axis-spectrometer on single crystals with x = 0.0 and x = 0.15 reveals that the response of the doped sample in the [0 0 1] direction is still inelastic.     

Thermal effects on the structural properties of tungsten oxide nanoparticles

Tungsten oxide nanoparticles are prepared by evaporating and oxidizing the tungsten boat in helium and oxygen atmosphere and then quenched to the liquid nitrogen temperature. The as-prepared tungsten oxide nanoparticles are porous-free with uniform size. The morphology and particle size distribution of the as-prepared and after sinter treatments tungsten oxide nanoparticles are revealed by TEM and AFM. The long-range order of these nanoparticles can be examined by X-ray diffraction technique. The as-prepared nanoparticles exhibit a mixture structure of monoclinic and hexagonal crystals. Preliminary X-ray diffraction results indicate that the hexagonal structure is transformed to monoclinic structure after annealing to above 600°C. In order to better distinguish the structural properties of the tungsten oxide (WO_{3− x}) nanoparticles before and after annealing, the X-ray absorption spectrum technique is utilized; thus, the detailed local atomic arrangement of oxygen and/or tungsten can be determined. According to the XAS result, the shape of the W L₃-edge undergoes no considerable changes. This infers that structural transformation of tungsten oxide nanoparticle may be caused by the migration of oxygen after sintering. From the O K-edge of absorption spectrum, it suggests that a mixture phase structure is obtained when sintered below 300°C. And this result indicates that heat treatment to approximately 600°C produces a stable structure of a monoclinic crystal of WO₃.     

Small angle x—ray scattering study on the conformation of polystyrene in toluene during adding anti—solvent CO2

The conformatiopn of polystyrene in the anti-solvent process of supercritical fluids(compressed CO2 polystyrene toluene)has been studied by small angle x-ray scattering with synchrotron radiation as an x-ray source.Coilto-globule transformation of the polystyrene chain was observed with the increase of the anti-solvent CO2 pressure;i.e.polystrene coiled at a prssure lower than the cloud point pressure(Pc)and turned into a globle with a uniform density at pressures higher than Pc.Fractal behaviour was also found in the chain contraction.and the mass fractal dimension increased with increasing CO2 pressure.     

Characterization of the globular oxide inclusion ratings in steel using laser-induced breakdown spectroscopy

Grade assessment of steel is generally performed via the metallographic method, which is timeconsuming and is not able to provide the elemental distribution information. In this paper, we present a method to measure the globular oxide inclusion ratings in steel using laser-induced breakdown spectroscopy (LIBS). The measurement is performed in two basic steps: steel samples are polished using metallographic sand paper and the Al₂O₃ inclusion number and size distribution in a marked area are observed using scanning electron microscope/energy dispersive X-ray spectroscopy (SEM/EDS) for further LIBS scanning analysis. The threshold intensity that distinguishes soluble aluminum and insoluble aluminum inclusions is determined using LIBS combined with the SEM/EDS statistical data. Carbon steel (the sample number is S9256) and bearing steel (the sample number is GCr15) are analyzed in scanning mode, and the number of Al₂O₃ inclusions in different size ranges is obtained from the statistical information derived from the Al₂O₃ size calibration curve. According to heavy and thin series for globular oxide inclusions grade assessment, the method we propose is comparable to the traditional metallographic method in terms of accuracy; however, the process is simplified and the measurement speed is significantly improved.     

A TEM study of α-phase stability in Zr-2.5 Nb pressure tubes following neutron irradiation (A TEM study of α-phase stability)

The α-phase in Zr-2.5 Nb pressure tubes has been analysed after irradiation with neutrons for temperatures between 523 and 573 K. The α-phase contains Nb in supersaturated solid solution (about 0.5−1 wt% Nb) in the as-fabricated condition. Irradiation results in the formation of small discrete precipitates having diameters of about 5 nm. Energy Dispersive X-ray (EDX) analysis using a scanning transmission electron microscope (STEM) was complicated by the presence of a self-generated X-rays in the irradiated material and by the fact that the precipitates were small relative to the foil thickness (typically 100–200 nm). Techniques developed to measure segregation of impurities at interfaces were employed to show that the precipitates were Nb-rich, their formation being consistent with a decrease in Nb concentration in the matrix.     

Magnetization and neutron scattering studies of the pressure effect on the magnetic transition in Er Y Co

Neutron powder diffraction was employed to study the pressure effect on the magnetic transition in the pseudobinary Laves-phase compound Er_0.57Y_0.43Co₂ and to determine the magnetic moments of the Er- and Co-subsystems. Our studies reveal that the onset of long-range magnetic order for both the localized 4 f (Er) and itinerant 3 d (Co) electron moments appears at about the same temperature at ambient pressure. The pressure effect on T_c is found to be negative and equal for both sublattices, namely T _c / p ∼ - 0.4 K/kbar. The values of the magnetic moments of the Er and the Co ions are found = 5.40±0.15μ _B /atom, = 0.50±0.07μ _B /atom and 5.35±0.15μ _B /atom, 0.37±0.09μ _B /atom, for p = 0 and 6 kbar, respectively. Our experimental results give evidence for short-range magnetic order formation at temperatures already above T_c and for a coexistence short- and long-range order below T_c down to 4 K. Received 20 December 2001 / Received in final form 12 June 2002 Published online 31 October 2002 RID="a" ID="a"e-mail: andrew.podlesnyak@psi.ch     

XPS depth profiling study on the passive oxide film of carbon steel in saturated calcium hydroxide solution and the effect of chloride on the film properties

X-ray photoelectron spectroscopy (XPS) was used to study the properties of passive oxide film that form on carbon steel in saturated calcium hydroxide solution and the effect of chloride on the film properties. The thickness of the oxide films was determined to be approximately 4 nm and was not affected by the exposure time. Near the film/substrate interface the concentration of the Fe²⁺ oxides was higher than the concentration of the Fe³⁺ oxides; the layers near the free surface of the film mostly contained Fe³⁺ oxides. Chloride exposure decreased the thickness of the oxide films and changed their stoichiometry such that near the film/substrate interface Fe³⁺/Fe²⁺ ratio increased.