CoxCu1-x复相纳米线阵列的制备及其磁性的研究

利用电化学沉积方法在同一种富Co²⁺溶液Co²⁺/Cu²⁺=10∶1中,利用不同的沉积电位成功地制备了一系列不同成分(x=0.38—0.87)和复合相结构的Co_xCu_1-x纳米线阵列.发现随着纳米线中Cu含量的变化,Co_xCu_1-x纳米线的复相结构随之发生规律的变化,最终导致纳米线的磁性也随之规律的变化.随着纳米线中Cu含量的不断增加,一部分Cu与Co形成面心立方结构(fcc)的CoCu固溶体,减弱了磁晶各向异性与形状各向异性的竞争,从而提高样品的方形度;一部分Cu以fcc结构的Cu单质的形式存在于纳米线中,并随着Cu颗粒大小的不同分别起到破坏磁晶各向异性和钉扎畴壁的作用,从而增加纳米线的方形度和矫顽力.对比不同成分的样品,发现Co_xCu_1-x纳米线的方形度和矫顽力的最大值分别出现在Co₇₅Cu₂₅和Co₆₀Cu₄₀中,并且由于其特殊的复相结构致使它们的值要好于相同直径的单相结构的结果. 关键词： 纳米线 电化学沉积 磁性     

Surfactant-free synthesis of novel copper oxide (CuO) nanowire–cobalt oxide (Co<Subscript>3</Subscript>O<Subscript>4</Subscript>) nanoparticle heterostructures and their morphological control

A simple and surfactant-free synthesis of novel heterostructures comprising of copper oxide (CuO) nanowires uniformly decorated with cobalt oxide (Co₃O₄) nanoparticles was demonstrated by combining thermal growth and wet-coating method. The heterostructures were synthesized by thermally decomposing cobalt salt (cobalt nitrate) into Co₃O₄ nanoparticles onto vapor–solid (VS)-grown CuO nanowires. X-ray diffraction (XRD) and high resolution transmission electron microscopy (TEM) confirmed the presence of CuO and Co₃O₄ phases as well as a narrow size distribution of Co₃O₄ nanoparticles (average diameter ~7.0 ± 1.5 nm) on CuO nanowires (average diameter of nanowire tips ~67.9 ± 18.6 nm). Unique interfacial lattice relationship was observed for (111) Co₃O₄ nanoparticles on (200) CuO nanowire surface resulting in hemispherical shape of the former. For the first time, further systematic studies were performed to understand the influence of various parameters (cobalt salt concentration and annealing temperature, atmosphere, and time) on the morphological evolution of Co₃O₄ nanoparticles on CuO nanowires. Interestingly, by varying these parameters, it was possible to grow Co₃O₄ in different shapes (spherical, triangular, rectangular, cubical, and hexagonal nanoparticles) and forms (shells and nanorods). It was observed that all these parameters play a critical role in influencing the surface migration, nucleation, and growth of Co₃O₄ nanoparticles on CuO nanowires and this assisted in understanding the involved growth mechanisms. Finally, UV–vis–NIR spectroscopy and band gap energies for these heterostructures were evaluated that showed higher photocatalytic degradation efficiency for Rhodamine B under low-power visible-light illumination.     

Sonochemical synthesis and characterization of Co3O4 nanocrystals in the presence of the ionic liquid [EMIM][BF4]

For the first time, a sonochemical process has been used to synthesis cobalt oxide Co₃O₄ nanoflowers and nanorods morphology in the presence of the ionic liquid 1-Ethyl-3-methylimidazolium tetrafluoroborate [EMIM][BF₄] as reaction media and morphology template. Different sonication time periods and different molar ratios of the ionic liquid (IL) were used to investigate their effects on the structural, optical, chemical and magnetic properties of the produced Co₃O₄ nanoparticles. During synthesis process brown powder contains cobalt hydroxide Co(OH)₂ and cobalt oxyhydroxide (Cobalt hydroxide oxide) CoO(OH) was formed, after calcination in air for 4 h at 400 °C a black powder of Co₃O₄ nanoparticles was produced. The produced Co₃O₄ nanoparticles properties were characterized by X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), transmission electron microscopy (TEM), FTIR spectroscopy, UV–vis spectroscopy, and Vibrating Sample Magnetometer (VSM). To explain the formation mechanism of Co₃O₄ NPs some investigations were carried on the brown powder before calcination.     

Effect of high magnetic field annealing on the microstructure and magnetic properties of Co-Fe layered double hydroxide

The effects of high magnetic field (10 T) on the products obtained by calcination of Co-Fe LDH precursors at different temperatures were investigated. The XRD results indicated that Fe^III substituted for Co^III in Co₃O₄ to yield Co^IICo^IIIFe^IIIO₄ under the calcination of Co-Fe LDH precursors at 400 °C. The products obtained by magnetic field annealing at 400 °C had a porous plate-like morphology, whereas the products without magnetic field annealing were composed of nanoparticles. It was seen that CoFe₂O₄ phase could be formed at low temperature (about 500 °C) under the magnetic field annealing. The grain size of products obtained by magnetic field annealing at 800 °C was larger than that of zero magnetic field. It was found that the saturation magnetization was significantly enhanced after magnetic field annealing, especially at lower temperature (≤600 °C). The possible reason for the effects on the microstructure and magnetic properties of products obtained by magnetic field annealing was discussed.     

A density functional theory study of the electronic structures and magnetic properties of Fe（1-x）Cox alloy nanowires encapsulated in （10,0） carbon nanotubes

Under the generalized gradient approximation, the electronic structures and magnetic properties of Fe_(1-x)Co_x alloy nanowires encapsulated inside zigzag (10,0) carbon nanotubes (CNTs) are investigated systematically using firstprinciple density functional theory calculations. For the fully relaxed Fe_(1-x)Co_x/CNT structures, all the C atoms relax outwards, and thus the diameters of the CNTs are slightly increased. Formation energy analysis shows that the combining processes of all Fe_(1-x)Co_x/CNT systems are exothermic, and therefore the Fe_(1-x)Co_xalloy nanowires can be encapsulated into semiconducting zigzag (10,0) CNTs and form stable hybrid structures. The charges are transferred from the Fe_(1-x)Co_xnanowires to the more electronegative CNTs, and the Fe-C/Co-C bonds formed have polar covalent bond characteristics. Both the spin polarization and total magnetic moment of the Fe_(1-x)Co_x/CNT system are smaller than those of the corresponding freestanding Fe_(1-x)Co_xnanowire, and the magnetic moment of the Fe_(1-x)Co_x/CNT system decreases monotonously with increasing Co concentration, but the Fe_(1-x)Co_x/CNT systems still have a large magnetic moment, implying that they can be utilized in high-density magnetic recording devices.     

Study of magnetic properties of ZnO nanoparticles codoped with Co and Cu

Here, we report on systematic studies of the magnetic properties of Co and Cu codoped ZnO nanoparticles prepared by sol–gel technique. The effect of hydrogenation and shape on the magnetic properties of Zn_0.93Co_0.05Cu_0.02O nanoparticles is presented. The Zn_0.93Co_0.05Cu_0.02O nanoparticles and well-aligned Zn_0.93Co_0.05Cu_0.02O nanorod array display ferromagnetic behavior at room temperature. Our results demonstrate the influence of shape and hydrogenation on the ferromagnetic properties of Zn_0.93Co_0.05Cu_0.02O nanoparticles at room temperature.     

Effects of annealing temperature on structure and magnetic properties of amorphous Fe61Co27P12 nanowire arrays

Arrays of Fe₆₁Co₂₇P₁₂ nanowire with an aspect ratio about 70 were prepared in anodic aluminum oxide templates by electrodeposition. The influences of annealing temperature on structure and magnetic properties of Fe₆₁Co₂₇P₁₂ nanowires were studied. When the specimens were annealed below 400 °C, there are no obvious changes in structure except relaxation. With the annealing temperature increasing from 400 to 600 °C, the Fe-Co phase is detected by X-ray diffraction and Mössbauer spectra. The crystalline fraction and hyperfine field can be derived from Mössbauer spectra. The room temperature magnetic hysteresis loops show that the coercivity and squareness of the nanowire arrays in parallel to the wire axis increase with the increasing of annealing temperature, which mainly attributes to the strengthening of anisotropy.     

Dual behaviors of magnetic CoxFe1−x (0≤x≤1) nanowires embedded in nanoporous with different diameters

Co_xFe_1−x nanowire arrays with various diameters and different composition were fabricated by ac electrodeposition using porous alumina template. Coercivity along the easy axis reaches to a maximum at 2330 Oe, for Co_xFe_1−x nanowires containing about 40 at% Co. The crystalline structure of the nanowires was concentration-independent and shows a bcc structure. The critical diameter for transition from coherent rotation to curling mode is 35 nm for CoFe containing less than 40 at% Co while it is 30 nm for those with more than 40 at% Co. Optimizing the magnetic properties of CoFe with different Co content was seen to be dependent on the diameter of nanowires. For 25 nm diameter, the optimum was shown below 50 at% Co while it was seen above 50 at% for nanowires with 50 nm diameter. The angular dependence of the coercivity with nanowires diameter were also studied.     

Preparation and magnetic properties of anisotropic (Sm,Pr)Co5/Co composite particles

Anisotropic (Sm,Pr)Co₅/Co nanocomposite particles have been fabricated by chemical coating the 2 h ball milled (Sm,Pr)Co₅ flakes with Co nanoparticles. The Co nanoparticles were synthesized with mean particle sizes in the range of 20-50 nm. The nanocomposite particles present [0 0 1] out-of-plane texture and improved magnetic properties, e.g., an enhanced remanent magnetization of 72 emu/g for (Sm,Pr)Co₅/Co and 66 emu/g for (Sm,Pr)Co₅. In addition, by using the 8 h ball milled powders (much smaller than the 2 h ball milled powders) as the starting materials, Co nanoparticles can also be successfully coated on the surface of the flakes. A plausible mechanism for the formation of Co nanoparticles on the surface of (Sm,Pr)Co₅ flakes is discussed.     

Charge-discharge characteristics of nanocrystalline Co3O4 powders via aerosol flame synthesis

Nanocrystalline Co₃O₄ powders were synthesized by aerosol flame synthesis (AFS) method for the anode of lithium ion batteries and the basic electrochemical properties were investigated. The effects of synthesis conditions and heat-treatment temperature on the morphology, crystallite size and electrochemical properties were investigated. As-prepared soot contained Co₃O₄, CoO and Co(OH)₂, which were eventually converted into cubic spinel Co₃O₄ by post heat treatment. The as-prepared particle size was in the range of 10-30 nm and grew to 50-85 nm by the heat treatment. With growing particle size and improved crystallinity, charge-discharge capacity and cycle performance were improved and the discharge capacity of the powder heat-treated at 700 °C was 571 mAh/g after 30 cycles, which was better than Co₃O₄ powder reported in the previous literature.     

Pulse electrodeposition of Co1−xZnx nanowire arrays: Magnetic improvement through electrolyte concentration,off-time between pulses and annealing

Using different electrolyte compositions and varying the off-time between pulses, Co_1xZn_x nanowire arrays were fabricated by ac pulse electrodeposition. The effect of deposition parameters on alloy contents was investigated by studying the microstructures and magnetic properties of as-deposited and annealed Co_1xZn_x nanowires. It is shown that Zn content in CoZn nanowires exponentially increases by increasing the zinc ions in the electrolyte. The Zn content initially increases to a maximum by increase in off-time between pulses and then falls off. Adding a certain amount of Zn to Co led to form amorphous CoZn nanowires. A significant increase in magnetization, coercivity and squareness of CoZn nanowires was observed after annealing. The rate of increase in magnetization of annealed samples was seen to be inversely proportional to their initial magnetization. Improvement of magnetic properties of annealed samples may be caused by magnetic cluster formation and pinning effect.     

Fabrication and magnetic properties of CoxPd1−x composite nanowire

A series of Co_xPd_1−x   (x=0.37–0.85$x=0.37–0.85$) nanowire arrays have been successfully deposited in a single Co²⁺/ Pd²⁺=20:1 solution by applying the various depositing potentials. We found that the nanowires are the composites of CoPd alloy with some Co and Pd clusters, but the overall structure of the composite wires followed the binary phase relation of Pd–Co. The existence of Pd content makes the nanowires structured in FCC phase, except for Co_0.85Pd_0.15 sample in which some HCP Co phase coexists with the dominating FCC phase. Between Co-rich and Pd-rich nanowires, we found that the optimized composition for Co_xPd_1−x nanowire is around Co_0.73Pd_0.27 in which the coercivity (H_c) and squareness (M_r/M_s) have their maximum values consistently.     

Study of the use of ionizing radiation for the modification of CoO/Co0.65Zn0.35 nanostructures

The paper presents the results of a study of the influence of heavy ions Xe²²⁺ on the morphology, phase composition, structural and conductive characteristics of CoO/Co_0.65Zn_0.35 nanowires obtained by the method of electrochemical synthesis. As a result of the research, it was established that an increase in the irradiation fluence leads to a change in the phase composition, due to the decomposition of the oxide phase CoO and the predominance of Co_0.65Zn_0.35 substitution in the structure of the cubic phase of solid solution. It has been established that an increase in the irradiation fluence and a decrease in the oxide phase in the structure leads to a decrease in the concentration of dislocations and vacancies in the nanowires, which indicates a partial relaxation of defects as a result of irradiation. It is established that a change in dislocation and vacancy density leads to an increase in the value of specific conductivity and a decrease in resistance.     

Structure and magnetic properties of CoxPb1−x nanowire arrays

Ordered Co_xPb_1−x nanowire arrays embedded in the porous anodic aluminum oxide (AAO) template have been fabricated by electrodeposition. XRD experiments prove that neither hexagonal-close-packed (hcp) nor face-centered-cubic (fcc) Co peaks are detected when the Co component (x) is below 0.91. The coercivity (H_c) and squareness (M_r/M_s) are found to increase with ferromagnetic Co component and the maximum value is at the position x=1 (pure Co nanowires). Annealing effects cause H_c and M_r/M_s increase, which surpasses the pure Co nanowires in the 0.2<x<0.6 at the annealing temperature of 700 °C. Microstructure change during annealing process is proposed to explain the magnetic properties change of samples.     

Fabrication and magnetic properties of amorphous Co0.71Pt0.29 nanowire arrays

Highly ordered Co_0.71Pt_0.29 alloy nanowire arrays have been fabricated successfully by direct current electro-deposition into the pores of a porous anodic aluminum oxide (AAO) template. SEM and TEM images reveal that the nanowires of array are uniform, well isolated, and parallel to one another. The aspect ratio of nanowires is over 200. XRD and EDS pattern indicates that amorphous Co_0.71Pt_0.29 structure was formed during electro-deposition. In amorphous sample, magnetocrystal anisotropy is very small, therefore, shape anisotropy plays a dominant role which leads to strong perpendicular anisotropy. High coercivity (Hc=1.7 kOe) and squareness (Mr/Ms) around 0.7 were obtained in the samples when the field was applied parallel to the axis of the nanowires. However, when it changed to polycrystalline structure after annealing, due to the competition of magnetocrystal anisotropy and shape anisotropy, the sample did not display perpendicular anisotropy.     

Synthesis and magnetic properties of antiferromagnetic Co3O4 nanoparticles

Antiferromagnetic Co₃O₄ nanoparticles with diameter around 30 nm have been synthesized by a solution-based method. The phase identification by the wide-angle X-ray powder diffraction indicates that the Co₃O₄ nanoparticle has a cubic spinel structure with a lattice constant of 0.80843(2) nm. The image of field emission scanning electron microscope shows that the nanoparticles are assembled together to form nanorods. The magnetic properties of Co₃O₄ fine particles have been measured by a superconducting quantum interference device magnetometer. A deviation of the Néel temperature from the bulk is observed, which can be well described by the theory of finite-size scaling. An enhanced coercivity as well as a loop shift are observed in the field-cooled hysteresis loop. The exchange bias field decreases with increasing temperature and diminishes at the Néel temperature. The training effect and the opening of the loop reveal the existence of the spin-glass-like surface spins.     

Light-induced antifungal activity of TiO2 nanoparticles/ZnO nanowires

Antifungal activity of TiO₂/ZnO nanostructures under visible light irradiation was investigated. A simple chemical method was used to synthesize ZnO nanowires. Zinc acetate dihydrate, Polyvinyl Pyrrolidone and deionized water were used as precursor, capping and solvent, respectively. TiO₂ nanoparticles were deposited on ZnO nanowires using an atmospheric pressure chemical vapor deposition system. X-ray diffraction pattern of TiO₂/ZnO nano-composite has represented the diffraction peaks relating to the crystal planes of the TiO₂ (anatase and rutile) and ZnO. TiO₂/ZnO nanostructure antifungal effect on Candida albicans biofilms was studied and compared with the activity of TiO₂ nanoparticles and ZnO nanowires. The high efficiency photocatalytic activity of TiO₂ nanoparticles leads to increased antifungal activity of ZnO nanowires. Scanning electron microscope was utilized to study the morphology of the as prepared nanostructures and the degradation of the yeast.     

The size and space arrangement roles on coercivity of electrodeposited Co1−xCux nanowires

Magnetization curves with various magnetic field orientations and nanowire diameters were measured at room temperature. The measured coercivity as a function of angle (θ) between the field and wire axis reveals that the coercivity decreases with increasing value of θ for various nanowires. Theoretically, based on Monte Carlo simulation we investigated the magnetization reversal modes of the Co_1−xCu_x nanowires and obtained also the θ dependence of the coercivity. Comparing the simulated with the experimental results, we find that the magnetocrystalline anisotropy plays an important role on the magnetic properties of Co_1−xCu_x nanowires, and the magnetization reversal process in the Co_1−xCu_x nanowires could not be understood by the classical uniform rotation mode in the chain-of-sphere model.     

Controlling the composition and the magnetic properties of hexagonal Co2Z ferrite powders synthesized using two different methods

Polycrystalline Co₂Z hexaferrite (Ba₃Co₂Fe₂₄O₄₁) powders have been prepared via two wet chemical routes: sol gel auto-combustion (SGA) and co-precipitation (CP) methods. The effects of synthesis conditions on the crystal structure, crystallite size, morphology, and magnetic properties were systematically studied. The results revealed that single Co₂Z hexaferrite phase was obtained at relatively low temperature 1250 ^°C for 5 h via the SGA method whereas it was formed at 1300 ^°C for 6 h using the CP pathway. The microstructures of the pure powders appeared as a hexagonal platelet-like structure. The particle size of the pure Co₂Z powders by CP method was higher than as obtained by the SGA method. The soft characteristic loops were obtained for single Co₂Z hexaferrite phase synthesized using both routes. High saturation magnetization (M _s =53.7 emu/g) was achieved for the Co₂Z powder synthesized via the CP method compared with the formed single phase synthesized via the SGA method (M _s =47.0 emu/g). Good dielectric and dynamic magnetic properties were obtained for the Co₂Z powder synthesized via the SGA method in comparison with the sample synthesized via CP method. The results obtained are discussed on the basis of electromagnetic theory.