Epitaxial growth and magnetic exchange anisotropy in Fe3O4<Emphasis Type="Bold">/NiO bilayers grown on MgO(001) and Al</Emphasis>2O3(0001)

Epitaxial Fe3O4/NiO bilayers were epitaxially grown on MgO(001) and Al2O3(0001) substrates to investigate the influence of the fully spin compensated (001) and the non-compensated (111) NiO interface planes between the ferromagnetic (F) and antiferromagnetic (AF) layers on the AF/F exchange coupling. Bilayers of different magnetite thicknesses and constant NiO thickness were investigated. The structural characterizations indicate a perfect epitaxy of the two layers for the both growth directions in the two Fe3O4/NiO/MgO(001) and NiO/Fe3O4/Al2O3(0001) systems. An epitaxial ferrimagnetic (Ni,Fe)Fe2O4 phase is observed at the AF/F interface when the NiO oxide is grown on the top of the Fe3O4 layer while a perfectly flat AF/F interface is observed in the Fe3O4/NiO/MgO(001) system exhibiting only a very slight interdiffusion. Magnetic measurements indicate a relative strong bias at 300 K for the bilayers grown on Al2O3(0001), which decreases with the inverse of the ferrimagnetic layer thickness as theoretically expected. On the contrary, a zero exchange biasing is observed at 300 K for the bilayers grown on MgO(001).     

Adsorptive removal and kinetics of methylene blue from aqueous solution using NiO/MCM-41 composite

Highly ordered mesoporous material MCM-41 was synthesized from tetraethylorthosilicate (TEOS) as Si source and cetyltrimethylammonium bromide (CTAB) as template. Well-dispersed NiO nanoparticles were introduced into the highly ordered mesoporous MCM-41 by chemical precipitation method to prepare the highly ordered mesoporous NiO/MCM-41 composite. X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM) and high-resolution TEM (HRTEM), and nitrogen adsorption–desorption measurement were used to examine the morphology and the microstructure of the obtained composite. The morphological study clearly revealed that the synthesized NiO/MCM-41 composite has a highly ordered mesoporous structure with a specific surface area of 435.9 m² g⁻¹. A possible formation mechanism is preliminary proposed for the formation of the nanostructure. The adsorption performance of NiO/MCM-41 composite as an adsorbent was further demonstrated in the removal azo dyes of methyl orange (MO), Congo red (CR), methylene blue (MB) and rhodaming B (RB) under visible light irradiation and dark, respectively. The kinetics and mechanism of removal methylene blue were studied. The results show that NiO/MCM-41 composite has a good removal capacity for organic pollutant MB from the wastewater under the room temperature. Compared with MCM-41 and NiO nanoparticles, 54.2% and 100% higher removal rate were obtained by the NiO/MCM-41 composite.     

Preparation and characterization of NiFe2O4/NiO composite film via a single-source precursor route

NiFe₂O₄/NiO nanocomposite thin films have been successfully prepared through a facile route using nickel iron layered double hydroxide (NiFe-LDH) as a single-source precursor. This synthetic approach mainly involves the formation of NiFe-LDH film by casting the slurry of NiFe-LDH precursor on the α-Al₂O₃ substrate, followed by high-temperature calcination. The composition, microstructure and properties of the films were characterized in detail by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), scanning electron microscopy (SEM), energy dispersive X-ray spectrometry (EDX) and vibrating sample magnetometer (VSM). The results indicate that NiFe₂O₄/NiO composite film was composed of granules with diameter less than 100 nm, and the thickness of the film was in the range 1-2 μm. The magnetization of the film can be tuned by alternating the Ni/Fe molar ratio of LDH precursor. In addition, the method developed should be easily extended to fabricate other MFe₂O₄/MO composite film systems with specific applications just by an appropriate combination of divalent/trivalent composition in the precursor of LDHs.     

Molecular dynamics simulations of interfaces between NiO and cubic ZrO2

The structures of eight heterophase interfaces between cubic ZrO₂ and NiO simulated by molecular dynamics (MD) are compared with those of the corresponding isolated surfaces to better understand the factors influencing interface formation and coherency in ceramic oxides. The near coincident site lattice (NCSL) theory used to construct initial configurations with small lattice mismatch between low index crystal planes is extended to describe interface planes with rectangular symmetry. Interface energies, works of adhesion, expansion volumes, lattice strains and planar structure factors are reported for several bicrystals. Most interfaces are found to consist of disordered, open structures with correspondingly high energies as a consequence of the strong repulsive forces between like-charged ions brought into close proximity. The exception is the (111) NiO//(100) c-ZrO₂ interface, which exhibits good coherency across the interphase boundary and consists of a shared oxygen plane. The relatively high crystallinity of the interface explains its low energies and small excess volume. The results are discussed in the context of developing a simulation-based method for identifying interface configurations with high lattice coherency and strong cohesiveness for optimizing the properties of composites of technologically important materials.     

γ-Fe_2O_3/NiO核-壳纳米花的合成、微结构与磁性

利用溶剂热/热分解的方法合成出微结构可控的γ-Fe_2O_3/NiO核-壳结构纳米花.分析表明NiO壳层是由单晶结构的纳米片构成,这些纳米片不规则地镶嵌在γ-Fe_2O_3核心的表面.Fe3O4/Ni(OH)_2前驱体的煅烧时间对γ-Fe_2O_3/NiO核-壳体系的晶粒生长、NiO相含量和壳层致密度均有很大的影响.振动样品磁强计和超导量子干涉仪的测试分析表明,尺寸效应、NiO相含量和铁磁-反铁磁界面耦合效应是决定γ-Fe_2O_3/NiO核-壳纳米花磁性能的重要因素.随着NiO相含量的增加,磁化强度减小,矫顽力增大.在5 K下,γ-Fe_2O_3/NiO核-壳纳米花表现出一定的交换偏置效应(H_E=46 Oe),这来自于(亚)铁磁性γ-Fe_2O_3和反铁磁性NiO之间的耦合相互作用.与此同时,这种交换耦合效应也进一步提高了样品的矫顽力(H_C=288 Oe).     

Oscillatory interlayer exchange coupling and its temperature dependence in [Pt/Co]3/NiO/[Co/Pt]3 multilayers with perpendicular anisotropy

Interlayer exchange coupling that oscillates between antiferromagnetic and ferromagnetic as a function of NiO thickness has been observed in [Pt(5 A)/Co(4 A)](3)/NiO(t(NiO) A)/[Co(4 A)/Pt(5 A)](3) multilayers with out-of-plane anisotropy. The period of oscillation corresponds to approximately 2 monolayers of NiO. This oscillatory behavior is possibly attributed to the antiferromagnetic ordering in NiO. The antiferromagnetic interlayer exchange coupling for the 11 A NiO layer shows an increase in coupling strength with increasing temperature, in agreement with the quantum interference model of Bruno for insulating spacer layers. A coexistence of exchange biasing and antiferromagnetic interlayer exchange coupling has been observed below T=250 K.     

High critical current density YBa2Cu3O7−δ tapes prepared by the surface-oxidation epitaxy method

YBa₂Cu₃O_7−δ (YBCO) films with high critical current density (J_c) were successfully fabricated on nickel tapes buffered with epitaxial NiO. NiO was prepared on the textured nickel tape by the surface-oxidation epitaxy (SOE) method. We have reported so far a critical temperature (T_c) of 87 K and J_c=4–6×10⁴ A/cm² (77 K, 0 T) for the YBCO films on NiO/Ni tapes. To enhance the superconducting properties of the YBCO films on the SOE-grown NiO, depositions of thin oxide cap layers such as YSZ, CeO₂, and MgO on NiO were investigated. These oxide cap layers were epitaxially grown on NiO and provided the template for the epitaxial growth of YBCO films. Substantially improved data of T_c=88 K and J_c=3×10⁵ A/cm² (77 K, 0 T) and 1×10⁴ A/cm² (77 K, Hc, 4 T) were obtained for YBCO film on NiO, by using a MgO cap layer with a thickness of 50 nm. The method described in this paper is a simple way to produce long YBCO tape conductors with high-J_c values.     

Direct experimental study of the effect of dislocations on the magnetization reversal in a quasi-two-dimensional ferromagnet with unidirectional anisotropy

The effect of dislocations on the elementary acts of the magnetization reversal in the epitaxial heterostructure NiFe/NiO/MgO(001) has been studied using the magneto-optical indicator film technique. It has been found that the edge dislocations grouped along the 〈110〉 slip planes lead to the formation of quasi-one-dimensional domains in the permalloy film with the induced uniaxial anisotropy oriented along these planes the direction of which differs by 90° from that of the uniaxial anisotropy in the dislocation-free part of the heterostructure. The micromechanism of the observed effect has been discussed taking into account the effect of dislocations on the orientation of spins in the antiferromagnet and their exchange interaction with the spins of the ferromagnet on the interphase plane.     

Effects of exchange interaction and spin-fluctuation on the magnetic and magneto-optic properties of NdF3

The exchange interaction between the electrons in the different magnetic ions and the spin-fluctuation of the magnetic ions exist in the paramagnetic media NdF3. The exchange interaction between the electrons in the different magnetic ions may be equivalent to an effective field Hin that is in direct proportion to the magnetization M. The spin-fluctuation of the magnetic ions leads the coefficient of the effective field to vary with temperature. The effective field is given as Hin = -（0.75 ＋ 0.22T） × 10^-5M in NdF3. When the secondary crystal field effect is taken into account, the magnetic susceptibility and Verdet constant are calculated for NdF3 by means of the effective field Hin and the applied field He. The calculated results are in agreement with the measured ones.     

A novel NiO/BaTiO3 heterojunction for piezocatalytic water purification under ultrasonic vibration

This work designed and prepared a novel heterojunction composite NiO/BaTiO₃ through a method of photodeposition and used it in piezocatalytic dye removal for the first time. Results of the piezocatalytic test indicated that the NiO/BaTiO₃ composite presented superior efficiency and stability in the RhB degradation under the vibration of ultrasonic waves. The best NiO/BaTiO₃ sample synthesized under light irradiation for 2 h displayed an RhB degradation rate of 2.41 h⁻¹, which was 6.3 times faster than that of pure BaTiO₃. By optimizing the piezocatalytic reaction conditions, the degradation rate constant of NiO/BaTiO₃ can further reach 4.14 h⁻¹ A variety of systematic characterizations were executed to determine the reason for the excellent piezocatalytic performance of NiO/BaTiO₃. The band potentials of NiO and BaTiO₃ are found to coincide, and at their contact interface, they may create a type-II p-n heterojunction structure. Driven by the potential difference and the built-in electric field, piezoelectrically enriched charge carriers can migrate between NiO and BaTiO₃, resulting in improved efficiency in charge separation and an increase in the piezoelectric catalytic performance. This study may provide a potential composite catalyst and a promising idea for the design of highly efficient catalysts in the field of piezoelectric catalysis.     

Optical CO gas sensing using nanostructured NiO and NiO/SiO2 nanocomposites fabricated by PLD and sol–gel methods

Several kinds of NiO-based nanostructured films were prepared by pulsed-laser deposition (PLD) and sol–gel method, and CO sensing properties (1%, balanced by N₂) of these films were studied. The sensitivity, defined as a difference of optical transmittance by gas atmospheric change (T=T(CO)-T(air)), increased with increasing NiO content for the sol–gel prepared films, and increased with the film thickness for the laser deposited NiO films. Sol–gel films exhibited shorter response time than NiO films prepared by PLD under low Ar pressure of 6.7×10^-2 Pa indicating a better gas permeability. A shorter response time was also obtained upon raising argon pressure from 6.7×10^-2 Pa to 8.0 Pa during laser ablation due to the morphological change. Covering a NiO film even with a very thin (0.8 nm) layer of SiO₂ by sputtering drastically reduced the CO sensitivity. The multilayered NiO/SiO₂ films were substantially less sensitive to the CO gas than NiO films due to the same reason. Sensing mechanism of the NiO films is due to catalytic CO oxidation that reduces the concentration of adsorbed O₂ species and results in optical transmittance increase upon change in the environment from air to CO. PACS 81.15.Fg; 81.20.Fw; 83.85.Gk     

The characterization of nanostructured CVD Ni powders using transmission electron microscopy

Studies of Ni powders using a state-of-the-art transmission electron microscope with a field-emission electron source show that this instrument can be an invaluable tool for studying the morphology and character of nanostructured Ni powder manufactured by a commercial nickel carbonyl vapor deposition process. This study has revealed the presence of surface coatings, including NiO and turbostratic graphite on some powders, which can degrade the electrical conductivity of the powder. Due to the high curvature of hexagonal carbon (graphene) planes, and subsequent high density of defects, the turbostratic graphitic nanocarbon may exhibit new properties.     

Optical diagnostics of physicochemical properties of NiO/Al2O3 nanocomposites upon exposure to different gases and heat

We have studied nanostructural and optical properties of composites of nanostructured nickel oxide films on a substrate from porous aluminum oxide NiO/Al₂O₃ in the UV, visible, and IR spectral ranges on exposure of composites to different gases, vacuum, and heat. We have found that, upon irradiation of NiO/Al₂O₃ composites by laser radiation at a wavelength of 633 nm, they demonstrate a high sensitivity to carbon monoxide CO in the range of the excitonic absorption of nickel oxide. We assume that an increase in the transmission coefficient of the composite in the excitonic absorption band is determined by luminescence that is caused by the oxidation reaction of carbon monoxide. The sensitivity of composites to CO is enhanced with decreasing the size of NiO nanoparticles and after evacuation. The values of the diffuse reflection coefficient at the laser radiation wavelength of 633 nm correlate with the size of nickel oxide nanoparticles. Spectral changes in the range of the fundamental absorption band of NiO that occur in the IR range and in diffuse reflection spectra are related to the appearance of carbon-containing compounds in the composite exposed to CO.     

3-D airflow measurement using smoke particles

A new 3-D PIV-technique that is applicable to low velocity airflow in a real space such as indoor airflow is proposed, and its performance is inspected through a simulation and an experimental application. In this technique, two parallel planes separated by short distance are illuminated by a pair of laser light sheets of different colors. The visualized images are separated with optical filters, and recorded on VTRs. The 2-D tracer pattern movement on visualized planes is tracked with pattern tracking and the movement normal to the visualized planes is calculated from the difference of tracer concentration between two planes. The simulation result showed that the algorithm proposed here can calculate 3-D velocity field adequately, but the experimental result showed that the luminous intensity difference between two visualized planes became the main source of experimental errors.     

Nanocrystallite interface effect and exchange bias phenomenology in Cr2O3 and NiO nanoparticles

Nanocrystalline Cr₂O₃ and NiO are prepared using high-energy ball milling. Average sizes of the particles obtained from Scanning Electron Microscopy and crystallite sizes obtained from X-ray diffraction are larger for Cr₂O₃ than NiO particles. At low temperature, large high-field magnetization and small coercivity lead to a weak exchange bias for Cr₂O₃, whereas small high-field magnetization and large coercivity lead to a considerable exchange bias for NiO. The training effect is observed for NiO at 4 K which could be described with a recursive formula constructed in the framework of the spin configurational relaxation model. The results suggest that the pinning mechanism at the interface between the antiferromagnetic and the weak ferromagnetic component ascribed to uncompensated spins leads to the exchange bias effect.     

Methyl orange adsorption by microporous and mesoporous TiO2-SiO2 and TiO2-SiO2-Al2O3 composite xerogels

We investigate the adsorption behavior of methyl orange (MO) on composite xerogels. Mesoporous TiO₂-SiO₂ and TiO₂-SiO₂-Al₂O₃ xerogels are prepared by hydrolysis of tetraethyl orthosilicate (TEOS), tetrabutyl orthotitanate (TBOT), and AlCl₃ ·6H₂O using HCl as a catalyst and cetyltrimethylammonium bromide (CTAB) as a templating agent. The corresponding microporous xerogels are also prepared without addition of CTAB. These xerogels are then characterized by XRD, FTIR, and BET.We find that MO is adsorbed by the mesoporous xerogels in acidic solutions, showing Langmuir type adsorption isotherms. We also find that the adsorption decreases with increasing temperature. It is suggested that adsorption exhibits a sieve effect and that MO is adsorbed through electrostatic attraction and hydrogen bonding between MO and the xerogels.     

纳米NiO的制备及其谱学特性研究

以醋酸镍、氢氧化钠为原料,吐温80为分散剂,通过固相反应制备了纳米级NiO。 用X射线衍射仪、透射电子显微镜、傅里叶红外光谱、紫外-可见分光光度等方法对材料的粒径、晶格畸变率、形貌以及红外、紫外-可见光的吸收性能进行了表征。结果表明：制得的纳米NiO产物为球形、属立方晶系,粒径大小在9～30 nm左右;晶格畸变率随粒径的增大而减小;纳米NiO红外吸收峰出现在437 cm-1处,与普通粒径的NiO光谱纯(484 cm-1)相比,其吸收峰红移了47 cm-1,体现了纳米NiO的表面效应;不同粒径大小的NiO对紫外-可见光的吸收特性不同。普通粒径的NiO光谱纯在紫外-可见光区域没有吸收,颗粒尺寸越小吸收波长越短,10 nm NiO的紫外-可见光吸收峰位于309 nm处,直接跃迁的光学能带隙约为4.2 eV,比体相材料(3.65 eV)增加0.55 eV,表现出明显的量子尺寸效应。对纳米NiO的谱学特性研究表明该材料在光电领域具有潜在的应用价值。     

光谱法研究羟基葫芦[6]脲与甲基橙的分子识别作用

采用紫外和荧光光谱法研究羟基葫芦[6]脲(HOCB6)与甲基橙(MO)之间的包结作用,考察了溶液的pH值、常见有机溶剂和表面活性剂等对该包结物的形成及荧光强度的影响。实验结果表明,随着主体分子的加入,MO荧光增强且蓝移,说明客体被纳入主体分子的疏水性穴腔,形成内包结物。主客体分子之间主要通过疏水作用形成1∶1型的HOCB6-MO包结物,其包结常数为1.41×102 L·mol-1。同时采用葫芦[6]脲(CB6)、对-二甲氨甲基杯[8]芳烃和β-环糊精与MO的作用进行比较。研究发现,MO也能与葫芦[6]脲形成1∶1型的内包结物,但包结常数较小(34.65 L·mol-1);与β-环糊精形成1∶2型的内包结物,其包结常数为6.14×106 L2·mol-2;与对-二甲氨甲基杯[8]芳烃形成1∶1型的外包结物,导致荧光强烈猝灭,包结常数为1.35×104 L·mol-1。     

Temperature dependence of spin pumping in YIG/NiOx/W multilayer

We report the temperature dependence of the spin pumping effect for Y₃Fe₅O₁₂ (YIG, 0.9 μm)/NiO (t_NiO)/W (6 nm) (t_NiO = 0 nm, 1 nm, 2 nm, and 10 nm) heterostructures. All samples exhibit a strong temperature-dependent inverse spin Hall effect (ISHE) signal I_c and sensitivity to the NiO layer thickness. We observe a dramatic decrease of I_c with inserting thin NiO layer between YIG and W layers indicating that the inserting of NiO layer significantly suppresses the spin transport from YIG to W. In contrast to the noticeable enhancement in YIG/NiO (t_NiO ≈ 1-2 nm)/Pt, the suppression of spin transport may be closely related to the specific interface-dependent spin scattering, spin memory loss, and spin conductance at the NiO/W interface. Besides, the I_c of YIG/NiO/W exhibits a maximum near the T_N of the AF NiO layer because the spins are transported dominantly by incoherent thermal magnons.